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Sample records for boracite-network-topology porous mof

  1. Synthesis and applications of MOF-derived porous nanostructures

    Directory of Open Access Journals (Sweden)

    Min Hui Yap

    2017-07-01

    Full Text Available Metal organic frameworks (MOFs represent a class of porous material which is formed by strong bonds between metal ions and organic linkers. By careful selection of constituents, MOFs can exhibit very high surface area, large pore volume, and excellent chemical stability. Research on synthesis, structures and properties of various MOFs has shown that they are promising materials for many applications, such as energy storage, gas storage, heterogeneous catalysis and sensing. Apart from direct use, MOFs have also been used as support substrates for nanomaterials or as sacrificial templates/precursors for preparation of various functional nanostructures. In this review, we aim to present the most recent development of MOFs as precursors for the preparation of various nanostructures and their potential applications in energy-related devices and processes. Specifically, this present survey intends to push the boundaries and covers the literatures from the year 2013 to early 2017, on supercapacitors, lithium ion batteries, electrocatalysts, photocatalyst, gas sensing, water treatment, solar cells, and carbon dioxide capture. Finally, an outlook in terms of future challenges and potential prospects towards industrial applications are also discussed. Keywords: Metal organic frameworks, Porous nanostructures, Supercapacitors, Lithium ion batteries, Heterogeneous catalyst

  2. Synthesis of Cr-MOF derived porous carbon for hydrogen storage applications

    CSIR Research Space (South Africa)

    Musyoka, Nicholas M

    2014-07-01

    Full Text Available Over the recent years, applications of porous metal-organic frameworks (MOFs) in hydrogen storage have received increasing attention in the scientific community. Conversion of organic moiety in MOFs to porous carbon, as well as the use of MOFs as a...

  3. Porous carbons prepared by direct carbonization of MOFs for supercapacitors

    Science.gov (United States)

    Yan, Xinlong; Li, Xuejin; Yan, Zifeng; Komarneni, Sridhar

    2014-07-01

    Three porous carbons were prepared by direct carbonization of HKUST-1, MOF-5 and Al-PCP without additional carbon precursors. The carbon samples obtained by carbonization at 1073 K were characterized by XRD, TEM and N2 physisorption techniques followed by testing for electrochemical performance. The BET surface areas of the three carbons were in the range of 50-1103 m2/g. As electrode materials for supercapacitor, the MOF-5 and Al-PCP derived carbons displayed the ideal capacitor behavior, whereas the HKUST-1 derived carbon showed poor capacitive behavior at various sweep rates and current densities. Among those carbon samples, Al-PCP derived carbons exhibited highest specific capacitance (232.8 F/g) in 30% KOH solution at the current density of 100 mA/g.

  4. Design and Synthesis of Novel Porous Metal-Organic Frameworks (MOFs) Toward High Hydrogen Storage Capacity

    Energy Technology Data Exchange (ETDEWEB)

    Mohamed, Eddaoudi [USF; Zaworotko, Michael [USF; Space, Brian [USF; Eckert, Juergen [USF

    2013-05-08

    Statement of Objectives: 1. Synthesize viable porous MOFs for high H2 storage at ambient conditions to be assessed by measuring H2 uptake. 2. Develop a better understanding of the operative interactions of the sorbed H2 with the organic and inorganic constituents of the sorbent MOF by means of inelastic neutron scattering (INS, to characterize the H2-MOF interactions) and computational studies (to interpret the data and predict novel materials suitable for high H2 uptake at moderate temperatures and relatively low pressures). 3. Synergistically combine the outcomes of objectives 1 and 2 to construct a made-to-order inexpensive MOF that is suitable for super H2 storage and meets the DOE targets - 6% H2 per weight (2kWh/kg) by 2010 and 9% H2 per weight (3kWh/kg) by 2015. The ongoing research is a collaborative experimental and computational effort focused on assessing H2 storage and interactions with pre-selected metal-organic frameworks (MOFs) and zeolite-like MOFs (ZMOFs), with the eventual goal of synthesizing made-to-order high H2 storage materials to achieve the DOE targets for mobile applications. We proposed in this funded research to increase the amount of H2 uptake, as well as tune the interactions (i.e. isosteric heats of adsorption), by targeting readily tunable MOFs:

  5. Extending the Use of Highly Porous and Functionalized MOFs to Th(IV) Capture.

    Science.gov (United States)

    Zhang, Nan; Yuan, Li-Yong; Guo, Wen-Lu; Luo, Shi-Zhong; Chai, Zhi-Fang; Shi, Wei-Qun

    2017-08-02

    Thorium separation has recently become a hot topic because of the potential application of thorium as a future nuclear fuel, while metal-organic framework (MOF) materials have received much attention in the separation field due to their unique properties. Herein, a highly porous and stable MOF, UiO-66, and its carboxyl derivatives (UiO-66-COOH and UiO-66-(COOH) 2 ) were synthesized and explored for the first time for Th(IV) capture from a weak acidic solution. Although the introduction of carboxyl groups into UiO-66 leads to an obvious decrease in the surface area and pore volume, the adsorbability toward Th(IV) is greatly enhanced. At pH = 3.0, the saturated sorption capacity for Th(IV) into UiO-66-(COOH) 2 reached 350 mg/g, representing one of the largest values for Th(IV) capture by solid extraction. Moreover, the functionalized MOFs show fast sorption kinetics and desirable selectivity toward Th(IV) over a range of competing metal ions. A possible mechanism for the selective recognition of Th(IV) by these MOFs was explored on the basis of extended X-ray absorption fine structure and Fourier transform infrared analysis. It is concluded that UiO-66-COOH and UiO-66-(COOH) 2 sorb Th(IV) through the coordination of carboxyl anions in the pores of the MOFs, whereas in the case of UiO-66, both the precipitation and the exchange with the organic solvent contribute to the Th(IV) uptake. This study contributes to the assessment of the feasibility of MOFs applied in actinides separation and better understanding of actinides sorption behavior in this kind of hybrid porous solid materials.

  6. A 3D porous zinc MOF constructed from a flexible tripodal ligand: Synthesis, structure, and photoluminescence property

    International Nuclear Information System (INIS)

    Wen Lili; Wang Dong'e; Wang Chenggang; Wang Feng; Li Dongfeng; Deng Kejian

    2009-01-01

    A new metal-organic framework, [Zn 5 (trencba) 2 (OH) 2 Cl 2 .4H 2 O] (1) [H 3 trencba=N,N,N',N',N'',N''-tris[(4-carboxylate-2-yl)methyl]-tris (2-aminoethyl)amine], constructed from a flexible tripodal ligand based on C 3 symmetric tris(2-aminoethyl)amine, has been synthesized hydrothermally and characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction analysis. Compound 1 contains an unprecedented linear penta-nuclear zinc cluster fragment. Each ligand links four penta-nuclear fragments, and every fragment links eight ligands to generate a three-dimensional non-interpenetrated porous framework. The uncoordinated water molecules were observed trapped in the void pores. Compound 1 represents the first example of (6,8)-connected 3D bi-nodal framework based on a single kind of organic ligand. The photoluminescence measurements showed that complex 1 exhibits relatively stronger blue emissions at room temperature than that of the ligand. - Graphical abstract: The MOF [Zn 5 (trencba) 2 (OH) 2 Cl 2 .4H 2 O] (H 3 trencba=N,N,N',N',N',N'-tris[(4-carboxylate-2-yl)methyl]-tris (2-aminoethyl)amine) reveals a (6,8)-connected bi-nodal three-dimensional porous framework with unprecedented penta-nuclear fragment, which appears to be a good candidate of hybrid inorganic-organic photoactive materials

  7. Porous carbon as electrode material in direct ethanol fuel cells (DEFCs) synthesized by the direct carbonization of MOF-5

    KAUST Repository

    Khan, Inayatali

    2014-01-12

    Porous carbon (PC-900) was prepared by direct carbonization of porous metal-organic framework (MOF)-5 (Zn4O(bdc)3, bdc=1,4-benzenedicarboxylate) at 900 °C. The carbon material was deposited with PtM (M=Fe, Ni, Co, and Cu (20 %) metal loading) nanoparticles using the polyol reduction method, and catalysts PtM/PC-900 were designed for direct ethanol fuel cells (DEFCs). However, herein, we are reporting PtFe/PC-900 catalyst combination which has exhibited superior performance among other options. This catalyst was characterized by powder XRD, high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and selected area electron diffraction (SAED) technique. The electrocatalytic capability of the catalyst for ethanol electrooxidation was investigated using cyclic voltammetry and direct ethanol single cell testing. The results were compared with those of PtFe and Pt supported on Vulcan XC72 carbon catalysts (PFe/CX-72 and Pt/XC-72) prepared via the same method. It has been observed that the catalyst PtFe/PC-900 developed in this work showed an outstanding normalized activity per gram of Pt (6.8 mA/g Pt) and superior power density (121 mW/cm2 at 90 °C) compared to commercially available carbon-supported catalysts. © Springer-Verlag Berlin Heidelberg 2014.

  8. Porous carbon as electrode material in direct ethanol fuel cells (DEFCs) synthesized by the direct carbonization of MOF-5

    KAUST Repository

    Khan, Inayatali; Badshah, Amin; Haider, Naghma; Ullah, Shafiq; Anjum, Dalaver H.; Nadeem, Muhammad Arif

    2014-01-01

    Porous carbon (PC-900) was prepared by direct carbonization of porous metal-organic framework (MOF)-5 (Zn4O(bdc)3, bdc=1,4-benzenedicarboxylate) at 900 °C. The carbon material was deposited with PtM (M=Fe, Ni, Co, and Cu (20 %) metal loading) nanoparticles using the polyol reduction method, and catalysts PtM/PC-900 were designed for direct ethanol fuel cells (DEFCs). However, herein, we are reporting PtFe/PC-900 catalyst combination which has exhibited superior performance among other options. This catalyst was characterized by powder XRD, high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and selected area electron diffraction (SAED) technique. The electrocatalytic capability of the catalyst for ethanol electrooxidation was investigated using cyclic voltammetry and direct ethanol single cell testing. The results were compared with those of PtFe and Pt supported on Vulcan XC72 carbon catalysts (PFe/CX-72 and Pt/XC-72) prepared via the same method. It has been observed that the catalyst PtFe/PC-900 developed in this work showed an outstanding normalized activity per gram of Pt (6.8 mA/g Pt) and superior power density (121 mW/cm2 at 90 °C) compared to commercially available carbon-supported catalysts. © Springer-Verlag Berlin Heidelberg 2014.

  9. NaCl as a solid solvent to assist the mechanochemical synthesis and post-synthesis of hierarchical porous MOFs with high I2 vapour uptake.

    Science.gov (United States)

    Yang, Junyi; Feng, Xiao; Lu, Guangnong; Li, Yulin; Mao, Chaochao; Wen, Zhongliang; Yuan, Wenbing

    2018-04-03

    The use of salts as grinding media to assist the mechanosynthesis, and the following one-pot mechanochemical post-synthesis, of hierarchically porous MOFs was carried out efficiently by ball milling. NaCl or KCl were used as a solid solvent to initially pre-grind with 1,3,5-benzenetricarboxylic acid (H3BTC) and copper acetate monhydrate, respectively, for 1 minute, then both mixtures were combined together for a further 20 minutes of grinding, and the resultant mixture was finally washed with ethanol and water to obtain the hierarchically micro-, meso- and macroporous HKUST-1 with a high yield. Moreover, the post-synthesis of these as-obtained hierarchically porous HKUST-1 was easily performed via grinding triethylenediamine (TED) with the above unwashed crude-products for 20 minutes. By adjusting the amount of NaCl and TED added, we simply fabricated the pore- and function-adjustable hierarchically porous HKUST-1. Furthermore, these as-obtained HKUST-1 products showed high performance in the capture of volatile iodine.

  10. Solvent-Induced Cadmium(II) Metal-Organic Frameworks with Adjustable Guest-Evacuated Porosity: Application in the Controllable Assembly of MOF-Derived Porous Carbon Materials for Supercapacitors.

    Science.gov (United States)

    Yue, Man-Li; Jiang, Yi-Fan; Zhang, Lin; Yu, Cheng-Yan; Zou, Kang-Yu; Li, Zuo-Xi

    2017-11-07

    In this work, five new cadmium metal-organic frameworks (Cd-MOFs 1-5) have been synthesized from solvothermal reactions of Cd(NO 3 ) 2 ⋅4 H 2 O with isophthalic acid and 1,4-bis(imidazol-1-yl)-benzene under different solvent systems of CH 3 OH, C 2 H 5 OH, (CH 3 ) 2 CHOH, DMF, and N-methyl-2-pyrrolidone (NMP), respectively. Cd-MOF 1 shows a 3D diamondoid framework with 1D rhombic and hexagonal channels, and the porosity is 12.9 %. Cd-MOF 2 exhibits a 2D (4,4) layer with a 1D parallelogram channel and porosity of 23.6 %. Cd-MOF 3 has an 8-connected dense network with the Schäfli symbol of [4 24 ⋅6 4 ] based on the Cd 6 cluster. Cd-MOFs 4-5 are isomorphous, and display an absolutely double-bridging 2D (4,4) layer with 1D tetragonal channels and porosities of 29.2 and 28.2 %, which are occupied by DMF and NMP molecules, respectively. Followed by the calcination-thermolysis procedure, Cd-MOFs 1-5 are employed as precursors to prepare MOF-derived porous carbon materials (labeled as PC-me, PC-eth, PC-ipr, PC-dmf and PC-nmp), which have the BET specific surface area of 23, 51, 10, 122, and 96 m 2  g -1 , respectively. The results demonstrate that the specific surface area of PCs is tuned by the porosity of Cd-MOFs, where the later is highly dependent on the solvent. Thereby, the specific surface area of PCs could be adjusted by the solvent used in the synthese of MOF precusors. Significantly, PCs have been further activated by KOH to obtain activated carbon materials (APCs), which possess even higher specific surface area and larger porosity. After a series of characterization and electrochemical investigations, the APC-dmf electrode exhibits the best porous properties and largest specific capacitances (153 F g -1 at 5 mV s -1 and 156 F g -1 at 0.5 Ag -1 ). Meanwhile, the APC-dmf electrode shows excellent cycling stability (ca. 84.2 % after 5000 cycles at 1 Ag -1 ), which can be applied as a suitable electrode material for

  11. Evaluation of MOF-74, MOF-177, and ZIF-8 for the Removal of Toxic Industrial Chemicals

    National Research Council Canada - National Science Library

    Peterson, Gregory W; Mahle, John; Balboa, Alex; Wagner, George; Sewell, Tara; Karwacki, Christopher J

    2008-01-01

    .... Metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) are two novel classes of materials that allow for specific functionalities to be designed directly into a porous framework...

  12. Asymmetric supercapacitors based on carbon nanotubes@NiO ultrathin nanosheets core-shell composites and MOF-derived porous carbon polyhedrons with super-long cycle life

    Science.gov (United States)

    Yi, Huan; Wang, Huanwen; Jing, Yuting; Peng, Tianquan; Wang, Xuefeng

    2015-07-01

    Aqueous electrolyte based asymmetric supercapacitors (ASCs) has recently attracted increasing interest by virtue of their operation voltage and high ionic conductivity. Herein, we developed a novel ASC based on carbon nanotubes@nickel oxide nanosheets (CNT@NiO) core-shell composites as positive electrode and porous carbon polyhedrons (PCPs) as negative electrode in aqueous KOH solution as electrolyte. The CNT@NiO core-shell hybrids were prepared through a facile chemical bath deposition method followed by thermal annealing, while PCPs were obtained by direct carbonization of Zn-based metal-organic frameworks (MOFs). Owing to their unique microstructures, outstanding electrochemical properties have been achieved in three-electrode configuration, e.g., 996 F g-1 at 1 A g-1, 500 at 20 A g-1 for the CNT@NiO electrode within 0-0.5 V window, and 245 F g-1 at 1 A g-1 for the PCPs electrode within -1-0 V window. Resulting from these merits, the as-fabricated CNT@NiO//PCPs ASC exhibits maximum energy density of 25.4 Wh kg-1 at a power density of 400 W kg-1 and even remains 9.8 Wh kg-1 at 16,000 W kg-1 (a full charge-discharge within 4.4 s) in the wide voltage region of 0-1.6 V. More importantly, the CNT@NiO//PCPs asymmetric supercapacitor shows ultralong cycling stability, with 93% capacitance retention after 10,000 cycles.

  13. Zirconium-based highly porous metal-organic framework (MOF-545) as an efficient adsorbent for vortex assisted-solid phase extraction of lead from cereal, beverage and water samples.

    Science.gov (United States)

    Tokalıoğlu, Şerife; Yavuz, Emre; Demir, Selçuk; Patat, Şaban

    2017-12-15

    In this study, zirconium-based highly porous metal-organic framework, MOF-545, was synthesized and characterized. The surface area of MOF-545 was found to be 2192m 2 /g. This adsorbent was used for the first time as an adsorbent for the vortex assisted-solid phase extraction of Pb(II) from cereal, beverage and water samples. Lead in solutions was determined by FAAS. The optimal experimental conditions were as follows: the amount of MOF-545, 10mg; pH of sample, 7; adsorption and elution time, 15min; and elution solvent, 2mL of 1molL -1 HCl. Under the optimal conditions of the method, the limit of detection, preconcentration factor and precision as RSD% were found to be 1.78μgL -1 , 125 and 2.6%, respectively. The adsorption capacity of the adsorbent for lead was found to be 73mgg -1 . The method was successfully verified by analyzing two certified reference materials (BCR-482 Lichen and SPS-WW1 Batch 114) and spiked chickpea, bean, wheat, lentil, cherry juice, mineral water, well water and wastewater samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Ligand flexibility and framework rearrangement in a new family of porous metal-organic frameworks

    DEFF Research Database (Denmark)

    Hawxwell, Samuel M; Espallargas, Guillermo Mínguez; Bradshaw, Darren

    2007-01-01

    Ligand flexibility permits framework rearrangement upon evacuation and gas uptake in a new family of porous MOFs.......Ligand flexibility permits framework rearrangement upon evacuation and gas uptake in a new family of porous MOFs....

  15. Experimental screening of porous materials for high pressure gas adsorption and evaluation in gas separations: application to MOFs (MIL-100 and CAU-10).

    Science.gov (United States)

    Wiersum, Andrew D; Giovannangeli, Christophe; Vincent, Dominique; Bloch, Emily; Reinsch, Helge; Stock, Norbert; Lee, Ji Sun; Chang, Jong-San; Llewellyn, Philip L

    2013-02-11

    A high-throughput gas adsorption apparatus is presented for the evaluation of adsorbents of interest in gas storage and separation applications. This instrument is capable of measuring complete adsorption isotherms up to 40 bar on six samples in parallel using as little as 60 mg of material. Multiple adsorption cycles can be carried out and four gases can be used sequentially, giving as many as 24 adsorption isotherms in 24 h. The apparatus has been used to investigate the effect of metal center (MIL-100) and functional groups (CAU-10) on the adsorption of N(2), CO(2), and light hydrocarbons on MOFs. This demonstrates how it can serve to evaluate sample quality and adsorption reversibility, to determine optimum activation conditions and to estimate separation properties. As such it is a useful tool for the screening of novel adsorbents for different applications in gas separation, providing significant time savings in identifying potentially interesting materials.

  16. Structural defects in metal–organic frameworks (MOFs): Formation, detection and control towards practices of interests

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2017-10-01

    Full Text Available Research on metal–organic framework (MOF) materials has gathered increasing interest starting from the early excitement as porous materials for gas storage down to various novel applications as catalysts, heat energy storage materials, chemical...

  17. Metal Organic Frameworks: Explorations and Design Strategies for MOF Synthesis

    KAUST Repository

    AbdulHalim, Rasha

    2016-11-27

    Metal-Organic Frameworks (MOFs) represent an emerging new class of functional crystalline solid-state materials. In the early discovery of this now rapidly growing class of materials significant challenges were often encountered. However, MOFs today, with its vast structural modularity, reflected by the huge library of the available chemical building blocks, and exceptional controlled porosity, stand as the most promising candidate to address many of the overbearing societal challenges pertaining to energy and environmental sustainability. A variety of design strategies have been enumerated in the literature which rely on the use of predesigned building blocks paving the way towards potentially more predictable structures. The two major design strategies presented in this work are the molecular building block (MBB) and supermolecular building block (SBB) -based approaches for the rationale assembly of functional MOF materials with the desired structural features. In this context, we targeted two highly connected MOF platforms, namely rht-MOF and shp-MOF. These two MOF platforms are classified based on their topology, defined as the underlying connectivity of their respective net, as edge transitive binodal nets; shp being (4,12)-connected net and rht being (3,24)-connected net. These highly connected nets were deliberately targeted due to the limited number of possible nets for connecting their associated basic building units. Two highly porous materials were designed and successfully constructed; namely Y-shp-MOF-5 and rht-MOF-10. The Y-shp-MOF-5 features a phenomenal water stability with an exquisite behavior when exposed to water, positioning this microporous material as the best adsorbent for moisture control applications. The shp-MOF platform proved to be modular to ligand functionalization and thus imparting significant behavioral changes when hydrophilic and hydrophobic functionalized ligands were introduced on the resultant MOF. On the other hand, rht-MOF

  18. Morphology and adsorption of chromium ion on uranium 1,2,4,5-benzenetetracarboxylic acid metal organic framework (MOF

    Directory of Open Access Journals (Sweden)

    Vala Remy M.K.

    2016-01-01

    Full Text Available In this paper, we report the synthesis of metal organic framework of uranium 1,2,4,5-benzene tetracarboxylic acid (U-H4btec MOF by solvothermal method. The obtained MOF was characterized by Fourier transform infrared spectroscopy (FTIR, Scanning electron microscopy (SEM, Transmission electron microscopy (TEM, X-ray diffraction spectroscopy (XRD, Energy dispersive spectroscopy (EDS, thermogravimetric and differential thermogravimetric analysis (TGA/DTA. The morphology of the uranium 1,2,4,5-benzene tetracarboxylic acid MOF observed by SEM, revealed the presence of flaky porous structure. Adsorption of Cr3+ from aqueous solution onto the uranium 1,2,4,5-benzene tetracarboxylic acid MOF was systematically studied. Langmuir and Freundlich adsorption isotherms were applied to determine the adsorption capacity of the MOF to form a monolayer. Kinetic determination of the adsorption of Cr3+ suggested both chemisorption and physisorption probably due to the presence of carbonyl groups within the MOF and its porous structure.

  19. Metal Organic Frameworks (MOFs)

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 12; Issue 11. Molecule Matters - Metal Organic Frameworks (MOFs). R Sarvanakumar S Sankararaman. Feature Article Volume 12 Issue 11 November 2007 pp 77-86. Fulltext. Click here to view fulltext PDF. Permanent link:

  20. Hybridization of MOFs and COFs: A New Strategy for Construction of MOF@COF Core-Shell Hybrid Materials.

    Science.gov (United States)

    Peng, Yongwu; Zhao, Meiting; Chen, Bo; Zhang, Zhicheng; Huang, Ying; Dai, Fangna; Lai, Zhuangchai; Cui, Xiaoya; Tan, Chaoliang; Zhang, Hua

    2018-01-01

    The exploration of new porous hybrid materials is of great importance because of their unique properties and promising applications in separation of materials, catalysis, etc. Herein, for the first time, by integration of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), a new type of MOF@COF core-shell hybrid material, i.e., NH 2 -MIL-68@TPA-COF, with high crystallinity and hierarchical pore structure, is synthesized. As a proof-of-concept application, the obtained NH 2 -MIL-68@TPA-COF hybrid material is used as an effective visible-light-driven photocatalyst for the degradation of rhodamine B. The synthetic strategy in this study opens up a new avenue for the construction of other MOF-COF hybrid materials, which could have various promising applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. High-throughput Molecular Simulations of MOFs for CO2 Separation: Opportunities and Challenges

    Science.gov (United States)

    Erucar, Ilknur; Keskin, Seda

    2018-02-01

    Metal organic frameworks (MOFs) have emerged as great alternatives to traditional nanoporous materials for CO2 separation applications. MOFs are porous materials that are formed by self-assembly of transition metals and organic ligands. The most important advantage of MOFs over well-known porous materials is the possibility to generate multiple materials with varying structural properties and chemical functionalities by changing the combination of metal centers and organic linkers during the synthesis. This leads to a large diversity of materials with various pore sizes and shapes that can be efficiently used for CO2 separations. Since the number of synthesized MOFs has already reached to several thousand, experimental investigation of each MOF at the lab-scale is not practical. High-throughput computational screening of MOFs is a great opportunity to identify the best materials for CO2 separation and to gain molecular-level insights into the structure-performance relationships. This type of knowledge can be used to design new materials with the desired structural features that can lead to extraordinarily high CO2 selectivities. In this mini-review, we focused on developments in high-throughput molecular simulations of MOFs for CO2 separations. After reviewing the current studies on this topic, we discussed the opportunities and challenges in the field and addressed the potential future developments.

  2. Energy Storage Analysis of a Mixed R161/MOF-5 Nanoparticle Nanofluid Based on Molecular Simulations.

    Science.gov (United States)

    Wang, Qiang; Tang, Shengli; Li, Leilei

    2018-05-20

    The thermal properties of refrigerants can be modified by adding porous nanoparticles into them. Here, molecular simulations, including molecular dynamics and grand canonical Monte Carlo, were employed to study the thermal energy storage properties of an R161/MOF-5 nanofluid. The results show that the thermodynamic energy change of MOF-5 nanoparticles is linear to the temperature. The adsorption heat calculated by grand canonical Monte Carlo is close to that calculated by the Clausius⁻Clapeyron equation. Additionally, a negative enhancement of the thermal energy storage capacity of the R161/MOF-5 nanofluid is found near the phase transition area.

  3. MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum Based soc-MOF for CH4, O2 and CO2 Storage

    KAUST Repository

    Alezi, Dalal

    2015-09-28

    The molecular building block approach was employed effectively to construct a series of novel isoreticular, highly porous and stable, aluminum based Metal-Organic Frameworks with soc topology. From this platform, three compounds were experimentally isolated and fully characterized, namely, the parent Al-soc-MOF-1 and its naphthalene and anthracene analogues. Al-soc-MOF-1 exhibits outstanding gravimetric methane uptake (total and working capacity). It is shown experimentally, for the first time, that the Al-soc-MOF platform can address the challenging Department of Energy dual target of 0.5 g/g (gravimetric) and 264 cm3 (STP)/cm3 (volumetric) methane storage. Furthermore, Al-soc-MOF exhibited the highest total gravimetric and volumetric uptake for carbon dioxide and the utmost total and deliverable uptake for oxygen at relatively high pressures among all microporous MOFs. In order to correlate the MOF pore structure and functionality to the gas storage properties, to better understand the structure-properties relationship, we performed a molecular simulation study and evaluated the methane storage performance of Al-soc-MOF platform using diverse organic linkers. It was found that shortening the parent Al-soc-MOF-1 linker resulted in a noticeable enhancement in the working volumetric capacity at specific temperatures and pressures with amply conserved gravimetric uptake/working capacity. In contrast, further expansion of the organic linker (branches and/or core) led to isostructural Al-soc-MOFs with enhanced gravimetric uptake but noticeably lower volumetric capacity. The collective experimental and simulation studies indicated that the parent Al-soc-MOF-1 exhibits the best compromise between the volumetric and gravimetric total and working uptakes in a wide range of pressure and temperature conditions.

  4. MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum Based soc-MOF for CH4, O2 and CO2 Storage

    KAUST Repository

    Alezi, Dalal; Belmabkhout, Youssef; Suetin, Mikhail; Bhatt, Prashant; Weselinski, Lukasz Jan; Solovyeva, Vera; Adil, Karim; Spanopoulos, Ioannis; Trikalitis, Pantelis N.; Emwas, Abdul-Hamid M.; Eddaoudi, Mohamed

    2015-01-01

    The molecular building block approach was employed effectively to construct a series of novel isoreticular, highly porous and stable, aluminum based Metal-Organic Frameworks with soc topology. From this platform, three compounds were experimentally isolated and fully characterized, namely, the parent Al-soc-MOF-1 and its naphthalene and anthracene analogues. Al-soc-MOF-1 exhibits outstanding gravimetric methane uptake (total and working capacity). It is shown experimentally, for the first time, that the Al-soc-MOF platform can address the challenging Department of Energy dual target of 0.5 g/g (gravimetric) and 264 cm3 (STP)/cm3 (volumetric) methane storage. Furthermore, Al-soc-MOF exhibited the highest total gravimetric and volumetric uptake for carbon dioxide and the utmost total and deliverable uptake for oxygen at relatively high pressures among all microporous MOFs. In order to correlate the MOF pore structure and functionality to the gas storage properties, to better understand the structure-properties relationship, we performed a molecular simulation study and evaluated the methane storage performance of Al-soc-MOF platform using diverse organic linkers. It was found that shortening the parent Al-soc-MOF-1 linker resulted in a noticeable enhancement in the working volumetric capacity at specific temperatures and pressures with amply conserved gravimetric uptake/working capacity. In contrast, further expansion of the organic linker (branches and/or core) led to isostructural Al-soc-MOFs with enhanced gravimetric uptake but noticeably lower volumetric capacity. The collective experimental and simulation studies indicated that the parent Al-soc-MOF-1 exhibits the best compromise between the volumetric and gravimetric total and working uptakes in a wide range of pressure and temperature conditions.

  5. Dependence of crystal size on the catalytic performance of a porous coordination polymer.

    Science.gov (United States)

    Kiyonaga, Tomokazu; Higuchi, Masakazu; Kajiwara, Takashi; Takashima, Yohei; Duan, Jingui; Nagashima, Kazuro; Kitagawa, Susumu

    2015-02-14

    Submicrosized MOF-76(Yb) exhibits a higher catalytic performance for esterification than microsized MOF-76(Yb). Control of the crystal size of porous heterogeneous catalysts, such as PCP/MOFs, offers a promising approach to fabricating high-performance catalysts based on accessibility to the internal catalytic sites.

  6. Design and synthesis of a water-stable anionic uranium-based metal-organic framework (MOF) with ultra large pores

    Energy Technology Data Exchange (ETDEWEB)

    Li, Peng; Vermeulen, Nicolaas A.; Gong, Xirui; Malliakas, Christos D.; Stoddart, J. Fraser; Hupp, Joseph T. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Farha, Omar K. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry

    2016-08-22

    Ionic metal-organic frameworks (MOFs) are a subclass of porous materials that have the ability to incorporate different charged species in confined nanospace by ion-exchange. To date, however, very few examples combining mesoporosity and water stability have been realized in ionic MOF chemistry. Herein, we report the rational design and synthesis of a water-stable anionic mesoporous MOF based on uranium and featuring tbo-type topology. The resulting tbo MOF exhibits exceptionally large open cavities (3.9 nm) exceeding those of all known anionic MOFs. By supercritical CO{sub 2} activation, a record-high Brunauer-Emmett-Teller (BET) surface area (2100 m{sup 2} g{sup -1}) for actinide-based MOFs has been obtained. Most importantly, however, this new uranium-based MOF is water-stable and able to absorb positively charged ions selectively over negatively charged ones, enabling the efficient separation of organic dyes and biomolecules.

  7. In situ growth of well-ordered NiFe-MOF-74 on Ni foam by Fe2+ induction as an efficient and stable electrocatalyst for water oxidation.

    Science.gov (United States)

    Xing, Jiale; Guo, Kailu; Zou, Zehua; Cai, Minmin; Du, Jing; Xu, Cailing

    2018-06-06

    Well-ordered NiFe-MOF-74 is in situ grown on Ni foam by the induction of Fe2+ and directly used as an OER electrocatalyst. Benefited from the intrinsic open porous structure of MOF-74, the in situ formed MOF arrays and the synergistic effect of Ni and Fe, outstanding water oxidation activity is obtained in alkaline electrolytes with an overpotential of 223 mV at 10 mA cm-2.

  8. Conductive MOF electrodes for stable supercapacitors with high areal capacitance.

    Science.gov (United States)

    Sheberla, Dennis; Bachman, John C; Elias, Joseph S; Sun, Cheng-Jun; Shao-Horn, Yang; Dincă, Mircea

    2017-02-01

    Owing to their high power density and superior cyclability relative to batteries, electrochemical double layer capacitors (EDLCs) have emerged as an important electrical energy storage technology that will play a critical role in the large-scale deployment of intermittent renewable energy sources, smart power grids, and electrical vehicles. Because the capacitance and charge-discharge rates of EDLCs scale with surface area and electrical conductivity, respectively, porous carbons such as activated carbon, carbon nanotubes and crosslinked or holey graphenes are used exclusively as the active electrode materials in EDLCs. One class of materials whose surface area far exceeds that of activated carbons, potentially allowing them to challenge the dominance of carbon electrodes in EDLCs, is metal-organic frameworks (MOFs). The high porosity of MOFs, however, is conventionally coupled to very poor electrical conductivity, which has thus far prevented the use of these materials as active electrodes in EDLCs. Here, we show that Ni 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 (Ni 3 (HITP) 2 ), a MOF with high electrical conductivity, can serve as the sole electrode material in an EDLC. This is the first example of a supercapacitor made entirely from neat MOFs as active materials, without conductive additives or other binders. The MOF-based device shows an areal capacitance that exceeds those of most carbon-based materials and capacity retention greater than 90% over 10,000 cycles, in line with commercial devices. Given the established structural and compositional tunability of MOFs, these results herald the advent of a new generation of supercapacitors whose active electrode materials can be tuned rationally, at the molecular level.

  9. Conductive MOF electrodes for stable supercapacitors with high areal capacitance

    Science.gov (United States)

    Sheberla, Dennis; Bachman, John C.; Elias, Joseph S.; Sun, Cheng-Jun; Shao-Horn, Yang; Dincă, Mircea

    2017-02-01

    Owing to their high power density and superior cyclability relative to batteries, electrochemical double layer capacitors (EDLCs) have emerged as an important electrical energy storage technology that will play a critical role in the large-scale deployment of intermittent renewable energy sources, smart power grids, and electrical vehicles. Because the capacitance and charge-discharge rates of EDLCs scale with surface area and electrical conductivity, respectively, porous carbons such as activated carbon, carbon nanotubes and crosslinked or holey graphenes are used exclusively as the active electrode materials in EDLCs. One class of materials whose surface area far exceeds that of activated carbons, potentially allowing them to challenge the dominance of carbon electrodes in EDLCs, is metal-organic frameworks (MOFs). The high porosity of MOFs, however, is conventionally coupled to very poor electrical conductivity, which has thus far prevented the use of these materials as active electrodes in EDLCs. Here, we show that Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 (Ni3(HITP)2), a MOF with high electrical conductivity, can serve as the sole electrode material in an EDLC. This is the first example of a supercapacitor made entirely from neat MOFs as active materials, without conductive additives or other binders. The MOF-based device shows an areal capacitance that exceeds those of most carbon-based materials and capacity retention greater than 90% over 10,000 cycles, in line with commercial devices. Given the established structural and compositional tunability of MOFs, these results herald the advent of a new generation of supercapacitors whose active electrode materials can be tuned rationally, at the molecular level.

  10. Coordination Driven Capture of Nicotine Inside a Mesoporous MOF.

    Science.gov (United States)

    Balestri, Davide; Capucci, Davide; Demitri, Nicola; Bacchi, Alessia; Pelagatti, Paolo

    2017-06-30

    Metal organic frameworks (MOFs) are a wide class of crystalline porous polymers studied in many fields, ranging from catalysis to gas storage. In the past few years, MOFs have been studied for the encapsulation of organic or organometallic molecules and for the development of potential drug carriers. Here, we report on the study of two structurally-related mesoporous Cu-MOFs, namely PCN-6 and PCN-6' (PCN stands for Porous Coordination Network), for nicotine trapping. Nicotine is a well-known alkaloid liquid molecule at room temperature, whose crystalline structure is still unknown. In this work, the loading process was monitored by electron ionization mass spectrometry by using a direct insertion probe (DIP-EI/MS), infrared (IR), and ultraviolet/visible (UV/VIS) analysis. Both nuclear magnetic resonance (NMR) spectroscopy and thermogravimetric (TGA) analysis showed evidence that nicotine trapping reaches remarkable uptakes up to 40 wt %. In the case of PCN-6@nicotine, X-ray structural resolution revealed that the guest uptake is triggered by coordination of the pyridine ring of nicotine to the copper nuclei of the paddle-wheel units composing the framework of PCN-6.

  11. Coordination Driven Capture of Nicotine Inside a Mesoporous MOF

    Directory of Open Access Journals (Sweden)

    Davide Balestri

    2017-06-01

    Full Text Available Metal organic frameworks (MOFs are a wide class of crystalline porous polymers studied in many fields, ranging from catalysis to gas storage. In the past few years, MOFs have been studied for the encapsulation of organic or organometallic molecules and for the development of potential drug carriers. Here, we report on the study of two structurally-related mesoporous Cu-MOFs, namely PCN-6 and PCN-6′ (PCN stands for Porous Coordination Network, for nicotine trapping. Nicotine is a well-known alkaloid liquid molecule at room temperature, whose crystalline structure is still unknown. In this work, the loading process was monitored by electron ionization mass spectrometry by using a direct insertion probe (DIP-EI/MS, infrared (IR, and ultraviolet/visible (UV/VIS analysis. Both nuclear magnetic resonance (NMR spectroscopy and thermogravimetric (TGA analysis showed evidence that nicotine trapping reaches remarkable uptakes up to 40 wt %. In the case of PCN-6@nicotine, X-ray structural resolution revealed that the guest uptake is triggered by coordination of the pyridine ring of nicotine to the copper nuclei of the paddle-wheel units composing the framework of PCN-6.

  12. Molecular simulation of polar molecules interaction with MOFs family materials

    International Nuclear Information System (INIS)

    De Toni, M.

    2012-01-01

    The topic of this thesis is the adsorption of simple molecular fluids in nano-porous materials. Many industrial processes are based on this phenomenon, including ionic exchange, selective separation and heterogeneous catalysis. I used molecular simulation to study the adsorption properties of polar molecules of industrial interest (CO 2 and H 2 O) in a new class of crystalline microporous hybrid organic-inorganic materials called Metal-Organic Frameworks (MOFs). They have exceptional adsorption properties due to their topological variety and their versatility, allowed by the large range of possibilities offered by organic and coordination chemistry and functionalizations. I first studied the adsorption of CO 2 in a family of materials called IRMOFs, which share the same topology but have different porous volume, in order to characterize the effect of confinement on their adsorption performance. In particular, a general behavior has been highlighted: the critical temperature decreases when the confinement increases. Then, I looked at a recently synthesized cationic MOF called Zn2(CBTACN). After having localized the extra-framework halogen anions in the unit cell of the material, something which was not possible experimentally, I characterized CO 2 adsorption in this system first as a pure gas and then as a component of different mixtures. Finally, I was interested in the hydrothermal stability of MOFs, a crucial issue for their use in industrial applications. I observed the hydration mechanism of system that is analogous to the MOF-5 (IRMOF-0h) and shed light on some collaborative effects of the attack of water that were unknown to in the literature. (author)

  13. Novel Applications for Oxalate-Phosphate-Amine Metal-Organic-Frameworks (OPA-MOFs): Can an Iron-Based OPA-MOF Be Used as Slow-Release Fertilizer?

    Science.gov (United States)

    Anstoetz, Manuela; Rose, Terry J.; Clark, Malcolm W.; Yee, Lachlan H.; Raymond, Carolyn A.; Vancov, Tony

    2015-01-01

    A porous iron-based oxalate-phosphate-amine metal-organic framework material (OPA-MOF) was investigated as a microbially-induced slow-release nitrogen (N) and phosphorus (P) fertilizer. Seedling growth, grain yields, nutrient uptake of wheat plants, and soil dynamics in incubated soil, were investigated using OPA-MOF vs standard P (triple-superphosphate) and N (urea) fertilizers in an acidic Ferralsol at two application rates (equivalent 120 and 40 kg N ha-1). While urea hydrolysis in the OPA-MOF treatment was rapid, conversion of ammonium to nitrate was significantly inhibited compared to urea treatment. Reduced wheat growth in OPA-MOF treatments was not caused by N-deficiency, but by limited P-bioavailability. Two likely reasons were slow P-mobilisation from the OPA-MOF or rapid P-binding in the acid soil. P-uptake and yield in OPA-MOF treatments were significantly higher than in nil-P controls, but significantly lower than in conventionally-fertilised plants. OPA-MOF showed potential as enhanced efficiency N fertilizer. However, as P-bioavailability was insufficient to meet plant demands, further work should determine if P-availability may be enhanced in alkaline soils, or whether central ions other than Fe, forming the inorganic metal-P framework in the MOF, may act as a more effective P-source in acid soils. PMID:26633174

  14. Versatile Rare Earth Hexanuclear Clusters for the Design and Synthesis of Highly-connected ftw-MOFs

    KAUST Repository

    Eddaoudi, Mohamed

    2015-04-15

    A series of highly porous MOFs were deliberately targeted to contain a 12-connected rare earth hexanuclear cluster and quadrangular tetracarboxylate ligands. The resultant MOFs have an underlying topology of ftw, (4, 12)-c ftw-MOFs. This targeted RE ftw-MOF platform offers potential to assess the effect of pore functionality and size, via ligand functionalization and/or expansion, on adsorption properties of relevant gases. Examination of gas adsorption properties of these compounds showed that the ftw-MOF-2 analogues, constructed from rigid ligands having a phenyl, a naphthyl or an anthracene core, exhibited a relatively high degree of porosity. The specific surface areas and pore volumes of these analogs are amongst the highest reported for rare earth based MOFs. Further studies reveal that Y-ftw-MOF-2 shows promising attributes as a storage media for methane (CH4) at high pressures. Furthermore, Y-ftw-MOF-2 shows potential as a separation agent for the selective removal of normal butane (n-C4H10) and propane (C3H8) from natural gas (NG) as well as interesting properties for the selective separation of n-C4H10 from C3H8 or isobutane (iso-C4H10).

  15. Interplay of metalloligand and organic ligand to tune micropores within isostructural mixed-metal organic frameworks (M'MOFs) for their highly selective separation of chiral and achiral small molecules

    NARCIS (Netherlands)

    Das, M. C.; Guo, Q.; He, Y.; Kim, J.; Zhao, C.-G.; Hong, K.; Xiang, S.; Zhang, Z.; Thomas, K. M.; Krishna, R.; Chen, B.

    2012-01-01

    Four porous isostructural mixed-metal-organic frameworks (M′MOFs) have been synthesized and structurally characterized. The pores within these M′MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly

  16. Crystallography of Representative MOFs Based on Pillared Cyanonickelate (PICNIC Architecture

    Directory of Open Access Journals (Sweden)

    Winnie Wong-Ng

    2016-09-01

    Full Text Available The pillared layer motif is a commonly used route to porous coordination polymers or metal organic frameworks (MOFs. Materials based on the pillared cyano-bridged architecture, [Ni’(LNi(CN4]n (L = pillar organic ligands, also known as PICNICs, have been shown to be especially diverse where pore size and pore functionality can be varied by the choice of pillar organic ligand. In addition, a number of PICNICs form soft porous structures that show reversible structure transitions during the adsorption and desorption of guests. The structural flexibility in these materials can be affected by relatively minor differences in ligand design, and the physical driving force for variations in host-guest behavior in these materials is still not known. One key to understanding this diversity is a detailed investigation of the crystal structures of both rigid and flexible PICNIC derivatives. This article gives a brief review of flexible MOFs. It also reports the crystal structures of five PICNICS from our laboratories including three 3-D porous frameworks (Ni-Bpene, NI-BpyMe, Ni-BpyNH2, one 2-D layer (Ni-Bpy, and one 1-D chain (Ni-Naph compound. The sorption data of BpyMe for CO2, CH4 and N2 is described. The important role of NH3 (from the solvent of crystallization as blocking ligands which prevent the polymerization of the 1-D chains and 2-D layers to become 3D porous frameworks in the Ni-Bpy and Ni-Naph compounds is also addressed.

  17. Porous Hydrogen-Bonded Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Yi-Fei Han

    2017-02-01

    Full Text Available Ordered porous solid-state architectures constructed via non-covalent supramolecular self-assembly have attracted increasing interest due to their unique advantages and potential applications. Porous metal-coordination organic frameworks (MOFs are generated by the assembly of metal coordination centers and organic linkers. Compared to MOFs, porous hydrogen-bonded organic frameworks (HOFs are readily purified and recovered via simple recrystallization. However, due to lacking of sufficiently ability to orientate self-aggregation of building motifs in predictable manners, rational design and preparation of porous HOFs are still challenging. Herein, we summarize recent developments about porous HOFs and attempt to gain deeper insights into the design strategies of basic building motifs.

  18. Construction of hierarchically porous metal-organic frameworks through linker labilization

    Science.gov (United States)

    Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; Li, Jialuo; Huang, Lan; Feng, Liang; Wang, Xuan; Bosch, Mathieu; Alsalme, Ali; Cagin, Tahir; Zhou, Hong-Cai

    2017-05-01

    A major goal of metal-organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.

  19. Influence of metal doping of a MOF-74 framework on hydrogen adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Botas, J.A.; Calleja, G.; Orcajo, M.G. [Rey Juan Carlos Univ., Madrid (Spain). Dept. of Chemical and Energy Technology; Sanchez-Sanchez, M. [CSIC, Madrid (Spain). Inst. de Catalisis y Petroleoquimica

    2010-07-01

    Microporous Metal-Organic Framework (MOF) adsorbents are considered an interesting option for hydrogen storage. Due to their porous nature and unusually high surface areas, these materials show an exceptional H{sub 2} uptake. Unfortunately, their interaction with H{sub 2} molecules is weak, so cryogenic temperatures are required to reach competitive H{sub 2} storage capacities. In this sense, the presence of coordinatively unsaturated and exposed metal centers in some MOF frameworks could increase the affinity for H{sub 2} through stronger metal-H{sub 2} interactions. In this preliminary work, the effect of doping a Zn{sup 2+}-MOF-74 framework with Co{sup 2+}, Cu{sup 2+} and Mg{sup 2+} on its adsorption properties for H{sub 2} has been studied. Characterization studies suggest that the samples prepared have actually the MOF-74 structure, in which the different tested heteroatom ions have been successfully incorporated. The differences in H{sub 2} adsorption at 77 K and 87 K between the MOF-74 samples doped with the mentioned divalent metal ions were discussed as a function of their free pore volume and amount of metal incorporation. (orig.)

  20. Pd Nanoparticles and MOFs Synergistically Hybridized Halloysite Nanotubes for Hydrogen Storage

    Science.gov (United States)

    Jin, Jiao; Ouyang, Jing; Yang, Huaming

    2017-03-01

    Natural halloysite nanotubes (HNTs) were hybridized with metal-organic frameworks (MOFs) to prepare novel composites. MOFs were transformed into carbon by carbonization calcination, and palladium (Pd) nanoparticles were introduced to build an emerging ternary compound system for hydrogen adsorption. The hydrogen adsorption capacities of HNT-MOF composites were 0.23 and 0.24 wt%, while those of carbonized products were 0.24 and 0.27 wt% at 25 °C and 2.65 MPa, respectively. Al-based samples showed higher hydrogen adsorption capacities than Zn-based samples on account of different selectivity between metal and hydrogen and approximate porous characteristics. More pore structures are generated by the carbonization reaction from metal-organic frameworks into carbon; high specific surface area, uniform pore size, and large pore volume benefited the hydrogen adsorption ability of composites. Moreover, it was also possible to promote hydrogen adsorption capacity by incorporating Pd. The hydrogen adsorption capacity of ternary compound, Pd-C-H3-MOFs(Al), reached 0.32 wt% at 25 °C and 2.65 MPa. Dissociation was assumed to take place on the Pd particles, then atomic and molecule hydrogen spilled over to the structure of carboxylated HNTs, MOFs, and the carbon products for enhancing the hydrogen adsorption capacity.

  1. Pd Nanoparticles and MOFs Synergistically Hybridized Halloysite Nanotubes for Hydrogen Storage.

    Science.gov (United States)

    Jin, Jiao; Ouyang, Jing; Yang, Huaming

    2017-12-01

    Natural halloysite nanotubes (HNTs) were hybridized with metal-organic frameworks (MOFs) to prepare novel composites. MOFs were transformed into carbon by carbonization calcination, and palladium (Pd) nanoparticles were introduced to build an emerging ternary compound system for hydrogen adsorption. The hydrogen adsorption capacities of HNT-MOF composites were 0.23 and 0.24 wt%, while those of carbonized products were 0.24 and 0.27 wt% at 25 °C and 2.65 MPa, respectively. Al-based samples showed higher hydrogen adsorption capacities than Zn-based samples on account of different selectivity between metal and hydrogen and approximate porous characteristics. More pore structures are generated by the carbonization reaction from metal-organic frameworks into carbon; high specific surface area, uniform pore size, and large pore volume benefited the hydrogen adsorption ability of composites. Moreover, it was also possible to promote hydrogen adsorption capacity by incorporating Pd. The hydrogen adsorption capacity of ternary compound, Pd-C-H3-MOFs(Al), reached 0.32 wt% at 25 °C and 2.65 MPa. Dissociation was assumed to take place on the Pd particles, then atomic and molecule hydrogen spilled over to the structure of carboxylated HNTs, MOFs, and the carbon products for enhancing the hydrogen adsorption capacity.

  2. Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74

    Directory of Open Access Journals (Sweden)

    Erika M. A. Fuentes-Fernandez

    2018-02-01

    Full Text Available The confined porous environment of metal organic frameworks (MOFs is an attractive system for studying reaction mechanisms. Compared to flat oxide surfaces, MOFs have the key advantage that they exhibit a well-defined structure and present significantly fewer challenges in experimental characterization. As an example of an important reaction, we study here the dissociation of water—which plays a critical role in biology, chemistry, and materials science—in MOFs and show how the knowledge of the structure in this confined environment allows for an unprecedented level of understanding and control. In particular, combining in-situ infrared spectroscopy and first-principles calculations, we show that the water dissociation reaction can be selectively controlled inside Zn-MOF-74 by alcohol, through both chemical and physical interactions. Methanol is observed to speed up water dissociation by 25% to 100%, depending on the alcohol partial pressure. On the other hand, co-adsorption of isopropanol reduces the speed of the water reaction, due mostly to steric interactions. In addition, we also investigate the stability of the product state after the water dissociation has occurred and find that the presence of additional water significantly stabilizes the dissociated state. Our results show that precise control of reactions within nano-porous materials is possible, opening the way for advances in fields ranging from catalysis to electrochemistry and sensors.

  3. Electrospun MOF nanofibers as hydrogen storage media

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2015-06-01

    Full Text Available showed that the incorporation of vacuum degassing was able to create visible porosity in and/or on the PAN nanofibers and the MOF nanocrystals inside the polymeric nanofibers were fully accessible by N2 and H2 gases. With 20 wt.% loading of MOF...

  4. Flexible MOFs under stress: pressure and temperature.

    Science.gov (United States)

    Clearfield, Abraham

    2016-03-14

    In the recent past an enormous number of Metal-Organic Framework type compounds (MOFs) have been synthesized. The novelty resides in their extremely high surface area and the ability to include additional features to their structure either during synthesis or as additives to the MOF. This versatility allows for MOFs to be designed for specific applications. However, the question arises as to whether a particular MOF can withstand the stress that may be encountered in fulfillment of the designated application. In this study we describe the behavior of two flexible MOFs under pressure and several others under temperature increase. The pressure study includes both experimental and theoretical calculations. In the thermal processes evidence for colossal negative thermal expansion were encountered.

  5. Ultrasensitive binder-free glucose sensors based on the pyrolysis of in situ grown Cu MOF

    DEFF Research Database (Denmark)

    Zhang, Xuan; Luo, Jiangshui; Tang, Pengyi

    2017-01-01

    A non-enzymatic glucose sensor based on carbon/Cu composite materials was developed by the in-situ growth and subsequent pyrolysis of metal-organic frameworks (MOFs) on Cu foam. After pyrolysis, SEM, HRTEM and STEM-EELS were employed to clarify the hierarchical Cu@porous carbon electrode. It is f......A non-enzymatic glucose sensor based on carbon/Cu composite materials was developed by the in-situ growth and subsequent pyrolysis of metal-organic frameworks (MOFs) on Cu foam. After pyrolysis, SEM, HRTEM and STEM-EELS were employed to clarify the hierarchical Cu@porous carbon electrode...... matrix electrode displays ultrahigh sensitivity (10.1 mA cm−2 mM−1), low detection limit (sensors....

  6. Advanced fabrication method for the preparation of MOF thin films: Liquid-phase epitaxy approach meets spin coating method.

    KAUST Repository

    Chernikova, Valeriya

    2016-07-14

    Here we report a new and advanced method for the fabrication of highly oriented/polycrystalline metal-organic framework (MOF) thin films. Building on the attractive features of the liquid-phase epitaxy (LPE) approach, a facile spin coating method was implemented to generate MOF thin films in a high-throughput fashion. Advantageously, this approach offers a great prospective to cost-effectively construct thin-films with a significantly shortened preparation time and a lessened chemicals and solvents consumption, as compared to the conventional LPE-process. Certainly, this new spin-coating approach has been implemented successfully to construct various MOF thin films, ranging in thickness from a few micrometers down to the nanometer scale, spanning 2-D and 3-D benchmark MOF materials including Cu2(bdc)2•xH2O, Zn2(bdc)2•xH2O, HKUST-1 and ZIF-8. This method was appraised and proved effective on a variety of substrates comprising functionalized gold, silicon, glass, porous stainless steel and aluminum oxide. The facile, high-throughput and cost-effective nature of this approach, coupled with the successful thin film growth and substrate versatility, represents the next generation of methods for MOF thin film fabrication. Thereby paving the way for these unique MOF materials to address a wide range of challenges in the areas of sensing devices and membrane technology.

  7. Computational Screening of MOFs for Acetylene Separation.

    Science.gov (United States)

    Nemati Vesali Azar, Ayda; Keskin, Seda

    2018-01-01

    Efficient separation of acetylene (C 2 H 2 ) from CO 2 and CH 4 is important to meet the requirement of high-purity acetylene in various industrial applications. Metal organic frameworks (MOFs) are great candidates for adsorption-based C 2 H 2 /CO 2 and C 2 H 2 /CH 4 separations due to their unique properties such as wide range of pore sizes and tunable chemistries. Experimental studies on the limited number of MOFs revealed that MOFs offer remarkable C 2 H 2 /CO 2 and C 2 H 2 /CH 4 selectivities based on single-component adsorption data. We performed the first large-scale molecular simulation study to investigate separation performances of 174 different MOF structures for C 2 H 2 /CO 2 and C 2 H 2 /CH 4 mixtures. Using the results of molecular simulations, several adsorbent performance evaluation metrics, such as selectivity, working capacity, adsorbent performance score, sorbent selection parameter, and regenerability were computed for each MOF. Based on these metrics, the best adsorbent candidates were identified for both separations. Results showed that the top three most promising MOF adsorbents exhibit C 2 H 2 /CO 2 selectivities of 49, 47, 24 and C 2 H 2 /CH 4 selectivities of 824, 684, 638 at 1 bar, 298 K and these are the highest C 2 H 2 selectivities reported to date in the literature. Structure-performance analysis revealed that the best MOF adsorbents have pore sizes between 4 and 11 Å, surface areas in the range of 600-1,200 m 2 /g and porosities between 0.4 and 0.6 for selective separation of C 2 H 2 from CO 2 and CH 4 . These results will guide the future studies for the design of new MOFs with high C 2 H 2 separation potentials.

  8. Computational Screening of MOFs for Acetylene Separation

    Science.gov (United States)

    Nemati Vesali Azar, Ayda; Keskin, Seda

    2018-02-01

    Efficient separation of acetylene (C2H2) from CO2 and CH4 is important to meet the requirement of high-purity acetylene in various industrial applications. Metal organic frameworks (MOFs) are great candidates for adsorption-based C2H2/CO2 and C2H2/CH4 separations due to their unique properties such as wide range of pore sizes and tunable chemistries. Experimental studies on the limited number of MOFs revealed that MOFs offer remarkable C2H2/CO2 and C2H2/CH4 selectivities based on single-component adsorption data. We performed the first large-scale molecular simulation study to investigate separation performances of 174 different MOF structures for C2H2/CO2 and C2H2/CH4 mixtures. Using the results of molecular simulations, several adsorbent performance evaluation metrics, such as selectivity, working capacity, adsorbent performance score, sorbent selection parameter and regenerability were computed for each MOF. Based on these metrics, the best adsorbent candidates were identified for both separations. Results showed that the top three most promising MOF adsorbents exhibit C2H2/CO2 selectivities of 49, 47, 24 and C2H2/CH4 selectivities of 824, 684, 638 at 1 bar, 298 K and these are the highest C2H2 selectivities reported to date in the literature. Structure-performance analysis revealed that the best MOF adsorbents have pore sizes between 4-11 Å, surface areas in the range of 600-1,200 m2/g and porosities between 0.4-0.6 for selective separation of C2H2 from CO2 and CH4. These results will guide the future studies for the design of new MOFs with high C2H2 separation potentials.

  9. Computational Screening of MOFs for Acetylene Separation

    Directory of Open Access Journals (Sweden)

    Ayda Nemati Vesali Azar

    2018-02-01

    Full Text Available Efficient separation of acetylene (C2H2 from CO2 and CH4 is important to meet the requirement of high-purity acetylene in various industrial applications. Metal organic frameworks (MOFs are great candidates for adsorption-based C2H2/CO2 and C2H2/CH4 separations due to their unique properties such as wide range of pore sizes and tunable chemistries. Experimental studies on the limited number of MOFs revealed that MOFs offer remarkable C2H2/CO2 and C2H2/CH4 selectivities based on single-component adsorption data. We performed the first large-scale molecular simulation study to investigate separation performances of 174 different MOF structures for C2H2/CO2 and C2H2/CH4 mixtures. Using the results of molecular simulations, several adsorbent performance evaluation metrics, such as selectivity, working capacity, adsorbent performance score, sorbent selection parameter, and regenerability were computed for each MOF. Based on these metrics, the best adsorbent candidates were identified for both separations. Results showed that the top three most promising MOF adsorbents exhibit C2H2/CO2 selectivities of 49, 47, 24 and C2H2/CH4 selectivities of 824, 684, 638 at 1 bar, 298 K and these are the highest C2H2 selectivities reported to date in the literature. Structure-performance analysis revealed that the best MOF adsorbents have pore sizes between 4 and 11 Å, surface areas in the range of 600–1,200 m2/g and porosities between 0.4 and 0.6 for selective separation of C2H2 from CO2 and CH4. These results will guide the future studies for the design of new MOFs with high C2H2 separation potentials.

  10. Benzoate Acid-Dependent Lattice Dimension of Co-MOFs and MOF-Derived CoS2@CNTs with Tunable Pore Diameters for Supercapacitors.

    Science.gov (United States)

    Zou, Kang-Yu; Liu, Yi-Chen; Jiang, Yi-Fan; Yu, Cheng-Yan; Yue, Man-Li; Li, Zuo-Xi

    2017-06-05

    Herein three novel cobalt metal-organic frameworks (Co-MOFs) with similar ingredients, [Co(bib)(o-bdc)] ∞ (1), [Co 2 (bib) 2 (m-bdc) 2 ] ∞ (2), and {[Co(bib)(p-bdc)(H 2 O)](H 2 O) 0.5 } ∞ (3), have been synthesized from the reaction of cobalt nitrate with 1,4-bis(imidazol-1-yl)benzene (bib) and structure-related aromatic acids (1,2-benzenedicarboxylic acid = o-bdc, 1,3-benzenedicarboxylic acid = m-bdc, and 1,4-benzenedicarboxylic acid = p-bdc) by the solvothermal method. It is aimed to perform systematic research on the relationship among the conformation of benzoate acid, lattice dimension of Co-MOF, and pore diameter of MOF-derived carbon composite. Through the precursor strategy, Co-MOFs 1-3 have been utilized to synthesize porous cobalt@carbon nanotube composites (Co@CNTs). After the in situ gas-sulfurization, secondary composites CoS 2 @CNTs were successfully obtained, which kept similar morphologies of corresponding Co@CNTs without destroying previous highly dispersed structures. Co-MOFs and two series of composites (Co@CNTs and CoS 2 @CNTs) have been well characterized. Topology and Brunauer-Emmett-Teller analyses elucidate that the bdc 2- ion could control the pore diameters of MOF-derived carbon composites by adjusting the lattice dimension of Co-MOFs. The systematic studies on electrochemical properties demonstrate that (p)-CoS 2 @CNT possesses hierarchical morphology, moderate specific surface area, proper pore diameter distribution, and high graphitization, which lead to remarkable specific capacitances (839 F g -1 at 5 mV s -1 and 825 F g -1 at 0.5 A g -1 ) in 2 M potassium hydroxide solution. In addition, the (p)-CoS 2 @CNT electrode exhibits good electrochemical stability and still retains 82.9% of initial specific capacitance at the current density of 1 A g -1 after 5000 cycles.

  11. Reticular Chemistry in Action: A Hydrolytically Stable MOF Capturing Twice Its Weight in Adsorbed Water

    KAUST Repository

    Towsif Abtab, Sk Md; Alezi, Dalal; Bhatt, Prashant; Shkurenko, Aleksander; Belmabkhout, Youssef; Aggarwal, Himanshu; Weselinski, Lukasz Jan; Alsadun, Norah Sadun; Samin, Umer; Hedhili, Mohamed N.; Eddaoudi, Mohamed

    2018-01-01

    Summary Hydrolytically stable adsorbents, with notable water uptake, are of prime importance and offer great potential for many water-adsorption-related applications. Nevertheless, deliberate construction of tunable porous solids with high porosity and high stability remains challenging. Here, we present the successful deployment of reticular chemistry to address this demand: we constructed Cr-soc-MOF-1, a chemically and hydrolytically stable chromium-based metal-organic framework (MOF) with underlying soc topology. Prominently, Cr-soc-MOF-1 offers the requisite thermal and chemical stability concomitant with unique adsorption properties, namely extraordinary high porosity (apparent surface area of 4,549 m2/g) affording a water vapor uptake of 1.95 g/g at 70% relative humidity. This exceptional water uptake is maintained over more than 100 adsorption-desorption cycles. Markedly, the adsorbed water can be fully desorbed by just the simple reduction of the relative humidity at 25°C. Cr-soc-MOF-1 offers great potential for use in applications pertaining to water vapor control in enclosed and confined spaces and dehumidification.

  12. A Confined Fabrication of Perovskite Quantum Dots in Oriented MOF Thin Film.

    Science.gov (United States)

    Chen, Zheng; Gu, Zhi-Gang; Fu, Wen-Qiang; Wang, Fei; Zhang, Jian

    2016-10-26

    Organic-inorganic hybrid lead organohalide perovskites are inexpensive materials for high-efficiency photovoltaic solar cells, optical properties, and superior electrical conductivity. However, the fabrication of their quantum dots (QDs) with uniform ultrasmall particles is still a challenge. Here we use oriented microporous metal-organic framework (MOF) thin film prepared by liquid phase epitaxy approach as a template for CH 3 NH 3 PbI 2 X (X = Cl, Br, and I) perovskite QDs fabrication. By introducing the PbI 2 and CH 3 NH 3 X (MAX) precursors into MOF HKUST-1 (Cu 3 (BTC) 2 , BTC = 1,3,5-benzene tricarboxylate) thin film in a stepwise approach, the resulting perovskite MAPbI 2 X (X = Cl, Br, and I) QDs with uniform diameters of 1.5-2 nm match the pore size of HKUST-1. Furthermore, the photoluminescent properties and stability in the moist air of the perovskite QDs loaded HKUST-1 thin film were studied. This confined fabrication strategy demonstrates that the perovskite QDs loaded MOF thin film will be insensitive to air exposure and offers a novel means of confining the uniform size of the similar perovskite QDs according to the oriented porous MOF materials.

  13. Reticular Chemistry in Action: A Hydrolytically Stable MOF Capturing Twice Its Weight in Adsorbed Water

    KAUST Repository

    Towsif Abtab, Sk Md

    2018-01-11

    Summary Hydrolytically stable adsorbents, with notable water uptake, are of prime importance and offer great potential for many water-adsorption-related applications. Nevertheless, deliberate construction of tunable porous solids with high porosity and high stability remains challenging. Here, we present the successful deployment of reticular chemistry to address this demand: we constructed Cr-soc-MOF-1, a chemically and hydrolytically stable chromium-based metal-organic framework (MOF) with underlying soc topology. Prominently, Cr-soc-MOF-1 offers the requisite thermal and chemical stability concomitant with unique adsorption properties, namely extraordinary high porosity (apparent surface area of 4,549 m2/g) affording a water vapor uptake of 1.95 g/g at 70% relative humidity. This exceptional water uptake is maintained over more than 100 adsorption-desorption cycles. Markedly, the adsorbed water can be fully desorbed by just the simple reduction of the relative humidity at 25°C. Cr-soc-MOF-1 offers great potential for use in applications pertaining to water vapor control in enclosed and confined spaces and dehumidification.

  14. Design and synthesis of a water-stable anionic uranium-based metal-organic framework (MOF) with ultra large pores

    Energy Technology Data Exchange (ETDEWEB)

    Li, Peng; Vermeulen, Nicolaas A.; Gong, Xirui; Malliakas, Christos D.; Stoddart, J. Fraser; Hupp, Joseph T. [Department of Chemistry, Northwestern University, Evanston, IL (United States); Farha, Omar K. [Department of Chemistry, Northwestern University, Evanston, IL (United States); Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah (Saudi Arabia)

    2016-08-22

    Ionic metal-organic frameworks (MOFs) are a subclass of porous materials that have the ability to incorporate different charged species in confined nanospace by ion-exchange. To date, however, very few examples combining mesoporosity and water stability have been realized in ionic MOF chemistry. Herein, we report the rational design and synthesis of a water-stable anionic mesoporous MOF based on uranium and featuring tbo-type topology. The resulting tbo MOF exhibits exceptionally large open cavities (3.9 nm) exceeding those of all known anionic MOFs. By supercritical CO{sub 2} activation, a record-high Brunauer-Emmett-Teller (BET) surface area (2100 m{sup 2} g{sup -1}) for actinide-based MOFs has been obtained. Most importantly, however, this new uranium-based MOF is water-stable and able to absorb positively charged ions selectively over negatively charged ones, enabling the efficient separation of organic dyes and biomolecules. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Encapsulation of Ibuprofen in CD-MOF and Related Bioavailability Studies.

    Science.gov (United States)

    Hartlieb, Karel J; Ferris, Daniel P; Holcroft, James M; Kandela, Irawati; Stern, Charlotte L; Nassar, Majed S; Botros, Youssry Y; Stoddart, J Fraser

    2017-05-01

    Although ibuprofen is one of the most widely used nonsteroidal anti-inflammatory drugs (NSAIDs), it exhibits poor solubility in aqueous and physiological environments as a free acid. In order to improve its oral bioavailability and rate of uptake, extensive research into the development of new formulations of ibuprofen has been undertaken, including the use of excipients as well as ibuprofen salts, such as ibuprofen lysinate and ibuprofen, sodium salt. The ultimate goals of these studies are to reduce the time required for maximum uptake of ibuprofen, as this period of time is directly proportional to the rate of onset of analgesic/anti-inflammatory effects, and to increase the half-life of the drug within the body; that is, the duration of action of the effects of the drug. Herein, we present a pharmaceutical cocrystal of ibuprofen and the biocompatible metal-organic framework called CD-MOF. This metal-organic framework (MOF) is based upon γ-cyclodextrin (γ-CD) tori that are coordinated to alkali metal cations (e.g., K + ions) on both their primary and secondary faces in an alternating manner to form a porous framework built up from (γ-CD) 6 cubes. We show that ibuprofen can be incorporated within CD-MOF-1 either by (i) a crystallization process using the potassium salt of ibuprofen as the alkali cation source for production of the MOF or by (ii) absorption and deprotonation of the free-acid, leading to an uptake of 23-26 wt % of ibuprofen within the CD-MOF. In vitro viability studies revealed that the CD-MOF is inherently not affecting the viability of the cells with no IC 50 value determined up to a concentration of 100 μM. Bioavailability investigations were conducted on mice, and the ibuprofen/CD-MOF pharmaceutical cocrystal was compared to control samples of the potassium salt of ibuprofen in the presence and absence of γ-CD. From these animal studies, we observed that the ibuprofen/CD-MOF-1 cocrystal exhibits the same rapid uptake of ibuprofen as the

  16. Performance and plasticization behavior of polymer–MOF membranes for gas separation at elevated pressures

    NARCIS (Netherlands)

    Shahid, S.; Nijmeijer, Dorothea C.

    2014-01-01

    Mixed matrix membranes (MMMs) based on three distinctively different MOFs (MIL-53(Al) (breathing MOF), ZIF-8 (flexible MOF) and Cu3BTC2 (rigid MOF)) dispersed in Matrimid®-PI have been investigated. MOF loading was varied between 0 wt% and 30 wt%. The fabricated MOF-MMMs were characterized for pure

  17. Aluminium fumarate and CPO-27(Ni) MOFs: Characterization and thermodynamic analysis for adsorption heat pump applications

    International Nuclear Information System (INIS)

    Elsayed, Eman; AL-Dadah, Raya; Mahmoud, Saad; Elsayed, Ahmed; Anderson, Paul A.

    2016-01-01

    Highlights: • CPO-27(Ni) and aluminium fumarate were investigated for adsorption heating, cooling and desalination applications. • Both MOFs have high potential in adsorption applications. • The optimum desorption temperature for the CPO-27(Ni) is higher than 90 °C, and for aluminium fumarate, it is 55–70 °C. • CPO-27(Ni) outperforms aluminium fumarate at low evaporation temperature (5 °C). • Aluminium fumarate outperforms CPO-27(Ni) at high evaporation temperature (20 °C). - Abstract: Metal-organic framework (MOF) materials are new porous materials with high surface area, pore size and volume, and tunable pore geometry thus providing high adsorption capacity. Currently, limited MOF materials with high water adsorption capabilities and hydrothermal stability are available on a large scale. Two MOF materials, namely CPO-27(Ni) and aluminium fumarate, have been identified to have a high hydrothermal stability, high water uptake of 0.47 g_H_2_O_.g_a_d_s"−"1 and 0.53 g_H_2_O_.g_a_d_s"−"1 at a relative pressure of 0.9 and are commercially available. This work aims to measure the water adsorption characteristics of these two MOF materials in terms of isotherms, kinetics and cyclic stability. Also the thermodynamic cycle performance of such materials based on their equilibrium adsorption data was investigated under different operating conditions for various adsorption applications such as heating, cooling and water desalination. Results showed that the CPO-27(Ni)/water pair outperformed the aluminium fumarate/water pair at low evaporation temperatures (5 °C) and high desorption temperatures (≥90 °C), while the aluminium fumarate/water pair was more suitable for applications requiring high evaporation temperature (20 °C) and/or low desorption temperature (70 °C).

  18. Liquid phase epitaxial growth of heterostructured hierarchical MOF thin films

    KAUST Repository

    Chernikova, Valeriya; Shekhah, Osama; Spanopoulos, Ioannis; Trikalitis, Pantelis N.; Eddaoudi, Mohamed

    2017-01-01

    Precise control of epitaxial growth of MOF-on-MOF thin films, for ordered hierarchical tbo-type structures is demonstrated. The heterostructured MOF thin film was fabricated by successful sequential deposition of layers from two different MOFs. The 2-periodic layers, edge-transitive 4,4-square lattices regarded as supermolecular building layers, were commendably cross-linked using a combination of inorganic/organic and organic pillars.

  19. Liquid phase epitaxial growth of heterostructured hierarchical MOF thin films

    KAUST Repository

    Chernikova, Valeriya

    2017-05-10

    Precise control of epitaxial growth of MOF-on-MOF thin films, for ordered hierarchical tbo-type structures is demonstrated. The heterostructured MOF thin film was fabricated by successful sequential deposition of layers from two different MOFs. The 2-periodic layers, edge-transitive 4,4-square lattices regarded as supermolecular building layers, were commendably cross-linked using a combination of inorganic/organic and organic pillars.

  20. A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol.

    Science.gov (United States)

    Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

    2017-06-16

    The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K₂CO₃ base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.

  1. Reticular Chemistry at Its Best: Directed Assembly of Hexagonal Building Units into the Awaited Metal-Organic Framework with the Intricate Polybenzene Topology, pbz-MOF

    KAUST Repository

    Alezi, Dalal

    2016-10-05

    The ability to direct the assembly of hexagonal building units offers great prospective to construct the awaited and looked-for hypothetical polybenzene (pbz) or “cubic graphite” structure, described 70 years ago. Here, we demonstrate the successful use of reticular chemistry as an appropriate strategy for the design and deliberate construction of a zirconium-based metal–organic framework (MOF) with the intricate pbz underlying net topology. The judicious selection of the perquisite hexagonal building units, six connected organic and inorganic building blocks, allowed the formation of the pbz-MOF-1, the first example of a Zr(IV)-based MOF with pbz topology. Prominently, pbz-MOF-1 is highly porous, with associated pore size and pore volume of 13 Å and 0.99 cm3 g–1, respectively, and offers high gravimetric and volumetric methane storage capacities (0.23 g g–1 and 210.4 cm3 (STP) cm–3 at 80 bar). Notably, the pbz-MOF-1 pore system permits the attainment of one of the highest CH4 adsorbed phase density enhancements at high pressures (0.15 and 0.21 g cm–3 at 35 and 65 bar, respectively) as compared to benchmark microporous MOFs.

  2. Reticular Chemistry at Its Best: Directed Assembly of Hexagonal Building Units into the Awaited Metal-Organic Framework with the Intricate Polybenzene Topology, pbz-MOF

    KAUST Repository

    Alezi, Dalal; Spanopoulos, Ioannis; Tsangarakis, Constantinos; Shkurenko, Aleksander; Adil, Karim; Belmabkhout, Youssef; O'Keeffe, Michael; Eddaoudi, Mohamed; Trikalitis, Pantelis N.

    2016-01-01

    The ability to direct the assembly of hexagonal building units offers great prospective to construct the awaited and looked-for hypothetical polybenzene (pbz) or “cubic graphite” structure, described 70 years ago. Here, we demonstrate the successful use of reticular chemistry as an appropriate strategy for the design and deliberate construction of a zirconium-based metal–organic framework (MOF) with the intricate pbz underlying net topology. The judicious selection of the perquisite hexagonal building units, six connected organic and inorganic building blocks, allowed the formation of the pbz-MOF-1, the first example of a Zr(IV)-based MOF with pbz topology. Prominently, pbz-MOF-1 is highly porous, with associated pore size and pore volume of 13 Å and 0.99 cm3 g–1, respectively, and offers high gravimetric and volumetric methane storage capacities (0.23 g g–1 and 210.4 cm3 (STP) cm–3 at 80 bar). Notably, the pbz-MOF-1 pore system permits the attainment of one of the highest CH4 adsorbed phase density enhancements at high pressures (0.15 and 0.21 g cm–3 at 35 and 65 bar, respectively) as compared to benchmark microporous MOFs.

  3. The relevance of metal organic frameworks (MOFs)

    Indian Academy of Sciences (India)

    The metal organic frameworks (MOFs) have evolved to be an important family and a corner stone for research in the area of inorganic chemistry. The progress made since 2000 has attracted researchers from other disciplines to actively engage themselves in this area. This cooperative synergy of different scientific believes ...

  4. A Tunable Bimetallic MOF-74 for Adsorption Chiller Applications: A Tunable Bimetallic MOF-74 for Adsorption Chiller Applications

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jian [Pacific Northwest National Laboratory, 99352 Richland WA USA; Zheng, Jian [Pacific Northwest National Laboratory, 99352 Richland WA USA; Barpaga, Dushyant [Pacific Northwest National Laboratory, 99352 Richland WA USA; Sabale, Sandip [Pacific Northwest National Laboratory, 99352 Richland WA USA; P.G. Department of Chemistry, Jaysingpur College, 416101 Jaysingpur Maharashtra India; Arey, Bruce [Environmental Molecular Sciences Laboratory (EMSL), Pacific Northwest National Laboratory, 99352 Richland WA USA; Derewinski, Miroslaw A. [Pacific Northwest National Laboratory, 99352 Richland WA USA; McGrail, B. Peter [Pacific Northwest National Laboratory, 99352 Richland WA USA; Motkuri, Radha Kishan [Pacific Northwest National Laboratory, 99352 Richland WA USA

    2018-02-12

    A mixed metal strategy, in which two different metal nodes coexist in one MOF framework, was examined using MOF-74. The Ni salt precursor for the MOF-74(Ni) analogue was partially replaced during synthesis with relatively inexpensive Zn salt. These bimetallic MOFs were developed and examined for water sorption for potential use in adsorption cooling/chiller applications. Varying concentration ratios of Ni:Zn in MOF-74 achieved using this mixed metal strategy were shown to provide unique impacts on H2O uptake while significantly mitigating the costs of synthesis

  5. Tunable Robust pacs-MOFs: a Platform for Systematic Enhancement of the C2H2 Uptake and C2H2/C2H4 Separation Performance.

    Science.gov (United States)

    Chen, Di-Ming; Sun, Chun-Xiao; Zhang, Nan-Nan; Si, Huan-Huan; Liu, Chun-Sen; Du, Miao

    2018-03-05

    As a modulatable class of porous crystalline materials, metal-organic frameworks (MOFs) have gained intensive research attention in the domain of gas storage and separation. In this study, we report on the synthesis and gas adsorption properties of two robust MOFs with the general formula [Co 3 (μ 3 -OH)(cpt) 3 Co 3 (μ 3 -OH)(L) 3 (H 2 O) 9 ](NO 3 ) 4 (guests) n [L = 3-amino-1,2,4-triazole (1) and 3,5-diamino-1,2,4-triazole (2); Hcpt = 4-(4-carboxyphenyl)-1,2,4-triazole], which show the same pacs topology. Both MOFs are isostructural to each other and show MIL-88-type frameworks whose pore spaces are partitioned by different functionlized trinuclear 1,2,4-triazolate-based clusters. The similar framework components with different amounts of functional groups make them an ideal platform to permit a systematic gas sorption/separation study to evaluate the effects of distinctive parameters on the C 2 H 2 uptake and separation performance. Because of the presence of additional amido groups, the MOF 2 equipped with a datz-based cluster (Hdatz = 3,5-diamino-1,2,4-triazole) shows a much improved C 2 H 2 uptake capacity and separation performance over that of the MOF 1 equipped with atz-based clusters (Hatz = 3-amino-1,2,4-triazole), although the surface area of the MOF 1 is almost twice than that of the MOF 2. Moreover, the high density of open metal sites, abundant free amido groups, and charged framework give the MOF 2 an excellent C 2 H 2 separation performance, with ideal adsorbed solution theory selectivity values reaching up to 11.5 and 13 for C 2 H 2 /C 2 H 4 (1:99) and C 2 H 2 /CO 2 (50:50) at 298 K and 1 bar, showing potential for use in natural gas purification.

  6. Quest for Highly-connected MOF Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs.

    KAUST Repository

    Alezi, Dalal

    2015-04-07

    Gaining control over the assembly of highly porous rare-earth (RE) based metal-organic frameworks (MOFs) remains challenging. Here we report the latest discoveries on our continuous quest for highly-connected nets. The topological exploration based on the non-compatibility of 12-connected RE polynuclear carboxylate-based cluster, points of extension matching the 12 vertices of the cuboctahedron (cuo), with 3-connected organic ligands led to the discovery of two fascinating and highly-connected minimal edge-transitive nets, pek and aea. The reduced symmetry of the employed triangular tricarboxylate ligand, as compared to the prototype highly symmetrical 1,3,5-benzene(tris)benzoic acid guided the concurrent occurrence of nonanuclear [RE9(μ3-OH)12(μ3-O)2(O2C–)12] and hexanuclear [RE6(OH)8(O2C–)8] carboxylate-based clusters as 12-connected and 8-connected molecular building blocks in the structure of a 3-periodic pek-MOF based on a novel (3,8,12)-c trinodal net. The use of a tricarboxylate ligand with modified angles between carboxylate moieties led to the formation of a second MOF containing solely nonanuclear clusters and exhibiting once more a novel and a highly-connected (3,12,12)-c trinodal net with aea topology. Notably, it is the first time that RE-MOFs with double six-membered ring (d6R) secondary building units are isolated, representing therefore a critical step forward toward the design of novel and highly coordinated materials using the supermolecular building layer approach while considering the d6Rs as building pillars. Lastly, the potential of these new MOFs for gas separation/storage was investigated by performing gas adsorption studies of various probe gas molecules over a wide range of pressures. Noticeably, pek-MOF-1 showed excellent volumetric CO2 and CH4 uptakes at high pressures.

  7. MOF-derived Cu/nanoporous carbon composite and its application for electro-catalysis of hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Raoof, Jahan-Bakhsh; Hosseini, Sayed Reza; Ojani, Reza; Mandegarzad, Sakineh

    2015-01-01

    In this work, metal-organic framework Cu_3(BTC)_2 [BTC = 1,3,5-benzenetricarboxylate] (commonly known as MOF-199 or HKUST-1), is used as porous template for preparation of a Cu/nanoporous carbon composite. The MOF-derived Cu/nanoporous carbon composite (Cu/NPC composite) is synthesized by direct carbonization of the MOF-199 without any carbon precursor additive. The physical characterization of the solid catalyst is achieved by using a variety of different techniques, including XRD (X-ray powder diffraction), scanning electron microscopy, thermo-gravimetric analysis, and nitrogen physisorption measurements. The electrochemical results have shown that the Cu/NPC composite modified glassy carbon electrode (Cu/NPC/GCE) as a non-platinum electrocatalyst exhibited favorable catalytic activity for hydrogen evolution reaction, in spite of high resistance to faradic process. This behavior can be attributed to existence of Cu metal confirmed by XRD and/or high effective pore surface area (1025 m"2 g"−"1) in the Cu/NPC composite. The electron transfer coefficient and exchange current density for the Cu/NPC/GCE is calculated by Tafel plot at about 0.34 and 1.2 × 0"−"3 mAcm"−"2, respectively. - Graphical abstract: Metal organic framework-derived Cu/nanoporous carbon composite (Cu/NPC composite) was prepared by direct carbonization of MOF-199 without addition of any carbon source at 900 °C. The Cu/NPC/GCE demonstrated an excellent electrocatalytic activity towards hydrogen evolution reaction compared with bare GCE. - Highlights: • MDNPC (MOF-199 derived nanoporous carbon) is prepared by direct carbonization. • MOF-199 is utilized as a template without addition of carbon resource. • The MDNPC has a good electrocatalytic activity in hydrogen evolution reaction. • High BET surface area and hydrogen adsorption property improved catalyst activity.

  8. Construction of flexible metal-organic framework (MOF) papers through MOF growth on filter paper and their selective dye capture.

    Science.gov (United States)

    Park, Jeehyun; Oh, Moonhyun

    2017-09-14

    The conjugation of metal-organic frameworks (MOFs) with other materials is an excellent strategy for the production of advanced materials having desired properties and so appropriate applicability. In particular, the integration of MOFs with a flexible paper is expected to form valuable materials in separation technology. Here we report a simple method for the generation of MOF papers through the compact and uniform growth of MOF nanoparticles on the cellulose surface of a carboxymethylated filter paper. The resulting MOF papers show a selective capture ability for negatively charged organic dyes and they can be used for dye separation through simple filtration of a dye solution on the MOF papers. In addition, MOF papers can be reused after a simple washing process without losing their effective dye capture ability.

  9. Single-Crystal-to-Single-Crystal Anion Exchange in a Gadolinium MOF: Incorporation of POMs and [AuCl4]−

    Directory of Open Access Journals (Sweden)

    Javier López-Cabrelles

    2016-04-01

    Full Text Available The encapsulation of functional molecules inside porous coordination polymers (also known as metal-organic frameworks, MOFs has become of great interest in recent years at the field of multifunctional materials. In this article, we present a study of the effects of size and charge in the anion exchange process of a Gd based MOF, involving molecular species like polyoxometalates (POMs, and [AuCl4]−. This post-synthetic modification has been characterized by IR, EDAX, and single crystal diffraction, which have provided unequivocal evidence of the location of the anion molecules in the framework.

  10. One-step synthesis for FeBTC-MOF/iron oxide composite

    Energy Technology Data Exchange (ETDEWEB)

    Nascimento, R.F.F. do; Gentil, G.; Junior, S.A.; Azevedo, W.M. de; Rodrigues, A.R.; Campello, S.L. [Universidade Federal de Pernambuco (UFPE), PE (Brazil)

    2016-07-01

    characteristic strongly dependent on the initial synthesis parameters. Summarizing we have succeed to synthesized highly porous and magnetic Fe?BTC MOF/iron oxide composite using a simple sonochemical method. (author)

  11. Synthesis and Transport Properties of Novel MOF/PIM-1/MOF Sandwich Membranes for Gas Separation.

    Science.gov (United States)

    Fuoco, Alessio; Khdhayyer, Muhanned R; Attfield, Martin P; Esposito, Elisa; Jansen, Johannes C; Budd, Peter M

    2017-02-11

    Metal-organic frameworks (MOFs) were supported on polymer membrane substrates for the fabrication of composite polymer membranes based on unmodified and modified polymer of intrinsic microporosity (PIM-1). Layers of two different MOFs, zeolitic imidazolate framework-8 (ZIF-8) and Copper benzene tricarboxylate ((HKUST-1), were grown onto neat PIM-1, amide surface-modified PIM-1 and hexamethylenediamine (HMDA) -modified PIM-1. The surface-grown crystalline MOFs were characterized by a combination of several techniques, including powder X-ray diffraction, infrared spectroscopy and scanning electron microscopy to investigate the film morphology on the neat and modified PIM-1 membranes. The pure gas permeabilities of He, H₂, O₂, N₂, CH₄, CO₂ were studied to understand the effect of the surface modification on the basic transport properties and evaluate the potential use of these membranes for industrially relevant gas separations. The pure gas transport was discussed in terms of permeability and selectivity, highlighting the effect of the MOF growth on the diffusion coefficients of the gas in the new composite polymer membranes. The results confirm that the growth of MOFs on polymer membranes can enhance the selectivity of the appropriately functionalized PIM-1, without a dramatic decrease of the permeability.

  12. Synthesis and Transport Properties of Novel MOF/PIM-1/MOF Sandwich Membranes for Gas Separation

    Directory of Open Access Journals (Sweden)

    Alessio Fuoco

    2017-02-01

    Full Text Available Metal-organic frameworks (MOFs were supported on polymer membrane substrates for the fabrication of composite polymer membranes based on unmodified and modified polymer of intrinsic microporosity (PIM-1. Layers of two different MOFs, zeolitic imidazolate framework-8 (ZIF-8 and Copper benzene tricarboxylate ((HKUST-1, were grown onto neat PIM-1, amide surface-modified PIM-1 and hexamethylenediamine (HMDA -modified PIM-1. The surface-grown crystalline MOFs were characterized by a combination of several techniques, including powder X-ray diffraction, infrared spectroscopy and scanning electron microscopy to investigate the film morphology on the neat and modified PIM-1 membranes. The pure gas permeabilities of He, H2, O2, N2, CH4, CO2 were studied to understand the effect of the surface modification on the basic transport properties and evaluate the potential use of these membranes for industrially relevant gas separations. The pure gas transport was discussed in terms of permeability and selectivity, highlighting the effect of the MOF growth on the diffusion coefficients of the gas in the new composite polymer membranes. The results confirm that the growth of MOFs on polymer membranes can enhance the selectivity of the appropriately functionalized PIM-1, without a dramatic decrease of the permeability.

  13. Synthesis and Transport Properties of Novel MOF/PIM-1/MOF Sandwich Membranes for Gas Separation

    Science.gov (United States)

    Fuoco, Alessio; Khdhayyer, Muhanned R.; Attfield, Martin P.; Esposito, Elisa; Jansen, Johannes C.; Budd, Peter M.

    2017-01-01

    Metal-organic frameworks (MOFs) were supported on polymer membrane substrates for the fabrication of composite polymer membranes based on unmodified and modified polymer of intrinsic microporosity (PIM-1). Layers of two different MOFs, zeolitic imidazolate framework-8 (ZIF-8) and Copper benzene tricarboxylate ((HKUST-1), were grown onto neat PIM-1, amide surface-modified PIM-1 and hexamethylenediamine (HMDA) -modified PIM-1. The surface-grown crystalline MOFs were characterized by a combination of several techniques, including powder X-ray diffraction, infrared spectroscopy and scanning electron microscopy to investigate the film morphology on the neat and modified PIM-1 membranes. The pure gas permeabilities of He, H2, O2, N2, CH4, CO2 were studied to understand the effect of the surface modification on the basic transport properties and evaluate the potential use of these membranes for industrially relevant gas separations. The pure gas transport was discussed in terms of permeability and selectivity, highlighting the effect of the MOF growth on the diffusion coefficients of the gas in the new composite polymer membranes. The results confirm that the growth of MOFs on polymer membranes can enhance the selectivity of the appropriately functionalized PIM-1, without a dramatic decrease of the permeability. PMID:28208658

  14. MOFs for the Sensitive Detection of Ammonia: Deployment of fcu-MOF Thin Films as Effective Chemical Capacitive Sensors.

    Science.gov (United States)

    Assen, Ayalew H; Yassine, Omar; Shekhah, Osama; Eddaoudi, Mohamed; Salama, Khaled N

    2017-09-22

    This work reports on the fabrication and deployment of a select metal-organic framework (MOF) thin film as an advanced chemical capacitive sensor for the sensing/detection of ammonia (NH 3 ) at room temperature. Namely, the MOF thin film sensing layer consists of a rare-earth (RE) MOF (RE-fcu-MOF) deposited on a capacitive interdigitated electrode (IDE). Purposely, the chemically stable naphthalene-based RE-fcu-MOF (NDC-Y-fcu-MOF) was elected and prepared/arranged as a thin film on a prefunctionalized capacitive IDE via the solvothermal growth method. Unlike earlier realizations, the fabricated MOF-based sensor showed a notable detection sensitivity for NH 3 at concentrations down to 1 ppm, with a detection limit appraised to be around 100 ppb (at room temperature) even in the presence of humidity and/or CO 2 . Distinctly, the NDC-Y-fcu-MOF based sensor exhibited the required stability to NH 3 , in contrast to other reported MOFs, and a remarkable detection selectivity toward NH 3 vs CH 4 , NO 2 , H 2 , and C 7 H 8 . The NDC-Y-fcu-MOF based sensor exhibited excellent performance for sensing ammonia for simulated breathing system in the presence of the mixture of carbon dioxide and/or humidity (water vapor), with no major alteration in the detection signal.

  15. MOFs for the Sensitive Detection of Ammonia: Deployment of fcu-MOF Thin-Films as Effective Chemical Capacitive Sensors.

    KAUST Repository

    Assen, Ayalew Hussen Assen

    2017-08-15

    This work reports on the fabrication and deployment of a select metal-organic framework (MOF) thin film as an advanced chemical capacitive sensor for the sensing/detection of ammonia (NH3) at room temperature. Namely, the MOF thin film sensing layer consists of a rare-earth (RE) MOF (RE-fcu-MOF) deposited on a capacitive interdigitated electrode (IDE). Purposely, the chemically stable naphthalene-based RE-fcu-MOF (NDC-Y-fcu-MOF) was elected and prepared/arranged as a thin film on a pre-functionalized capacitive IDE via the solvothermal growth method. Unlike earlier realizations, the fabricated MOF-based sensor showed a notable detection sensitivity for NH3 at concentrations down to 1 ppm, with a detection limit appraised to be around 100 ppb (at room temperature) even in the presence of humidity and/or CO2. Distinctly, the NDC-Y-fcu-MOF based sensor exhibited the required stability to NH3, in contract to other reported MOFs, and a remarkable detection selectivity towards NH3 vs. CH4, NO2, H2 and C7H8. The NDC-Y-fcu-MOF based sensor exhibited excellent performance for sensing ammonia for simulated breathing system in the presence of the mixture of carbon dioxide and/or humidity (water vapor), with no major alteration in the detection signal.

  16. Reticular Chemistry for the Highly Connected Porous Crystalline Frameworks and Their Potential Applications

    KAUST Repository

    Chen, Zhijie

    2018-03-31

    Control at the molecular level over porous solid-state materials is of prime importance for fine-tuning the local structures, as well as the resultant properties. Traditional porous solid-state materials such as zeolite and activated carbon are the benchmarks in the current market with vital applications in sorption and heterogeneous catalysis. However, the adjustments of pore size and geometry of those materials, which are essential for the broader aspect of modern prominent applications, remain challenging. Reticular chemistry has emerged as a dominant tool toward the ‘designed syntheses’ of porous crystalline frameworks (e.g. metal-organic frameworks (MOFs)) with a specific pore system. This dissertation illustrates the power of reticular chemistry and its use in the directional assembly of highly coordinated MOF materials, as well as their potential applications such as gas storage, natural gas upgrading, and light hydrocarbon separation. Highly connected minimal edge-transitive derived and related nets, obtained via the deconstruction of nodes of the edge-transitive nets, are suitable blueprints and can potentially be deployed in the future ‘designed syntheses’ of MOFs. The further employment of the conceptual net-coded building units (e.g. highly connected MBBs and edge-transitive SBLs) in the practical reticular synthesis results in the rational design and construction of functional MOF platforms like shp-, alb-, kce-, kex- and eea- MOFs. In addition, the isoreticular synthesis of Al-cea-MOF-2 with functionalized pendant acid moieties inside pore channels in comparison to the parent Al-cea-MOF-1 led to enhanced light hydrocarbons separation performance. Moreover, controlling the molecular defects in Zr-fum-fcu-MOFs resulted in the development of an ultramicroporous adsorbent with an engineered aperture size for the highly efficient separation of butane/iso-butane.

  17. The quest for modular nanocages: Tbo -MOF as an archetype for mutual substitution, functionalization, and expansion of quadrangular pillar building blocks

    KAUST Repository

    Eubank, Jarrod F.

    2011-09-14

    A new blueprint network for the design and synthesis of porous, functional 3D metal-organic frameworks (MOFs) has been identified, namely, the tbo net. Accordingly, tbo-MOFs based on this unique (3,4)-connected net can be exclusively constructed utilizing a combination of well-known and readily targeted [M(R-BDC)]n MOF layers [i.e., supermolecular building layers (SBLs)] based on the edge-transitive 4,4 square lattice (sql) (i.e., 2D four-building units) and a novel pillaring strategy based on four proximal isophthalate ligands from neighboring SBL membered rings (i.e., two pairs from each layer) covalently cross-linked through an organic quadrangular core (e.g., tetrasubstituted benzene). Our strategy permits the rational design and synthesis of isoreticular structures, functionalized and/or expanded, that possess extra-large nanocapsule-like cages, high porosity, and potential for gas separation and storage, among others. Thus, tbo-MOF serves as an archetypal tunable, isoreticular MOF platform for targeting desired applications. © 2011 American Chemical Society.

  18. The quest for modular nanocages: Tbo -MOF as an archetype for mutual substitution, functionalization, and expansion of quadrangular pillar building blocks

    KAUST Repository

    Eubank, Jarrod F.; Mouttaki, Hasnaa; Cairns, Amy; Belmabkhout, Youssef; Wojtas, Łukasz; Luebke, Ryan; Al Kordi, Mohamed; Eddaoudi, Mohamed

    2011-01-01

    A new blueprint network for the design and synthesis of porous, functional 3D metal-organic frameworks (MOFs) has been identified, namely, the tbo net. Accordingly, tbo-MOFs based on this unique (3,4)-connected net can be exclusively constructed utilizing a combination of well-known and readily targeted [M(R-BDC)]n MOF layers [i.e., supermolecular building layers (SBLs)] based on the edge-transitive 4,4 square lattice (sql) (i.e., 2D four-building units) and a novel pillaring strategy based on four proximal isophthalate ligands from neighboring SBL membered rings (i.e., two pairs from each layer) covalently cross-linked through an organic quadrangular core (e.g., tetrasubstituted benzene). Our strategy permits the rational design and synthesis of isoreticular structures, functionalized and/or expanded, that possess extra-large nanocapsule-like cages, high porosity, and potential for gas separation and storage, among others. Thus, tbo-MOF serves as an archetypal tunable, isoreticular MOF platform for targeting desired applications. © 2011 American Chemical Society.

  19. Synthesis and electrochemical properties of Fe3O4@MOF core-shell microspheres as an anode for lithium ion battery application

    Science.gov (United States)

    Sun, Xuemin; Gao, Ge; Yan, Dongwei; Feng, Chuanqi

    2017-05-01

    The Fe3O4@MOF composite with a microspheric core and a porous metal-organic framework (MOF HKUST-1) shell has been successfully synthesized utilizing a versatile Layer-by-Layer (LBL) assembly method. The structure was identified by X-ray diffraction (XRD), and the morphology was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The Fe3O4@MOF composite exhibited outstanding electrochemical properties when it was used as an anode material for lithium ion batteries (LIBs). After 100 discharge-charge cycles at a current density of 100 mA g-1, the reversible capacity of Fe3O4@MOF could maintain ∼1002 mAh g-1, which was much higher than that of the bare Fe3O4 counterpart (696 mAh g-1). Moreover, load the current density as high as 2 A g-1 (after 70 cycles at the current density step increased from 0.1 to 2 A g-1), it still delivered a reversible capacity of ∼429 mAh g-1. The results demonstrate that the cycling stability of Fe3O4 as an anode could be significantly improved by coating Cu3(1,3,5-benzenetricarboxylate)2 (HKUST-1). This strategy may offer new route to prepare other composite materials using different particles and suitable Metal-organic frameworks (MOFs) for LIBs application.

  20. Ubiquitylation of the acetyltransferase MOF in Drosophila melanogaster.

    Science.gov (United States)

    Schunter, Sarah; Villa, Raffaella; Flynn, Victoria; Heidelberger, Jan B; Classen, Anne-Kathrin; Beli, Petra; Becker, Peter B

    2017-01-01

    The nuclear acetyltransferase MOF (KAT8 in mammals) is a subunit of at least two multi-component complexes involved in transcription regulation. In the context of complexes of the 'Non-Specific-Lethal' (NSL) type it controls transcription initiation of many nuclear housekeeping genes and of mitochondrial genes. While this function is conserved in metazoans, MOF has an additional, specific function in Drosophila in the context of dosage compensation. As a subunit of the male-specific-lethal dosage compensation complex (MSL-DCC) it contributes to the doubling of transcription output from the single male X chromosome by acetylating histone H4. Proper dosage compensation requires finely tuned levels of MSL-DCC and an appropriate distribution of MOF between the regulatory complexes. The amounts of DCC formed depends directly on the levels of the male-specific MSL2, which orchestrates the assembly of the DCC, including MOF recruitment. We found earlier that MSL2 is an E3 ligase that ubiquitylates most MSL proteins, including MOF, suggesting that ubiquitylation may contribute to a quality control of MOF's overall levels and folding state as well as its partitioning between the complex entities. We now used mass spectrometry to map the lysines in MOF that are ubiquitylated by MSL2 in vitro and identified in vivo ubiquitylation sites of MOF in male and female cells. MSL2-specific ubiquitylation in vivo could not be traced due to the dominance of other, sex-independent ubiquitylation events and conceivably may be rare or transient. Expressing appropriately mutated MOF derivatives we assessed the importance of the ubiquitylated lysines for dosage compensation by monitoring DCC formation and X chromosome targeting in cultured cells, and by genetic complementation of the male-specific-lethal mof2 allele in flies. Our study provides a comprehensive analysis of MOF ubiquitylation as a reference for future studies.

  1. Ubiquitylation of the acetyltransferase MOF in Drosophila melanogaster.

    Directory of Open Access Journals (Sweden)

    Sarah Schunter

    Full Text Available The nuclear acetyltransferase MOF (KAT8 in mammals is a subunit of at least two multi-component complexes involved in transcription regulation. In the context of complexes of the 'Non-Specific-Lethal' (NSL type it controls transcription initiation of many nuclear housekeeping genes and of mitochondrial genes. While this function is conserved in metazoans, MOF has an additional, specific function in Drosophila in the context of dosage compensation. As a subunit of the male-specific-lethal dosage compensation complex (MSL-DCC it contributes to the doubling of transcription output from the single male X chromosome by acetylating histone H4. Proper dosage compensation requires finely tuned levels of MSL-DCC and an appropriate distribution of MOF between the regulatory complexes. The amounts of DCC formed depends directly on the levels of the male-specific MSL2, which orchestrates the assembly of the DCC, including MOF recruitment. We found earlier that MSL2 is an E3 ligase that ubiquitylates most MSL proteins, including MOF, suggesting that ubiquitylation may contribute to a quality control of MOF's overall levels and folding state as well as its partitioning between the complex entities. We now used mass spectrometry to map the lysines in MOF that are ubiquitylated by MSL2 in vitro and identified in vivo ubiquitylation sites of MOF in male and female cells. MSL2-specific ubiquitylation in vivo could not be traced due to the dominance of other, sex-independent ubiquitylation events and conceivably may be rare or transient. Expressing appropriately mutated MOF derivatives we assessed the importance of the ubiquitylated lysines for dosage compensation by monitoring DCC formation and X chromosome targeting in cultured cells, and by genetic complementation of the male-specific-lethal mof2 allele in flies. Our study provides a comprehensive analysis of MOF ubiquitylation as a reference for future studies.

  2. The growth of high density network of MOF nano-crystals across macroporous metal substrates - Solvothermal synthesis versus rapid thermal deposition

    Science.gov (United States)

    Maina, James W.; Gonzalo, Cristina Pozo; Merenda, Andrea; Kong, Lingxue; Schütz, Jürg A.; Dumée, Ludovic F.

    2018-01-01

    Fabrication of metal organic framework (MOF) films and membranes across macro-porous metal substrates is extremely challenging, due to the large pore sizes across the substrates, poor wettability, and the lack of sufficient reactive functional groups on the surface, which prevent high density nucleation of MOF crystals. Herein, macroporous stainless steel substrates (pore size 44 × 40 μm) are functionalized with amine functional groups, and the growth of ZIF-8 crystals investigated through both solvothermal synthesis and rapid thermal deposition (RTD), to assess the role of synthesis routes in the resultant membranes microstructure, and subsequently their performance. Although a high density of well interconnected MOF crystals was observed across the modified substrates following both techniques, RTD was found to be a much more efficient route, yielding high quality membranes under 1 h, as opposed to the 24 h required for solvothermal synthesis. The RTD membranes also exhibited high gas permeance, with He permeance of up to 2.954 ± 0.119 × 10-6 mol m-2 s-1 Pa-1, and Knudsen selectivities for He/N2, Ar/N2 and CO2/N2, suggesting the membranes were almost defect free. This work opens up route for efficient fabrication of MOF films and membranes across macro-porous metal supports, with potential application in electrically mediated separation applications.

  3. Application of MD Simulations to Predict Membrane Properties of MOFs

    Directory of Open Access Journals (Sweden)

    Elda Adatoz

    2015-01-01

    Full Text Available Metal organic frameworks (MOFs are a new group of nanomaterials that have been widely examined for various chemical applications. Gas separation using MOF membranes has become an increasingly important research field in the last years. Several experimental studies have shown that thin-film MOF membranes can outperform well known polymer and zeolite membranes due to their higher gas permeances and selectivities. Given the very large number of available MOF materials, it is impractical to fabricate and test the performance of every single MOF membrane using purely experimental techniques. In this study, we used molecular simulations, Monte Carlo and Molecular Dynamics, to estimate both single-gas and mixture permeances of MOF membranes. Predictions of molecular simulations were compared with the experimental gas permeance data of MOF membranes in order to validate the accuracy of our computational approach. Results show that computational methodology that we described in this work can be used to accurately estimate membrane properties of MOFs prior to extensive experimental efforts.

  4. Investigation of the adsorption properties and structures of porous materials for adsorptive removal of pollutants from water

    OpenAIRE

    ZAHRA ABBASI

    2017-01-01

    Adsorption is a low cost and effective method for the removal of non-biodegradable and harmful pollutants from water which has been widely used in industry. Porous and nanoporous materials such as metal organic frameworks (MOFs) and fly ash wastes were used as adsorbents for the removal of pollutants from water. The study showed MOF adsorbent could be fabricated as beads for easy handling and recycling due to the very low buoyancy. Temperature of heat treatment had significant effect on adsor...

  5. Enzyme-MOF (metal-organic framework) composites.

    Science.gov (United States)

    Lian, Xizhen; Fang, Yu; Joseph, Elizabeth; Wang, Qi; Li, Jialuo; Banerjee, Sayan; Lollar, Christina; Wang, Xuan; Zhou, Hong-Cai

    2017-06-06

    The ex vivo application of enzymes in various processes, especially via enzyme immobilization techniques, has been extensively studied in recent years in order to enhance the recyclability of enzymes, to minimize enzyme contamination in the product, and to explore novel horizons for enzymes in biomedical applications. Possessing remarkable amenability in structural design of the frameworks as well as almost unparalelled surface tunability, Metal-Organic Frameworks (MOFs) have been gaining popularity as candidates for enzyme immobilization platforms. Many MOF-enzyme composites have achieved unprecedented results, far outperforming free enzymes in many aspects. This review summarizes recent developments of MOF-enzyme composites with special emphasis on preparative techniques and the synergistic effects of enzymes and MOFs. The applications of MOF-enzyme composites, primarily in transferation, catalysis and sensing, are presented as well. The enhancement of enzymatic activity of the composites over free enzymes in biologically incompatible conditions is emphasized in many cases.

  6. MOFs for the Sensitive Detection of Ammonia: Deployment of fcu-MOF Thin-Films as Effective Chemical Capacitive Sensors.

    KAUST Repository

    Assen, Ayalew Hussen Assen; Yassine, Omar; Shekhah, Osama; Eddaoudi, Mohamed; Salama, Khaled N.

    2017-01-01

    This work reports on the fabrication and deployment of a select metal-organic framework (MOF) thin film as an advanced chemical capacitive sensor for the sensing/detection of ammonia (NH3) at room temperature. Namely, the MOF thin film sensing layer

  7. Interaction of Hydrogen with MOF-5.

    Science.gov (United States)

    Bordiga, Silvia; Vitillo, Jenny G; Ricchiardi, Gabriele; Regli, Laura; Cocina, Donato; Zecchina, Adriano; Arstad, Bjørnar; Bjørgen, Morten; Hafizovic, Jasmina; Lillerud, Karl Petter

    2005-10-06

    Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals.

  8. General Theory of Absorption in Porous Materials: Restricted Multilayer Theory.

    Science.gov (United States)

    Aduenko, Alexander A; Murray, Andy; Mendoza-Cortes, Jose L

    2018-04-18

    In this article, we present an approach for the generalization of adsorption of light gases in porous materials. This new theory goes beyond Langmuir and Brunauer-Emmett-Teller theories, which are the standard approaches that have a limited application to crystalline porous materials by their unphysical assumptions on the amount of possible adsorption layers. The derivation of a more general equation for any crystalline porous framework is presented, restricted multilayer theory. Our approach allows the determination of gas uptake considering only geometrical constraints of the porous framework and the interaction energy of the guest molecule with the framework. On the basis of this theory, we calculated optimal values for the adsorption enthalpy at different temperatures and pressures. We also present the use of this theory to determine the optimal linker length for a topologically equivalent framework series. We validate this theoretical approach by applying it to metal-organic frameworks (MOFs) and show that it reproduces the experimental results for seven different reported materials. We obtained the universal equation for the optimal linker length, given the topology of a porous framework. This work applied the general equation to MOFs and H 2 to create energy-storage materials; however, this theory can be applied to other crystalline porous materials and light gases, which opens the possibility of designing the next generations of energy-storage materials by first considering only the geometrical constraints of the porous materials.

  9. Covalent immobilization of glucose oxidase on amino MOFs via post-synthetic modification

    NARCIS (Netherlands)

    Tudisco, C.G.; Zolubas, G.; Seoane de la Cuesta, B.; Zafarani, H.; Kazemzad Asiabi, M.; Gascon Sabate, J.; Hagedoorn, P.L.; Rassaei, L.

    2016-01-01

    The post-synthetic modification (PSM) of two amino-MOFs with glucose oxidase is reported in this study. The multi-step approach preserved the MOFs' structure and allowed the production of enzyme-functionalized MOFs (MOFs@GOx), which retained the enzymatic activity and showed selective properties

  10. MOFzyme: Intrinsic protease-like activity of Cu-MOF

    Science.gov (United States)

    Li, Bin; Chen, Daomei; Wang, Jiaqiang; Yan, Zhiying; Jiang, Liang; Deliang Duan; He, Jiao; Luo, Zhongrui; Zhang, Jinping; Yuan, Fagui

    2014-10-01

    The construction of efficient enzyme mimetics for the hydrolysis of peptide bonds in proteins is challenging due to the high stability of peptide bonds and the importance of proteases in biology and industry. Metal-organic frameworks (MOFs) consisting of infinite crystalline lattices with metal clusters and organic linkers may provide opportunities for protease mimic which has remained unknown. Herein, we report that Cu2(C9H3O6)4/3 MOF (which is well known as HKUST-1 and denoted as Cu-MOF here), possesses an intrinsic enzyme mimicking activity similar to that found in natural trypsin to bovine serum albumin (BSA) and casein. The Michaelis constant (Km) of Cu-MOF is about 26,000-fold smaller than that of free trypsin indicating a much higher affinity of BSA for Cu-MOF surface. Cu-MOF also exhibited significantly higher catalytic efficiency than homogeneous artificial metalloprotease Cu(II) complexes and could be reused for ten times without losing in its activity. Moreover, Cu-MOF was successfully used to simulate trypsinization in cell culture since it dissociated cells in culture even without EDTA.

  11. Electrochemical Performance of Ni-MOFs for Supercapacitors

    Science.gov (United States)

    Li, Yujuan; Song, Lili; Han, Yinghui; Wang, Guangyou

    2018-03-01

    In this work, the Ni-MOFs of electrode material has been synthesized, characterized and studied for the electrochemical properties of electrode materials. The effects of the doping amount of Ni, calcination temperature and time were studied in detail. The results suggested that the electrochemical properties were obviously improved by the Ni-MOFs of electrode material and the best preparation conditions can also improve the electrochemical properties of electrode materials. These results open a way for the design of tailored MOFs as electrode materials for supercapacitors.

  12. High-throughput screening of small-molecule adsorption in MOF-74

    Science.gov (United States)

    Thonhauser, T.; Canepa, P.

    2014-03-01

    Using high-throughput screening coupled with state-of-the-art van der Waals density functional theory, we investigate the adsorption properties of four important molecules, H2, CO2, CH4, and H2O in MOF-74-  with  = Be, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Nb, Ru, Rh, Pd, La, W, Os, Ir, and Pt. We show that high-throughput techniques can aid in speeding up the development and refinement of effective materials for hydrogen storage, carbon capture, and gas separation. The exploration of the configurational adsorption space allows us to extract crucial information concerning, for example, the competition of water with CO2 for the adsorption binding sites. We find that only a few noble metals--Rh, Pd, Os, Ir, and Pt--favor the adsorption of CO2 and hence are potential candidates for effective carbon-capture materials. Our findings further reveal significant differences in the binding characteristics of H2, CO2, CH4, and H2O within the MOF structure, indicating that molecular blends can be successfully separated by these nano-porous materials. Supported by DOE DE-FG02-08ER46491.

  13. Interactions on External MOF Surfaces: Desorption of Water and Ethanol from CuBDC Nanosheets.

    Science.gov (United States)

    Elder, Alexander C; Aleksandrov, Alexandr B; Nair, Sankar; Orlando, Thomas M

    2017-10-03

    The external surfaces of metal-organic framework (MOF) materials are difficult to experimentally isolate due to the high porosities of these materials. MOF surface surrogates in the form of copper benzenedicarboxylate (CuBDC) nanosheets were synthesized using a bottom-up approach, and the surface interactions of water and ethanol were investigated by temperature-programmed desorption (TPD). A method of analysis of diffusion-influenced TPD was developed to measure the desorption properties of these porous materials. This approach also allows the extraction of diffusion coefficients from TPD data. The transmission Fourier transform infrared spectra, powder X-ray diffraction patterns, and TPD data indicate that water desorbs from CuBDC nanosheets with activation energies of 44 ± 2 kJ/mol at edge sites and 58 ± 1 kJ/mol at external surface and internal and pore sites. Ethanol desorbs with activation energies of 58 ± 1 kJ/mol at internal pore sites and 66 ± 0.4 kJ/mol at external surface sites. Co-adsorption of water and ethanol was also investigated. The presence of ethanol was found to inhibit the desorption of water, resulting in a water desorption process with an activation energy of 68 ± 0.7 kJ/mol.

  14. Processing and Performance of MOF (Metal Organic Framework)-Loaded PAN Nanofibrous Membrane for CO2 Adsorption

    Science.gov (United States)

    Wahiduzzaman; Khan, Mujibur R.; Harp, Spencer; Neumann, Jeffrey; Sultana, Quazi Nahida

    2016-04-01

    The objective of this experimental study is to produce a nanofibrous membrane functionalized with adsorbent particles called metal organic framework (MOF) in order to adsorb CO2 from a gas source. Therefore, Polyacrylonitrile (PAN) was chosen as the precursor for nanofibers and HKUST-1, a Cu-based MOF, was chosen as adsorbent. The experimental process consists of electrospinning PAN solution blended with HKUST-1 to produce a nanofibrous mat as working substrates. The fibers were collected in a cylindrical canister model. SEM image of this mat showed nanofibers with the presence of small adsorbent particles, impregnated into the as-spun fibers discretely. To increase the amount of MOF particles for effectual gas adsorption, a secondary solvothermal process of producing MOF particles on the fibers was required. This process consists of multiple growth cycles of HKUST-1 particles by using a sol-gel precursor. SEM images showed uniform distribution of porous MOF particles of 2-4 µm in size on the fiber surface. Energy dispersive spectroscopy report of the fiber confirmed the presence of MOF particles through the identification of characteristic Copper elemental peaks of HKUST-1. To determine the thermal stability of the fibrous membrane, Thermogravimetric analysis of HKUST-1 consisting of PAN fiber was performed where a total weight loss of 40% between 210 and 360 °C was observed, hence proving the high-temperature durability of the synthesized membrane. BET surface area of the fiber membrane was measured as 540.73 m2/g. The fiber membrane was then placed into an experimental test bench containing a mixed gas inflow of CO2 and N2. Using non-dispersive infrared CO2 sensors connected to the inlet and outlet port of the bench, significant reduction of CO2 in concentration was measured. Comparative IR spectroscopic analysis between the gas-treated and gas untreated fiber samples showed the presence of characteristic peak in the vicinity of 2300 and 2400 cm-1 which

  15. Zn-based porous coordination solid as diclofenac sodium carrier

    Science.gov (United States)

    Lucena, Guilherme Nunes; Alves, Renata Carolina; Abuçafy, Marina Paiva; Chiavacci, Leila Aparecida; da Silva, Isabel Cristiane; Pavan, Fernando Rogério; Frem, Regina Célia Galvão

    2018-04-01

    Drug delivery systems produced with biocompatible components can be used to reduce adverse effects and improve therapy efficacy. Most of the carrier materials reported in the literature show poor drug loading and rapid release. However, porous hybrid solids, such as metal-organic frameworks, are well suited to serve as carriers for delivery and imaging applications. In this work, a luminescent and nontoxic porous Zn(II) coordination polymer with 4,4‧-biphenyl-dicarboxylic acid (BPDC) and adenine linkers (BioMOF-Zn) was synthesized by a solvothermal process and characterized by PXRD, TGA, SEM-FEG, and FTIR. Nitrogen adsorption measurements revealed the presence of micropores as well as mesopores in the framework after activation of the material. The blue-emitting BioMOF-Zn exhibited an outstanding loading capacity (1.72 g g-1) and satisfactory release capability (56% after two days) for diclofenac sodium.

  16. Expanded Organic Building Units for the Construction of Highly Porous Metal-Organic Frameworks

    NARCIS (Netherlands)

    Kong, G.Q.; Han, Z.D.; He, Y.; Qu, S.; Zhou, W.; Yildirim, T.; Krishna, R.; Zou, C.; Chen, B.; Wu, C.D.

    2013-01-01

    wo new organic building units that contain dicarboxylate sites for their self-assembly with paddlewheel [Cu2(CO2)4] units have been successfully developed to construct two isoreticular porous metal-organic frameworks (MOFs), ZJU-35 and ZJU-36, which have the same tbo topologies (Reticular Chemistry

  17. Structure and Mobility of Metal Clusters in MOFs: Au, Pd, and AuPd Clusters in MOF-74

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Walton, Krista S.; Sholl, David S.

    2012-01-01

    is just as important for nanocluster adsorption as open Zn or Mg metal sites. Using the large number of clusters generated by the GA, we developed a systematic method for predicting the mobility of adsorbed clusters. Through the investigation of diffusion paths a relationship between the cluster......Understanding the adsorption and mobility of metal–organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density...... functional theory (DFT) calculations with a genetic algorithm (GA) to reliably predict the structure of the adsorbed clusters. This approach allows comparison of hundreds of adsorbed configurations for each cluster. From the investigation of Au8, Pd8, and Au4Pd4 we find that the organic part of the MOF...

  18. Dual-Channel, Molecular-Sieving Core/Shell ZIF@MOF Architectures as Engineered Fillers in Hybrid Membranes for Highly Selective CO2 Separation.

    Science.gov (United States)

    Song, Zhuonan; Qiu, Fen; Zaia, Edmond W; Wang, Zhongying; Kunz, Martin; Guo, Jinghua; Brady, Michael; Mi, Baoxia; Urban, Jeffrey J

    2017-11-08

    A novel core/shell porous crystalline structure was prepared using a large pore metal organic framework (MOF, UiO-66-NH 2 , pore size, ∼ 0.6 nm) as core surrounded by a small pore zeolitic imidazolate framework (ZIF, ZIF-8, pore size, ∼ 0.4 nm) through a layer-by-layer deposition method and subsequently used as an engineered filler to construct hybrid polysulfone (PSF) membranes for CO 2 capture. Compared to traditional fillers utilizing only one type of porous material with rigid channels (either large or small), our custom designed core/shell fillers possess clear advantages via pore engineering: the large internal channels of the UiO-66-NH 2 MOFs create molecular highways to accelerate molecular transport through the membrane, while the thin shells with small pores (ZIF-8) or even smaller pores generated at the interface by the imperfect registry between the overlapping pores of ZIF and MOF enhance molecular sieving thus serving to distinguish slightly larger N 2 molecules (kinetic diameter, 0.364 nm) from smaller CO 2 molecules (kinetic diameter, 0.33 nm). The resultant core/shell ZIF@MOF and as-prepared hybrid PSF membranes were characterized by transmission electron microscopy, X-ray diffraction, wide-angle X-ray scattering, scanning electron microscopy, Fourier transform infrared, thermogravimetric analysis, differential scanning calorimetry, and contact angle tests. The dependence of the separation performance of the membranes on the MOF/ZIF ratio was also studied by varying the number of layers of ZIF coatings. The integrated PSF-ZIF@MOF hybrid membrane (40 wt % loading) with optimized ZIF coating cycles showed improved hydrophobicity and excellent CO 2 separation performance by simultaneously increasing CO 2 permeability (CO 2 permeability of 45.2 barrer, 710% higher than PSF membrane) and CO 2 /N 2 selectivity (CO 2 /N 2 selectivity of 39, 50% higher than PSF membrane), which is superior to most reported hybrid PSF membranes. The strategy of using

  19. Metal–organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2S

    KAUST Repository

    Belmabkhout, Youssef

    2017-01-06

    platform with the requisite hydrolytic stability, H2S stability, and exceptional gas selectivity for ROG and NG upgrading. Finally, the soc-MOF was deployed as a continuous film on a porous support, and its gas permeation properties as a membrane were evaluated.

  20. Porous carbon-coated ZnO nanoparticles derived from low carbon content formic acid-based Zn(II) metal-organic frameworks towards long cycle lithium-ion anode material

    International Nuclear Information System (INIS)

    Gao, Song; Fan, Ruiqing; Li, Bingjiang; Qiang, Liangsheng; Yang, Yulin

    2016-01-01

    Graphical abstract: The nanocomposites constructed from Zn-based MOFs exhibit low carbon content with super-high rate capability and long cycling life. - Highlights: • Novel ZnO@porous carbon matrix nanocomposites are constructed by pyrolysis of Zn-based MOFs. • The nanocomposites constructed with Zn-based MOFs show low carbon content. • The constructed nanocomposites exhibit high energy density, super-high rate capability and long cycling life. - Abstract: Single-C formic acid-based metal-organic frameworks (MOFs) are used to construct novel ZnO@porous carbon matrix nanocomposites by controlled pyrolysis. In the constructed nanocomposites, the porous carbon matrices act as a confined support to prevent agglomeration of the ZnO nanoparticles and create a rapid electron conductive network. Meanwhile, the well-defined, continuous porous structured MOFs provide a large specific surface area, which increases the contact of electrolyte-electrode and improves the penetration of electrolyte. Especially, the reasonable choice of formic acid-based MOFs construct the low carbon content composite, which contribute to the high energy density and long cycle life. The constructed nanocomposites show stable, ultrahigh rate lithium ion storage properties of 650 mAh g −1 at charge/discharge rate of 1 C even after 200 cycles.

  1. Porous carbons

    Indian Academy of Sciences (India)

    R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

    Abstract. Carbon in dense as well as porous solid form is used in a variety of applications. Activated porous carbons are made through pyrolysis and activation of carbonaceous natural as well as synthetic precursors. Pyrolysed woods replicate the structure of original wood but as such possess very low surface areas and ...

  2. Loading of Two Related Metal-Organic Frameworks (MOFs, [Cu2(bdc2(dabco] and [Cu2(ndc2(dabco], with Ferrocene

    Directory of Open Access Journals (Sweden)

    Wolfgang Wenzel

    2011-09-01

    Full Text Available We have studied the loading of two related, similar porous metal-organic frameworks (MOFs [Cu2(bdc2(dabco] (1, and [Cu2(ndc2(dabco] (2 with ferrocene by exposing bulk powder samples to the corresponding vapor. On the basis of powder X-ray diffraction data and molecular dynamics (MD calculations we propose that each pore can store one ferrocene molecule. Despite the rather pronounced similarity of the two MOFs a quite different behavior is observed, for 1 loading with ferrocene leads to an anisotropic 1% contraction, whereas for 2 no deformation is observed. Mössbauer spectroscopy studies reveal that the Fe oxidation level remains unchanged during the process. Time dependent studies reveal that the diffusion constant governing the loading from the gas-phase for 1 is approximately three times larger than the value for 2.

  3. Photocatalytic Performance of a Novel MOF/BiFeO3 Composite

    Directory of Open Access Journals (Sweden)

    Yunhui Si

    2017-10-01

    Full Text Available In this study, MOF/BiFeO3 composite (MOF, metal-organic framework has been synthesized successfully through a one-pot hydrothermal method. The MOF/BiFeO3 composite samples, pure MOF samples and BiFeO3 samples were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive spectroscopy (EDS, and by UV–vis spectrophotometry. The results and analysis reveal that MOF/BiFeO3 composite has better photocatalytic behavior for methylene blue (MB compared to pure MOF and pure BiFeO3. The enhancement of photocatalytic performance should be due to the introduction of MOF change the surface morphology of BiFeO3, which will increase the contact area with MB. This composing strategy of MOF/BiFeO3 composite may bring new insight into the designing of highly efficient photocatalysts.

  4. Direct observations of the MOF (UiO-66) structure by transmission electron microscopy

    KAUST Repository

    Zhu, Liangkui; Zhang, Daliang; Xue, Ming; Li, Huan; Qiu, Shilun

    2013-01-01

    As a demonstration of ab initio structure characterizations of nano metal organic framework (MOF) crystals by high resolution transmission electron microscopy (HRTEM) and electron diffraction tomography methods, a Zr-MOF (UiO-66) structure

  5. Strategies for the design of functional MOFs: addressing energy-intensive separations

    KAUST Repository

    Eddaoudi, Mohamed

    2017-01-01

    Metal Organic Frameworks (MOFs) are a promising class of crystalline solid-state materials amenable to tailoring their porosity and functionality towards various applications. MOF reticular chemistry using the Molecular Building Block (MBB) approach

  6. Synthesis and electrochemical properties of Fe_3O_4@MOF core-shell microspheres as an anode for lithium ion battery application

    International Nuclear Information System (INIS)

    Sun, Xuemin; Gao, Ge; Yan, Dongwei; Feng, Chuanqi

    2017-01-01

    Highlights: • Fe_3O_4 particles are encapsulated by HKUST-1 to form core-shell microspheres composite. • The composite exhibits outstanding electrochemical performances as a novel anode. • The typical approach can be used to prepare some novel electrode materials. - Abstract: The Fe_3O_4@MOF composite with a microspheric core and a porous metal-organic framework (MOF HKUST-1) shell has been successfully synthesized utilizing a versatile Layer-by-Layer (LBL) assembly method. The structure was identified by X-ray diffraction (XRD), and the morphology was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The Fe_3O_4@MOF composite exhibited outstanding electrochemical properties when it was used as an anode material for lithium ion batteries (LIBs). After 100 discharge-charge cycles at a current density of 100 mA g"−"1, the reversible capacity of Fe_3O_4@MOF could maintain ∼1002 mAh g"−"1, which was much higher than that of the bare Fe_3O_4 counterpart (696 mAh g"−"1). Moreover, load the current density as high as 2 A g"−"1 (after 70 cycles at the current density step increased from 0.1 to 2 A g"−"1), it still delivered a reversible capacity of ∼429 mAh g"−"1. The results demonstrate that the cycling stability of Fe_3O_4 as an anode could be significantly improved by coating Cu_3(1,3,5-benzenetricarboxylate)_2 (HKUST-1). This strategy may offer new route to prepare other composite materials using different particles and suitable Metal-organic frameworks (MOFs) for LIBs application.

  7. Synthesis and electrochemical properties of Fe{sub 3}O{sub 4}@MOF core-shell microspheres as an anode for lithium ion battery application

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Xuemin; Gao, Ge [Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for Synthesis and Applications of Organic Functional Molecules, Hubei University, Wuhan 430062 (China); Yan, Dongwei, E-mail: dwyan@iccas.ac.cn [Advance Technology & Materials Co. Ltd., China Iron & Steel Research Institute Group, No. 76 Xueyuan Nanlu, Haidian District, Beijing 100081 (China); Feng, Chuanqi, E-mail: cfeng@hubu.edu.cn [Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for Synthesis and Applications of Organic Functional Molecules, Hubei University, Wuhan 430062 (China)

    2017-05-31

    Highlights: • Fe{sub 3}O{sub 4} particles are encapsulated by HKUST-1 to form core-shell microspheres composite. • The composite exhibits outstanding electrochemical performances as a novel anode. • The typical approach can be used to prepare some novel electrode materials. - Abstract: The Fe{sub 3}O{sub 4}@MOF composite with a microspheric core and a porous metal-organic framework (MOF HKUST-1) shell has been successfully synthesized utilizing a versatile Layer-by-Layer (LBL) assembly method. The structure was identified by X-ray diffraction (XRD), and the morphology was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The Fe{sub 3}O{sub 4}@MOF composite exhibited outstanding electrochemical properties when it was used as an anode material for lithium ion batteries (LIBs). After 100 discharge-charge cycles at a current density of 100 mA g{sup −1}, the reversible capacity of Fe{sub 3}O{sub 4}@MOF could maintain ∼1002 mAh g{sup −1}, which was much higher than that of the bare Fe{sub 3}O{sub 4} counterpart (696 mAh g{sup −1}). Moreover, load the current density as high as 2 A g{sup −1} (after 70 cycles at the current density step increased from 0.1 to 2 A g{sup −1}), it still delivered a reversible capacity of ∼429 mAh g{sup −1}. The results demonstrate that the cycling stability of Fe{sub 3}O{sub 4} as an anode could be significantly improved by coating Cu{sub 3}(1,3,5-benzenetricarboxylate){sub 2} (HKUST-1). This strategy may offer new route to prepare other composite materials using different particles and suitable Metal-organic frameworks (MOFs) for LIBs application.

  8. Comparison of MOF-5- and Cr-MOF-derived carbons for hydrogen storage application

    CSIR Research Space (South Africa)

    Segakweng, T

    2015-11-01

    Full Text Available Nanoporous carbons which possess high surface areas and narrow pore size distributions have become one of the most important classes of porous materials with potential to be utilized for hydrogen storage. In recent times, several metal...

  9. Gas storage in porous metal-organic frameworks for clean energy applications.

    Science.gov (United States)

    Ma, Shengqian; Zhou, Hong-Cai

    2010-01-07

    Depletion of fossil oil deposits and the escalating threat of global warming have put clean energy research, which includes the search for clean energy carriers such as hydrogen and methane as well as the reduction of carbon dioxide emissions, on the urgent agenda. A significant technical challenge has been recognized as the development of a viable method to efficiently trap hydrogen, methane and carbon dioxide gas molecules in a confined space for various applications. This issue can be addressed by employing highly porous materials as storage media, and porous metal-organic frameworks (MOFs) which have exceptionally high surface areas as well as chemically-tunable structures are playing an unusual role in this respect. In this feature article we provide an overview of the current status of clean energy applications of porous MOFs, including hydrogen storage, methane storage and carbon dioxide capture.

  10. Magnetic MOF for AO7 Removal and Targeted Delivery

    Directory of Open Access Journals (Sweden)

    Xue-Qing Zhan

    2018-06-01

    Full Text Available Owing to their high surface area and porosity, metal-organic frameworks (MOFs have been gradually employed for a myriad of applications ranging from sensing, pollutant adsorption, and drug delivery to environmental remediation and catalysis. Magnetic nanoparticles-metal-organic frameworks (MMOFs hybrid materials can facilitate facile removal of MOFs from solutions. In this report, we report the synthesis of Fe3O4@UiO-66 by encapsulation and simulated the drug loading and release by studying the adsorption and release of AO7. Thus, we loaded these MMOFs with AO7 and found that they were able to trigger and control its release by simply applying an external magnetic field. The magnetic field heats the magnets in the MOF, which causes the load to burst from the framework.

  11. 2D MOF Nanoflake-Assembled Spherical Microstructures for Enhanced Supercapacitor and Electrocatalysis Performances

    Science.gov (United States)

    Xia, Huicong; Zhang, Jianan; Yang, Zhao; Guo, Shiyu; Guo, Shihui; Xu, Qun

    2017-10-01

    Metal-organic frameworks (MOFs) are of great interest as potential electrochemically active materials. However, few studies have been conducted into understanding whether control of the shape and components of MOFs can optimize their electrochemical performances due to the rational realization of their shapes. Component control of MOFs remains a significant challenge. Herein, we demonstrate a solvothermal method to realize nanostructure engineering of 2D nanoflake MOFs. The hollow structures with Ni/Co- and Ni-MOF (denoted as Ni/Co-MOF nanoflakes and Ni-MOF nanoflakes) were assembled for their electrochemical performance optimizations in supercapacitors and in the oxygen reduction reaction (ORR). As a result, the Ni/Co-MOF nanoflakes exhibited remarkably enhanced performance with a specific capacitance of 530.4 F g-1 at 0.5 A g-1 in 1 M LiOH aqueous solution, much higher than that of Ni-MOF (306.8 F g-1) and ZIF-67 (168.3 F g-1), a good rate capability, and a robust cycling performance with no capacity fading after 2000 cycles. Ni/Co-MOF nanoflakes also showed improved electrocatalytic performance for the ORR compared to Ni-MOF and ZIF-67. The present work highlights the significant role of tuning 2D nanoflake ensembles of Ni/Co-MOF in accelerating electron and charge transportation for optimizing energy storage and conversion devices. [Figure not available: see fulltext.

  12. Molecular simulations of MOF membranes for separation of ethane/ethene and ethane/methane mixtures.

    Science.gov (United States)

    Altintas, Cigdem; Keskin, Seda

    2017-11-11

    Metal organic framework (MOF) membranes have been widely investigated for gas separation applications. Several MOFs have been recently examined for selective separation of C 2 H 6 . Considering the large number of available MOFs, it is not possible to fabricate and test the C 2 H 6 separation performance of every single MOF membrane using purely experimental methods. In this study, we used molecular simulations to assess the membrane-based C 2 H 6 /C 2 H 4 and C 2 H 6 /CH 4 separation performances of 175 different MOF structures. This is the largest number of MOF membranes studied to date for C 2 H 6 separation. We computed adsorption selectivity, diffusion selectivity, membrane selectivity and gas permeability of MOFs for C 2 H 6 /C 2 H 4 and C 2 H 6 /CH 4 mixtures. Our results show that a significant number of MOF membranes are C 2 H 6 selective for C 2 H 6 /C 2 H 4 separation in contrast to traditional nanoporous materials. Selectivity and permeability of MOF membranes were compared with other membrane materials, such as polymers, zeolites, and carbon molecular sieves. Several MOFs were identified to exceed the upper bound established for polymeric membranes and many MOF membranes exhibited higher gas permeabilities than zeolites and carbon molecular sieves. Examining the structure-performance relations of MOF membranes revealed that MOFs with cavity diameters between 6 and 9 Å, porosities lower than 0.50, and surface areas between 500-1000 m 2 g -1 have high C 2 H 6 selectivities. The results of this study will be useful to guide the experiments to the most promising MOF membranes for efficient separation of C 2 H 6 and to accelerate the development of new MOFs with high C 2 H 6 selectivities.

  13. Peptide Assembly-Driven Metal-Organic Framework (MOF) Motors for Micro Electric Generator

    Science.gov (United States)

    Ikezoe, Yasuhiro; Fang, Justin; Wasik, Tomasz L.; Uemura, Takashi; Zheng, Yongtai; Kitagawa, Susumu

    2014-01-01

    Peptide-MOF motors, whose motions are driven by anisotropic surface gradients created via peptide self-assembly around nanopores of MOFs, can rotate microscopic rotors and magnet fast enough to generate electric power of 0.1 µW. To make the peptide-MOF generator recyclable, a new MOF is applied as a host motor engine, which has a more rigid framework with higher H2O affinity so that peptide release occurs more efficiently via guest exchange without the destruction of MOF. PMID:25418936

  14. Design and construction of porous metal-organic frameworks based on flexible BPH pillars

    Science.gov (United States)

    Hao, Xiang-Rong; Yang, Guang-sheng; Shao, Kui-Zhan; Su, Zhong-Min; Yuan, Gang; Wang, Xin-Long

    2013-02-01

    Three metal-organic frameworks (MOFs), [Co2(BPDC)2(4-BPH)·3DMF]n (1), [Cd2(BPDC)2(4-BPH)2·2DMF]n (2) and [Ni2(BDC)2(3-BPH)2 (H2O)·4DMF]n (3) (H2BPDC=biphenyl-4,4'-dicarboxylic acid, H2BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N'-dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has "single-pillared" MOF-5-like motif with inner cage diameters of up to 18.6 Å. Framework 2 has "double pillared" MOF-5-like motif with cage diameters of 19.2 Å while 3 has "double pillared" 8-connected framework with channel diameters of 11.0 Å. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework.

  15. Drosophila MOF regulates DIAP1 and induces apoptosis in a JNK dependent pathway.

    Science.gov (United States)

    Pushpavalli, Sreerangam N C V L; Sarkar, Arpita; Ramaiah, M Janaki; Koteswara Rao, G; Bag, Indira; Bhadra, Utpal; Pal-Bhadra, Manika

    2016-03-01

    Histone modulations have been implicated in various cellular and developmental processes where in Drosophila Mof is involved in acetylation of H4K16. Reduction in the size of larval imaginal discs is observed in the null mutants of mof with increased apoptosis. Deficiency involving Hid, Reaper and Grim [H99] alleviated mof (RNAi) induced apoptosis in the eye discs. mof (RNAi) induced apoptosis leads to activation of caspases which is suppressed by over expression of caspase inhibitors like P35 and Diap1 clearly depicting the role of caspases in programmed cell death. Also apoptosis induced by knockdown of mof is rescued by JNK mutants of bsk and tak1 indicating the role of JNK in mof (RNAi) induced apoptosis. The adult eye ablation phenotype produced by ectopic expression of Hid, Rpr and Grim, was restored by over expression of Mof. Accumulation of Mof at the Diap1 promoter 800 bp upstream of the transcription start site in wild type larvae is significantly higher (up to twofolds) compared to mof (1) mutants. This enrichment coincides with modification of histone H4K16Ac indicating an induction of direct transcriptional up regulation of Diap1 by Mof. Based on these results we propose that apoptosis triggered by mof (RNAi) proceeds through a caspase-dependent and JNK mediated pathway.

  16. Fluorometric sensing of Triton X-100 based organized media in water by a MOF

    Energy Technology Data Exchange (ETDEWEB)

    Dey, Biswajit, E-mail: bdeychem@gmail.com [Department of Chemistry, Visva-Bharati University, Santiniketan 731235 (India); Mondal, Ranjan Kumar; Dhibar, Subhendu [Department of Chemistry, Visva-Bharati University, Santiniketan 731235 (India); Chattopadhyay, Asoke Prasun [Department of Chemistry, University of Kalyani, Kalyani 741235 (India); Bhattacharya, Subhash Chandra [Department of Chemistry, Jadavpur University, Kolkata 700032 (India)

    2016-04-15

    The fluorescent property of the aqueous solution of a metal organic framework (MOF) of Mn(II), having a sedimentary rocks like microstructure in solid-state, has been investigated. The luminescent feature of the the aqueous solution of MOF has been employed for studying the interactions of MOF with different surfactants including neutral, cationic, and anionic types in water medium. Interestingly, the MOF can very selective sense Triton X-100 based micelle in water medium. During the sensing process the fluorescent monomer of the MOF gets accommodated at the palisade layer of Triton X-100 in water medium and this has also been justified by simple fluorescence spectral and FE-SEM microstructural analysis. Thus, a MOF of Mn(II) can act as a selective fluorescent sensor for Triton X-100 based organized medium in water. - Highlights: • Microstructural and crystallographic studies of a water-soluble MOF are performed. • The luminescent property of MOF in water medium is explored. • The interaction between Triton X-100 and the MOF in water medium is studied by fluorometric and microstructural analysis. • The MOF acts as a selective fluorometric sensor for the Triton X-100 based organized media in water. • The monomer of MOF presents in the Triton X-100 micelle in water.

  17. Fluorometric sensing of Triton X-100 based organized media in water by a MOF

    International Nuclear Information System (INIS)

    Dey, Biswajit; Mondal, Ranjan Kumar; Dhibar, Subhendu; Chattopadhyay, Asoke Prasun; Bhattacharya, Subhash Chandra

    2016-01-01

    The fluorescent property of the aqueous solution of a metal organic framework (MOF) of Mn(II), having a sedimentary rocks like microstructure in solid-state, has been investigated. The luminescent feature of the the aqueous solution of MOF has been employed for studying the interactions of MOF with different surfactants including neutral, cationic, and anionic types in water medium. Interestingly, the MOF can very selective sense Triton X-100 based micelle in water medium. During the sensing process the fluorescent monomer of the MOF gets accommodated at the palisade layer of Triton X-100 in water medium and this has also been justified by simple fluorescence spectral and FE-SEM microstructural analysis. Thus, a MOF of Mn(II) can act as a selective fluorescent sensor for Triton X-100 based organized medium in water. - Highlights: • Microstructural and crystallographic studies of a water-soluble MOF are performed. • The luminescent property of MOF in water medium is explored. • The interaction between Triton X-100 and the MOF in water medium is studied by fluorometric and microstructural analysis. • The MOF acts as a selective fluorometric sensor for the Triton X-100 based organized media in water. • The monomer of MOF presents in the Triton X-100 micelle in water.

  18. Unifying approach for model transformations in the MOF metamodeling architecture

    NARCIS (Netherlands)

    Ivanov, Ivan; van den Berg, Klaas

    2004-01-01

    In the Meta Object Facility (MOF) metamodeling architecture a number of model transformation scenarios can be identified. It could be expected that a metamodeling architecture will be accompanied by a transformation technology supporting the model transformation scenarios in a uniform way. Despite

  19. The relevance of metal organic frameworks (MOFs) in inorganic ...

    Indian Academy of Sciences (India)

    nal design.3 The assemblage of the many components in a MOF structure ... in a short span of time. This approach .... single-crystal to-single-crystal (SCSC) transformation ..... The exchanges through the carboxylate bridges linking the metal ...

  20. Porous Iron-Carboxylate Metal-Organic Framework: A Novel Bioplatform with Sustained Antibacterial Efficacy and Nontoxicity.

    Science.gov (United States)

    Lin, Sha; Liu, Xiangmei; Tan, Lei; Cui, Zhenduo; Yang, Xianjin; Yeung, Kelvin W K; Pan, Haobo; Wu, Shuilin

    2017-06-07

    Sustained drug release plays a critical role in targeting the therapy of local diseases such as bacterial infections. In the present work, porous iron-carboxylate metal-organic framework [MOF-53(Fe)] nanoparticles (NPs) were designed to entrap the vancomycin (Van) drugs. This system exhibited excellent chemical stability under acidic conditions (pH 7.4, 6.5, and 5.5) and much higher drug-loading capability because of the high porosity and large surface area of MOF NPs. The results showed that the drug-loading ratio of Van could reach 20 wt % and that the antibacterial ratio of the MOF-53(Fe)/Van system against Staphylococcus aureus could reach up to 90%. In addition, this MOF-53(Fe)/Van system exhibited excellent biocompatibility because of its chemical stability and sustained release of iron ions. Hence, these porous MOF NPs are a promising bioplatform not only for local therapy of bacterial infections but also for other biomedical therapies for tissue regeneration.

  1. A Metal Chelating Porous Polymeric Support: The Missing Link for a Defect-free Metal-Organic Framework Composite Membrane

    KAUST Repository

    Barankova, Eva

    2017-02-06

    Since the discovery of size-selective metal-organic frameworks (MOFs), researchers have tried to incorporate these materials into gas separation membranes. Impressive gas selectivities were found, but these MOF membranes were mostly made on inorganic supports, which are generally too bulky and expensive for industrial gas separation. Forming MOF layers on porous polymer supports is industrially attractive but technically challenging. Two features to overcome these problems are described: 1) a metal chelating support polymer to bind the MOF layer, and 2) control of MOF crystal growth by contra-diffusion, aiming at a very thin nanocrystalline MOF layer. Using a metal chelating polythiosemicarbazide (PTSC) support and adjusting the metal and organic ligand concentrations carefully, a very compact ZIF-8 (ZIF=zeolitic imidazolate framework) layer was produced that displayed interference colors because of its smooth surface and extreme thinness-within the range of visible light. High performances were measured in terms of hydrogen/propane (8350) and propylene/propane (150) selectivity.

  2. 2-periodic metal-organic frameworks (MOFs) as supermolecular building layers (SBLs) for making targeted 3-periodic MOFs

    KAUST Repository

    Eddaoudi, Mohamed; Eubank, Jarrod F.

    2015-01-01

    Embodiments of the present disclosure provide for chemical assemblies, multidimensional metal-organic frameworks (MOFs), supermolecular building layers (SBLs), inorganic molecular building blocks (MBBs), organic MBBs (designed ligands), methods of making each, and methods of using each, and the like. In an embodiment, the composition can be used in catalysis, separations, gas storage, and drug delivery.

  3. 2-periodic metal-organic frameworks (MOFs) as supermolecular building layers (SBLs) for making targeted 3-periodic MOFs

    KAUST Repository

    Eddaoudi, Mohamed

    2015-09-22

    Embodiments of the present disclosure provide for chemical assemblies, multidimensional metal-organic frameworks (MOFs), supermolecular building layers (SBLs), inorganic molecular building blocks (MBBs), organic MBBs (designed ligands), methods of making each, and methods of using each, and the like. In an embodiment, the composition can be used in catalysis, separations, gas storage, and drug delivery.

  4. Synthesis and CO2 adsorption study of modified MOF-5 with multi-wall carbon nanotubes and expandable graphite

    International Nuclear Information System (INIS)

    Ullah, Sami; Bustam, M. A.; Shariff, A. M.; Elkhalifah, Ali E. I.; Murshid, G.; Riaz, Nadia

    2014-01-01

    MOF-5 was synthesized by solvothermal method and its reactivation under anhydrous conditions. This research is conducted to investigate the effect of MOF-5 and MOF-5 modified with multi-wall carbon nanotubes (MWCNTs) and expandable graphite (EG) on the performance of CO 2 adsorption. The synthesized MOFs were characterized using Field emission scanning electron microscopy (FESEM) for surface morphology, Thermogravimetric analysis (TGA) for thermal stability, X-ray diffraction (XRD) for crystals plane, Brunauer-Emmet-Teller (BET) for surface area and CO 2 adsorption. The result had showed that the modified MOF-5 enhanced the CO 2 adsorption compared to the pure MOF-5. The increment in the CO 2 uptake capacities of MOF materials was attributed to the decrease in the pore size and enhancement of micropore volume of MOF-5 by multi-walled carbon nanotube and EG incorporation. The BET surface area of the synthesized MOF-5@MWCNTs is more than MOF-5. The CO 2 sorption capacities of MOF-5 and MOF-5@MWCNTs were observed to increase from 0.00008 to 0.00048 mol g-1 at 298 K and 1 bar. The modified MOF-5@MWCNTs resulted in the highest CO 2 adsorption followed by the modified MOF-5@ EG and lastly, MOF-5

  5. MOF-Derived ZnO Nanoparticles Covered by N-Doped Carbon Layers and Hybridized on Carbon Nanotubes for Lithium-Ion Battery Anodes.

    Science.gov (United States)

    Zhang, Hui; Wang, Yunsong; Zhao, Wenqi; Zou, Mingchu; Chen, Yijun; Yang, Liusi; Xu, Lu; Wu, Huaisheng; Cao, Anyuan

    2017-11-01

    Metal-organic frameworks (MOFs) have many promising applications in energy and environmental areas such as gas separation, catalysis, supercapacitors, and batteries; the key toward those applications is controlled pyrolysis which can tailor the porous structure, improve electrical conductivity, and expose metal ions in MOFs. Here, we present a systematic study on the structural evolution of zeolitic imidazolate frameworks hybridized on carbon nanotubes (CNTs) during the carbonization process. We show that a number of typical products can be obtained, depending on the annealing time, including (1) CNTs wrapped by relatively thick carbon layers, (2) CNTs grafted by ZnO nanoparticles which are covered by thin nitrogen-doped carbon layers, and (3) CNTs grafted by aggregated ZnO nanoparticles. We also investigated the electrochemical properties of those hybrid structures as freestanding membrane electrodes for lithium ion batteries, and the second one (CNT-supported ZnO covered by N-doped carbon) shows the best performance with a high specific capacity (850 mA h/g at a current density of 100 mA/g) and excellent cycling stability. Our results indicate that tailoring and optimizing the MOF-CNT hybrid structure is essential for developing high-performance energy storage systems.

  6. Insights on Capacitive Interdigitated Electrodes Coated with MOF Thin Films: Humidity and VOCs Sensing as a Case Study

    KAUST Repository

    Sapsanis, Christos

    2015-07-24

    A prototypical metal-organic framework (MOF), a 2D periodic porous structure based on the assembly of copper ions and benzene dicarboxylate (bdc) ligands (Cu(bdc)·xH2O), was grown successfully as a thin film on interdigitated electrodes (IDEs). IDEs have been used for achieving planar CMOS-compatible low-cost capacitive sensing structures for the detection of humidity and volatile organic compounds (VOCs). Accordingly, the resultant IDEs coated with the Cu(bdc)·xH2O thin film was evaluated, for the first time, as a capacitive sensor for gas sensing applications. A fully automated setup, using LabVIEW interfaces to experiment conduction and data acquisition, was developed in order to measure the associated gas sensing performance.

  7. Preparation of Cationic MOFs with Mobile Anions by Anion Stripping to Remove 2,4-D from Water

    Directory of Open Access Journals (Sweden)

    Tao Chen

    2017-07-01

    Full Text Available A cationic porous framework with mobile anions (MIL-101(Cr-Cl was easily and successfully synthesized by utilizing the stronger affinity of F− to Al3+ than Cr3+ in the charge-balanced framework of MIL-101(Cr. The structure, morphology and porosity of MIL-101(Cr-Cl were characterized. The obtained new materials retain the high surface area, good thermostability, and structure topology of MIL-101(Cr. With the mobile Cl− anion, MIL-101(Cr-Cl can be used as an ion-exchange material for anionic organic pollutions. In this work, 2,4-dichlorophenoxyacetic acid (2,4-D was used as a model to test the absorption performance of this new material. This new material exhibited improved adsorbability compared to that of the original metal-organic frameworks (MOFs. At the same time, this material also shows high anti-interference performance with changing solution pH.

  8. Thermal treatment induced transition from Zn3(OH)2(BDC)2 (MOF-69c) to Zn4O(BDC)3 (MOF-5)

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2013-01-01

    Full Text Available A simple thermal treatment induced transition from Zn3(OH)2(BDC)2 (MOF-69c) to Zn4O(BDC)3 (MOF-5) is reported. Phase crystallinity, pore characteristics and hydrogen storage capacities of the resulting crystals were investigated. It is shown...

  9. Synthesis and characterization of zinc adeninate metal-organic frameworks (bioMOF1) as potential anti-inflammatory drug delivery material

    Science.gov (United States)

    Usman, Ken Aldren S.; Buenviaje, Salvador C.; Razal, Joselito M.; Conato, Marlon T.; Payawan, Leon M.

    2018-05-01

    Zn8(ad)4(BPDC)6O•2Me2NH2 (bioMOF1), a porous metal-organic framework with zinc-adeninate secondary building units (SBUs), interconnected via biphenyldicarboxylate linkers, shows great potential for drug delivery applications due to its non-toxic and biocompatible components (zinc and adenine). In this study, bioMOF1 crystals synthesized solvothermally at 130°C for 24 hours, were characterized thoroughly and loaded with a known anti-inflammatory drug, nimesulide (NIM). The crystalline nature of the material was confirmed using powder x-ray diffraction crystallography (PXRD) along with morphology assessment using focused-ion beam/field emission scanning electron microscopy (FIB/FESEM). NIM was introduced to the crystals via solvent exchange accompanied with vigorous stirring and quantified using thermogravimetric analysis (TGA) with loading saturation of ˜30% attained during the 2nd to 3rd day of drug immersion. Drug release in phosphate buffer saline and in deionized water was done to monitor the kinetic of drug release in vitro. The drug release showed a controlled discharge profile which slowed down at the 24th and 48th hour of release. Drug release in buffer showed a faster release of drug from the material, which means that the presence of cations in the solution could further trigger the release of drug. Slow drug release was observed for all of the set-ups with maximum % drug release of 24.47%, and 16.14% for the bioMOF1 in buffer and bioMOF1 in water respectively for the span of 48 hours.

  10. MOFs for storage of natural gas in mobile applications

    Energy Technology Data Exchange (ETDEWEB)

    Marx, S.; Arnold, L.; Gaab, M.; Maurer, S.; Weickert, M.; Mueller, U. [BASF SE, Ludwigshafen (Germany); Gummaraju, R.; SantaMaria, M.; Wilson, K.; Garbotz, C.; Lynch, J. [BASF Corporation, Iselin, NJ (United States)

    2013-11-01

    Metal-organic frameworks (MOFs) are supposed to have high potential in gas storage, particular in the storage of natural gas (NG) for mobile applications. Due to the shale gas exploration and the cost advantage of natural gas on the North American market as well as the environmental benign behavior upon combustion, storage of gaseous fuels will become more important for future mobility. The main challenge with all gaseous fuels is the limited range of the fuel stored on board of a vehicle. Instead of increasing the pressure in the tank, which would lead to heavy tanks and high compression costs, MOFs might help to improve the energy density of the gas stored in a tank resulting in an increased driving distance or reduced space needed for the gas tanks. (orig.)

  11. Amorphous Red Phosphorus Embedded in Sandwiched Porous Carbon Enabling Superior Sodium Storage Performances.

    Science.gov (United States)

    Wu, Ying; Liu, Zheng; Zhong, Xiongwu; Cheng, Xiaolong; Fan, Zhuangjun; Yu, Yan

    2018-03-01

    The red P anode for sodium ion batteries has attracted great attention recently due to the high theoretical capacity, but the poor intrinsic electronic conductivity and large volume expansion restrain its widespread applications. Herein, the red P is successfully encapsulated into the cube shaped sandwich-like interconnected porous carbon building (denoted as P@C-GO/MOF-5) via the vaporization-condensation method. Superior cycling stability (high capacity retention of about 93% at 2 A g -1 after 100 cycles) and excellent rate performance (502 mAh g -1 at 10 A g -1 ) can be obtained for the P@C-GO/MOF-5 electrode. The superior electrochemical performance can be ascribed to the successful incorporation of red P into the unique carbon matrix with large surface area and pore volume, interconnected porous structure, excellent electronic conductivity and superior structural stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. S Sensors: Fumarate-Based fcu-MOF Thin Film Grown on a Capacitive Interdigitated Electrode

    KAUST Repository

    Yassine, Omar

    2016-10-31

    Herein we report the fabrication of an advanced sensor for the detection of hydrogen sulfide (H2S) at room temperature, using thin films of rare-earth metal (RE)-based metal-organic framework (MOF) with underlying fcu topology. This unique MOF-based sensor is made via the insitu growth of fumarate-based fcu-MOF (fum-fcu-MOF) thin film on a capacitive interdigitated electrode. The sensor showed a remarkable detection sensitivity for H2S at concentrations down to 100ppb, with the lower detection limit around 5ppb. The fum-fcu-MOF sensor exhibits a highly desirable detection selectivity towards H2S vs. CH4, NO2, H2, and C7H8 as well as an outstanding H2S sensing stability as compared to other reported MOFs. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Peptide assembly-driven metal-organic framework (MOF) motors for micro electric generators.

    Science.gov (United States)

    Ikezoe, Yasuhiro; Fang, Justin; Wasik, Tomasz L; Uemura, Takashi; Zheng, Yongtai; Kitagawa, Susumu; Matsui, Hiroshi

    2015-01-14

    Peptide-metal-organic framework (Pep-MOF) motors, whose motions are driven by anisotropic surface tension gradients created via peptide self-assembly around frameworks, can rotate microscopic rotors and magnets fast enough to generate an electric power of 0.1 μW. A new rigid Pep-MOF motor can be recycled by refilling the peptide fuel into the nanopores of the MOF. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Effects of Force Field Selection on the Computational Ranking of MOFs for CO2 Separations.

    Science.gov (United States)

    Dokur, Derya; Keskin, Seda

    2018-02-14

    Metal-organic frameworks (MOFs) have been considered as highly promising materials for adsorption-based CO 2 separations. The number of synthesized MOFs has been increasing very rapidly. High-throughput molecular simulations are very useful to screen large numbers of MOFs in order to identify the most promising adsorbents prior to extensive experimental studies. Results of molecular simulations depend on the force field used to define the interactions between gas molecules and MOFs. Choosing the appropriate force field for MOFs is essential to make reliable predictions about the materials' performance. In this work, we performed two sets of molecular simulations using the two widely used generic force fields, Dreiding and UFF, and obtained adsorption data of CO 2 /H 2 , CO 2 /N 2 , and CO 2 /CH 4 mixtures in 100 different MOF structures. Using this adsorption data, several adsorbent evaluation metrics including selectivity, working capacity, sorbent selection parameter, and percent regenerability were computed for each MOF. MOFs were then ranked based on these evaluation metrics, and top performing materials were identified. We then examined the sensitivity of the MOF rankings to the force field type. Our results showed that although there are significant quantitative differences between some adsorbent evaluation metrics computed using different force fields, rankings of the top MOF adsorbents for CO 2 separations are generally similar: 8, 8, and 9 out of the top 10 most selective MOFs were found to be identical in the ranking for CO 2 /H 2 , CO 2 /N 2 , and CO 2 /CH 4 separations using Dreiding and UFF. We finally suggested a force field factor depending on the energy parameters of atoms present in the MOFs to quantify the robustness of the simulation results to the force field selection. This easily computable factor will be highly useful to determine whether the results are sensitive to the force field type or not prior to performing computationally demanding

  15. Cationic and neutral copper(I) iodide cluster MOFs derived from ...

    Indian Academy of Sciences (India)

    Ashok Yadav

    These reactions yielded two new cluster-MOFs 2 and 3. While the ..... (a) Ortep plots at 50% ellipsoid probabilities for the cationic segments of 2; (b) View of the. 3D-MOF assembly of 2 ... identical emission colour of 2 at 298 K and 77 K under the. UV-lamp. .... C 2013 A multi-metal-cluster MOF with Cu4I4 and. Cu6S6 as ...

  16. Step-by-step seeding procedure for preparing HKUST-1 membrane on porous α-alumina support.

    Science.gov (United States)

    Nan, Jiangpu; Dong, Xueliang; Wang, Wenjin; Jin, Wanqin; Xu, Nanping

    2011-04-19

    Metal-organic framework (MOF) membranes have attracted considerable attention because of their striking advantages in small-molecule separation. The preparation of an integrated MOF membrane is still a major challenge. Depositing a uniform seed layer on a support for secondary growth is a main route to obtaining an integrated MOF membrane. A novel seeding method to prepare HKUST-1 (known as Cu(3)(btc)(2)) membranes on porous α-alumina supports is reported. The in situ production of the seed layer was realized in step-by-step fashion via the coordination of H(3)btc and Cu(2+) on an α-alumina support. The formation process of the seed layer was observed by ultraviolet-visible absorption spectroscopy and atomic force microscopy. An integrated HKUST-1 membrane could be synthesized by the secondary hydrothermal growth on the seeded support. The gas permeation performance of the membrane was evaluated. © 2011 American Chemical Society

  17. Zirconium-Based metal organic framework (Zr-MOF) material with high hydrostability for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2013-09-01

    Full Text Available Material-based solutions, such as metal organic frameworks (MOFs), continue to attract increasing attention as viable options for hydrogen storage applications. MOFs are widely regarded as promising materials for hydrogen storage due to their high...

  18. "One-for-All" Strategy in Fast Energy Storage: Production of Pillared MOF Nanorod-Templated Positive/Negative Electrodes for the Application of High-Performance Hybrid Supercapacitor.

    Science.gov (United States)

    Qu, Chong; Liang, Zibin; Jiao, Yang; Zhao, Bote; Zhu, Bingjun; Dang, Dai; Dai, Shuge; Chen, Yu; Zou, Ruqiang; Liu, Meilin

    2018-05-02

    Currently, metal-organic frameworks (MOFs) are intensively studied as active materials for electrochemical energy storage applications due to their tunable structure and exceptional porosities. Among them, water stable pillared MOFs with dual ligands have been reported to exhibit high supercapacitor (SC) performance. Herein, the "One-for-All" strategy is applied to synthesize both positive and negative electrodes of a hybrid SC (HSC) from a single pillared MOF. Specifically, Ni-DMOF-TM ([Ni(TMBDC)(DABCO) 0.5 ], TMBDC: 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid, DABCO: 1,4-diazabicyclo[2.2.2]-octane) nanorods are directly grown on carbon fiber paper (CFP) (denoted as CFP@TM-nanorods) with the help of triethylamine and function as the positive electrode of HSC under alkaline electrolyte. Meanwhile, calcinated N-doped hierarchical porous carbon nanorods (CFP@TM-NPCs) are produced and utilized as the negative counter-electrode from a one-step heat treatment of CFP@TM-nanorods. After assembling these two electrodes together to make a hybrid device, the TM-nanorods//TM-NPCs exhibit a wide voltage window of 1.5 V with a high sloping discharge plateau between 1-1.2 V, indicating its great potential for practical applications. This as-described "One-for-All" strategy is widely applicable and highly reproducible in producing MOF-based electrode materials for HSC applications, which shortens the gap between experimental synthesis and practical application of MOFs in fast energy storage. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Thermodynamic screening of metal-substituted MOFs for carbon capture.

    Science.gov (United States)

    Koh, Hyun Seung; Rana, Malay Kumar; Hwang, Jinhyung; Siegel, Donald J

    2013-04-07

    Metal-organic frameworks (MOFs) have emerged as promising materials for carbon capture applications due to their high CO2 capacities and tunable properties. Amongst the many possible MOFs, metal-substituted compounds based on M-DOBDC and M-HKUST-1 have demonstrated amongst the highest CO2 capacities at the low pressures typical of flue gasses. Here we explore the possibility for additional performance tuning of these compounds by computationally screening 36 metal-substituted variants (M = Be, Mg, Ca, Sr, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Sn, and Pb) with respect to their CO2 adsorption enthalpy, ΔH(T=300K). Supercell calculations based on van der Waals density functional theory (vdW-DF) yield enthalpies in good agreement with experimental measurements, out-performing semi-empirical (DFT-D2) and conventional (LDA & GGA) functionals. Our screening identifies 13 compounds having ΔH values within the targeted thermodynamic window -40 ≤ ΔH ≤ -75 kJ mol(-1): 8 are based on M-DODBC (M = Mg, Ca, Sr, Sc, Ti, V, Mo, and W), and 5 on M-HKUST-1 (M = Be, Mg, Ca, Sr and Sc). Variations in the electronic structure and the geometry of the structural building unit are examined and used to rationalize trends in CO2 affinity. In particular, the partial charge on the coordinatively unsaturated metal sites is found to correlate with ΔH, suggesting that this property may be used as a simple performance descriptor. The ability to rapidly distinguish promising MOFs from those that are "thermodynamic dead-ends" will be helpful in guiding synthesis efforts towards promising compounds.

  20. MOF Suppresses Replication Stress and Contributes to Resolution of Stalled Replication Forks.

    Science.gov (United States)

    Singh, Dharmendra Kumar; Pandita, Raj K; Singh, Mayank; Chakraborty, Sharmistha; Hambarde, Shashank; Ramnarain, Deepti; Charaka, Vijaya; Ahmed, Kazi Mokim; Hunt, Clayton R; Pandita, Tej K

    2018-03-15

    The human MOF (hMOF) protein belongs to the MYST family of histone acetyltransferases and plays a critical role in transcription and the DNA damage response. MOF is essential for cell proliferation; however, its role during replication and replicative stress is unknown. Here we demonstrate that cells depleted of MOF and under replicative stress induced by cisplatin, hydroxyurea, or camptothecin have reduced survival, a higher frequency of S-phase-specific chromosome damage, and increased R-loop formation. MOF depletion decreased replication fork speed and, when combined with replicative stress, also increased stalled replication forks as well as new origin firing. MOF interacted with PCNA, a key coordinator of replication and repair machinery at replication forks, and affected its ubiquitination and recruitment to the DNA damage site. Depletion of MOF, therefore, compromised the DNA damage repair response as evidenced by decreased Mre11, RPA70, Rad51, and PCNA focus formation, reduced DNA end resection, and decreased CHK1 phosphorylation in cells after exposure to hydroxyurea or cisplatin. These results support the argument that MOF plays an important role in suppressing replication stress induced by genotoxic agents at several stages during the DNA damage response. Copyright © 2018 American Society for Microbiology.

  1. Synthesis of highly monodispersed Ga-soc-MOF hollow cubes, colloidosomes and nanocomposites

    KAUST Repository

    Cai, Xuechao

    2016-07-06

    Ga-soc-MOF hollow cubes with an average size of about 300 nm were prepared by a polyvinylpyrrolidone (PVP) assisted acid etching process. Colloidosomes with sizes of around 5-10 mu m composed of single-layer tetrakaidecahedron building blocks (BBs) were synthesized for the first time. Au@Ga-soc-MOF nanocomposites with excellent catalytic properties were obtained.

  2. Synthesis of highly monodispersed Ga-soc-MOF hollow cubes, colloidosomes and nanocomposites

    KAUST Repository

    Cai, Xuechao; Deng, Xiaoran; Xie, Zhongxi; Bao, Shouxin; Shi, Yanshu; Lin, Jun; Pang, Maolin; Eddaoudi, Mohamed

    2016-01-01

    Ga-soc-MOF hollow cubes with an average size of about 300 nm were prepared by a polyvinylpyrrolidone (PVP) assisted acid etching process. Colloidosomes with sizes of around 5-10 mu m composed of single-layer tetrakaidecahedron building blocks (BBs) were synthesized for the first time. Au@Ga-soc-MOF nanocomposites with excellent catalytic properties were obtained.

  3. Computational Screening of MOF-Based Mixed Matrix Membranes for CO2/N2 Separations

    Directory of Open Access Journals (Sweden)

    Zeynep Sumer

    2016-01-01

    Full Text Available Atomically detailed simulations were used to examine CO2/N2 separation potential of metal organic framework- (MOF- based mixed matrix membranes (MMMs in this study. Gas permeability and selectivity of 700 new MMMs composed of 70 different MOFs and 10 different polymers were calculated for CO2/N2 separation. This is the largest number of MOF-based MMMs for which computational screening is done to date. Selecting the appropriate MOFs as filler particles in polymers resulted in MMMs that have higher CO2/N2 selectivities and higher CO2 permeabilities compared to pure polymer membranes. We showed that, for polymers that have low CO2 permeabilities but high CO2 selectivities, the identity of the MOF used as filler is not important. All MOFs enhanced the CO2 permeabilities of this type of polymers without changing their selectivities. Several MOF-based MMMs were identified to exceed the upper bound established for polymers. The methods we introduced in this study will create many opportunities to select the MOF/polymer combinations with useful properties for CO2 separation applications.

  4. Direct observations of the MOF (UiO-66) structure by transmission electron microscopy

    KAUST Repository

    Zhu, Liangkui

    2013-01-01

    As a demonstration of ab initio structure characterizations of nano metal organic framework (MOF) crystals by high resolution transmission electron microscopy (HRTEM) and electron diffraction tomography methods, a Zr-MOF (UiO-66) structure was determined and further confirmed by Rietveld refinements of powder X-ray diffraction. HRTEM gave direct imaging of the channels. © 2013 The Royal Society of Chemistry.

  5. Theoretical model estimation of guest diffusion in Metal-Organic Frameworks (MOFs)

    KAUST Repository

    Zheng, Bin; Huang, Kuo-Wei; Du, Huiling

    2015-01-01

    through gates, as this does not require specification of a force field for the MOF degrees of freedom. In the DFT calculation, we only considered one gate of MOFs each time; as this greatly reduced the computational cost. Based on the obtained energy

  6. Modulated synthesis of zirconium-metal organic framework (Zr-MOF) for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2014-01-01

    Full Text Available A modulated synthesis of Zr-metal organic framework (Zr-MOF) with improved ease of handling and decreased reaction time is reported to yield highly crystalline Zr-MOF with well-defined octahedral shaped crystals for practical hydrogen storage...

  7. Vapochromic behavior of MOF for selective sensing of ethanol

    Science.gov (United States)

    Wang, Zhenhua; Chen, Qianwang

    2018-04-01

    A MOF material, Co3[Co(CN)6]2 nanoparticles has been prepared for the effective detection of ethanol in vapor phase. When exposed to ethanol vapor, the material was changed from pink to purple, which is easily observed by naked eyes directly. We propose that the ethanol response is due to ethanol molecules entering the pores of the solid, where they alter the coordination geometry, leading to conversion of their Co centers from octahedral to tetrahedral coordination. Significantly, the change is reversible, which make the material reusable without subjecting to dynamic vacuum or slightly warming.

  8. Aerogels of 1D Coordination Polymers: From a Non-Porous Metal-Organic Crystal Structure to a Highly Porous Material

    Directory of Open Access Journals (Sweden)

    Adrián Angulo-Ibáñez

    2016-01-01

    Full Text Available The processing of an originally non-porous 1D coordination polymer as monolithic gel, xerogel and aerogel is reported as an alternative method to obtain novel metal-organic porous materials, conceptually different to conventional crystalline porous coordination polymer (PCPs or metal-organic frameworks (MOFs. Although the work herein reported is focused upon a particular kind of coordination polymer ([M(μ-ox(4-apy2]n, M: Co(II, Ni(II, the results are of interest in the field of porous materials and of MOFs, as the employed synthetic approach implies that any coordination polymer could be processable as a mesoporous material. The polymerization conditions were fixed to obtain stiff gels at the synthesis stage. Gels were dried at ambient pressure and at supercritical conditions to render well shaped monolithic xerogels and aerogels, respectively. The monolithic shape of the synthesis product is another remarkable result, as it does not require a post-processing or the use of additives or binders. The aerogels of the 1D coordination polymers are featured by exhibiting high pore volumes and diameters ranging in the mesoporous/macroporous regions which endow to these materials the ability to deal with large-sized molecules. The aerogel monoliths present markedly low densities (0.082–0.311 g·cm−3, an aspect of interest for applications that persecute light materials.

  9. Facile "modular assembly" for fast construction of a highly oriented crystalline MOF nanofilm.

    Science.gov (United States)

    Xu, Gang; Yamada, Teppei; Otsubo, Kazuya; Sakaida, Shun; Kitagawa, Hiroshi

    2012-10-10

    The preparation of crystalline, ordered thin films of metal-organic frameworks (MOFs) will be a critical process for MOF-based nanodevices in the future. MOF thin films with perfect orientation and excellent crystallinity were formed with novel nanosheet-structured components, Cu-TCPP [TCPP = 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin], by a new "modular assembly" strategy. The modular assembly process involves two steps: a "modularization" step is used to synthesize highly crystalline "modules" with a nanosized structure that can be conveniently assembled into a thin film in the following "assembly" step. With this method, MOF thin films can easily be set up on different substrates at very high speed with controllable thickness. This new approach also enabled us to prepare highly oriented crystalline thin films of MOFs that cannot be prepared in thin-film form by traditional techniques.

  10. Molecule@MOF: A New Class of Opto-electronic Materials.

    Energy Technology Data Exchange (ETDEWEB)

    Talin, Albert Alec [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Jones, Reese E. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Spataru, Dan Catalin [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Leonard, Francois Leonard [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); He, Yuping [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Foster, Michael E. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Allendorf, Mark D. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Stavila, Vitalie [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Hopkins, Patrick E. [Univ. of Virginia, Charlottesville, VA (United States)

    2017-09-01

    Metal organic frameworks (MOFs) are extended, nanoporous crystalline compounds consisting of metal ions interconnected by organic ligands. Their synthetic versatility suggest a disruptive class of opto - electronic materials with a high degree of electrical tunability and without the property - degrading disorder of organic conductors. In this project we determined the factors controlling charge and energy transport in MOFs and evaluated their potential for thermoelectric energy conversion. Two strategies for a chieving electronic conductivity in MOFs were explored: 1) using redox active 'guest' molecules introduced into the pores to dope the framework via charge - transfer coupling (Guest@MOF), 2) metal organic graphene analogs (MOGs) with dispersive band structur es arising from strong electronic overlap between the MOG metal ions and its coordinating linker groups. Inkjet deposition methods were developed to facilitate integration of the guest@MOF and MOG materials into practical devices.

  11. Design and construction of porous metal–organic frameworks based on flexible BPH pillars

    International Nuclear Information System (INIS)

    Hao, Xiang-Rong; Yang, Guang-sheng; Shao, Kui-Zhan; Su, Zhong-Min; Yuan, Gang; Wang, Xin-Long

    2013-01-01

    Three metal–organic frameworks (MOFs), [Co 2 (BPDC) 2 (4-BPH)·3DMF] n (1), [Cd 2 (BPDC) 2 (4-BPH) 2 ·2DMF] n (2) and [Ni 2 (BDC) 2 (3-BPH) 2 (H 2 O)·4DMF] n (3) (H 2 BPDC=biphenyl-4,4′-dicarboxylic acid, H 2 BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N′-dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has “single-pillared” MOF-5-like motif with inner cage diameters of up to 18.6 Å. Framework 2 has “double pillared” MOF-5-like motif with cage diameters of 19.2 Å while 3 has “double pillared” 8-connected framework with channel diameters of 11.0 Å. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework. - Graphical abstract: By insertion of flexible BPH pillars based on “pillaring” strategy, three metal–organic frameworks are obtained showing that the porous frameworks can be constructed in a much greater variety. Highlights: ► Frameworks 1 and 2 have MOF-5 like motif. ► The cube-like cages in 1 and 2 are quite large, comparable to the IRMOF-10. ► Framework 1 is “single-pillared” mode while 2 is “double-pillared” mode. ► PXRD and gas adsorption analysis show that 3 is a dynamic porous framework.

  12. Design and construction of porous metal-organic frameworks based on flexible BPH pillars

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Xiang-Rong; Yang, Guang-sheng; Shao, Kui-Zhan [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China); Su, Zhong-Min, E-mail: zmsu@nenu.edu.cn [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China); Yuan, Gang; Wang, Xin-Long [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China)

    2013-02-15

    Three metal-organic frameworks (MOFs), [Co{sub 2}(BPDC){sub 2}(4-BPH){center_dot}3DMF]{sub n} (1), [Cd{sub 2}(BPDC){sub 2}(4-BPH){sub 2}{center_dot}2DMF]{sub n} (2) and [Ni{sub 2}(BDC){sub 2}(3-BPH){sub 2} (H{sub 2}O){center_dot}4DMF]{sub n} (3) (H{sub 2}BPDC=biphenyl-4,4 Prime -dicarboxylic acid, H{sub 2}BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N Prime -dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has 'single-pillared' MOF-5-like motif with inner cage diameters of up to 18.6 A. Framework 2 has 'double pillared' MOF-5-like motif with cage diameters of 19.2 A while 3 has 'double pillared' 8-connected framework with channel diameters of 11.0 A. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework. - Graphical abstract: By insertion of flexible BPH pillars based on 'pillaring' strategy, three metal-organic frameworks are obtained showing that the porous frameworks can be constructed in a much greater variety. Highlights: Black-Right-Pointing-Pointer Frameworks 1 and 2 have MOF-5 like motif. Black-Right-Pointing-Pointer The cube-like cages in 1 and 2 are quite large, comparable to the IRMOF-10. Black-Right-Pointing-Pointer Framework 1 is 'single-pillared' mode while 2 is 'double-pillared' mode. Black-Right-Pointing-Pointer PXRD and gas adsorption analysis show that 3 is a dynamic porous framework.

  13. Drosophila MOF controls Checkpoint protein2 and regulates genomic stability during early embryogenesis.

    Science.gov (United States)

    Pushpavalli, Sreerangam N C V L; Sarkar, Arpita; Ramaiah, M Janaki; Chowdhury, Debabani Roy; Bhadra, Utpal; Pal-Bhadra, Manika

    2013-01-24

    In Drosophila embryos, checkpoints maintain genome stability by delaying cell cycle progression that allows time for damage repair or to complete DNA synthesis. Drosophila MOF, a member of MYST histone acetyl transferase is an essential component of male X hyperactivation process. Until recently its involvement in G2/M cell cycle arrest and defects in ionizing radiation induced DNA damage pathways was not well established. Drosophila MOF is highly expressed during early embryogenesis. In the present study we show that haplo-insufficiency of maternal MOF leads to spontaneous mitotic defects like mitotic asynchrony, mitotic catastrophe and chromatid bridges in the syncytial embryos. Such abnormal nuclei are eliminated and digested in the yolk tissues by nuclear fall out mechanism. MOF negatively regulates Drosophila checkpoint kinase 2 tumor suppressor homologue. In response to DNA damage the checkpoint gene Chk2 (Drosophila mnk) is activated in the mof mutants, there by causing centrosomal inactivation suggesting its role in response to genotoxic stress. A drastic decrease in the fall out nuclei in the syncytial embryos derived from mof¹/+; mnkp⁶/+ females further confirms the role of DNA damage response gene Chk2 to ensure the removal of abnormal nuclei from the embryonic precursor pool and maintain genome stability. The fact that mof mutants undergo DNA damage has been further elucidated by the increased number of single and double stranded DNA breaks. mof mutants exhibited genomic instability as evidenced by the occurance of frequent mitotic bridges in anaphase, asynchronous nuclear divisions, disruption of cytoskeleton, inactivation of centrosomes finally leading to DNA damage. Our findings are consistent to what has been reported earlier in mammals that; reduced levels of MOF resulted in increased genomic instability while total loss resulted in lethality. The study can be further extended using Drosophila as model system and carry out the interaction of MOF

  14. Drosophila MOF controls Checkpoint protein2 and regulates genomic stability during early embryogenesis

    Directory of Open Access Journals (Sweden)

    Pushpavalli Sreerangam NCVL

    2013-01-01

    Full Text Available Abstract Background In Drosophila embryos, checkpoints maintain genome stability by delaying cell cycle progression that allows time for damage repair or to complete DNA synthesis. Drosophila MOF, a member of MYST histone acetyl transferase is an essential component of male X hyperactivation process. Until recently its involvement in G2/M cell cycle arrest and defects in ionizing radiation induced DNA damage pathways was not well established. Results Drosophila MOF is highly expressed during early embryogenesis. In the present study we show that haplo-insufficiency of maternal MOF leads to spontaneous mitotic defects like mitotic asynchrony, mitotic catastrophe and chromatid bridges in the syncytial embryos. Such abnormal nuclei are eliminated and digested in the yolk tissues by nuclear fall out mechanism. MOF negatively regulates Drosophila checkpoint kinase 2 tumor suppressor homologue. In response to DNA damage the checkpoint gene Chk2 (Drosophila mnk is activated in the mof mutants, there by causing centrosomal inactivation suggesting its role in response to genotoxic stress. A drastic decrease in the fall out nuclei in the syncytial embryos derived from mof1/+; mnkp6/+ females further confirms the role of DNA damage response gene Chk2 to ensure the removal of abnormal nuclei from the embryonic precursor pool and maintain genome stability. The fact that mof mutants undergo DNA damage has been further elucidated by the increased number of single and double stranded DNA breaks. Conclusion mof mutants exhibited genomic instability as evidenced by the occurance of frequent mitotic bridges in anaphase, asynchronous nuclear divisions, disruption of cytoskeleton, inactivation of centrosomes finally leading to DNA damage. Our findings are consistent to what has been reported earlier in mammals that; reduced levels of MOF resulted in increased genomic instability while total loss resulted in lethality. The study can be further extended using

  15. A luminescent Lanthanide-free MOF nanohybrid for highly sensitive ratiometric temperature sensing in physiological range.

    Science.gov (United States)

    Zhou, You; Zhang, Denan; Zeng, Jin; Gan, Ning; Cuan, Jing

    2018-05-01

    Luminescent MOF materials with tunable emissions and energy/charge transfer processes have been extensively explored as ratiometric temperature sensors. However, most of the ratiometric MOF thermometers reported thus far are based on the MOFs containing photoactive lanthanides, which are potentially facing cost issue and serious supply shortage. Here, we present a ratiometric luminescent thermometer based on a dual-emitting lanthanide-free MOF hybrid, which is developed by encapsulation of a fluorescent dye into a robust nanocrystalline zirconium-based MOF through a one-pot synthesis approach. The structure and morphology of the hybrid product was characterized by Powder X-ray diffraction (PXRD), N 2 adsorption-desorption measurement and Scanning electron microscopy (SEM). The pore confinement effect well isolates the guest dye molecules and therefore suppresses the nonradiative energy transfer process between dye molecules. The incorporated dye emission is mainly sensitized by the organic linkers within MOF through fluorescence resonance energy transfer. The ratiometric luminescence of the MOF hybrid shows a significant response to temperature due to the thermal-related back energy transfer process from dye molecules and organic linkers, thus can be exploited for self-calibrated temperature sensing. The maximum thermometric sensitivity is 1.19% °C -1 in the physiological temperature range, which is among the highest for the ratiomtric MOF thermometers that operating in 25-45°C. The temperature resolution is better than 0.1°C over the entire operative range (20-60°C). By integrating the advantages of excellent stability, nanoscale nature, and high sensitivity and precision in the physiological temperature range, this dye@MOF hybrid might have potential application in biomedical diagnosis. What' more, this work has expanded the possibility of non-lanthanide luminescent MOF materials for the development of ratiometric temperature sensors. Copyright © 2018

  16. Synthesis and characterization of polymorphs of photoluminescent Eu(III)-(2,5-furandicarboxylic acid, oxalic acid) MOFs

    International Nuclear Information System (INIS)

    Shi, Fa-Nian; Ananias, Duarte; Yang, Ting-Hai; Rocha, João

    2013-01-01

    A novel metal organic framework (MOF) formulated as [Eu(H 2 O) 2 (fdc)(ox) 0.5 ·(H 2 O)] n (1, fdc 2− =2,5-furandicarboxylate, ox 2− =oxalate), was hydrothermally synthesized via in situ ox 2− generation from the partial decomposition of the fdc 2− ligand. This material crystallizes in the monoclinic space group C2/c, unit cell parameters of 1: a=16.7570(10), b=10.5708(7), c=13.5348(14) Å, β=116.917(2)° (Z=8), and exhibits a three-dimensional (3D)-porous framework, with guest water molecules residing in the channel linking all other ligands (H 2 O, ox 2− and fdc 2− ) via hydrogen bonding interactions. Compound 2 is a polymorph of 1 crystallizing in monoclinic P21/c space group. The photoluminescence properties of 1 and 2 were studied at room temperature. The spectra show the typical Eu 3+ red emission and the differences observed reflects the slightly different structures of these polymorphs. - Graphical abstract: Exploring metal organic framework polymorphism in the system Eu(H 2 O) 2 (fdc)(ox) 0.5 ·(H 2 O)] n (fdc 2− =2,5-furandicarboxylate, ox 2− =oxalate) for tuning light emission. Display Omitted - Highlights: • Synthesis of Eu(III)-(2,5-furandicarboxylic acid, oxalic acid) MOF polymorphs. • Detailed single-crystal study of polymorphs including hydrogen-bonding networks. • Photoluminescence spectroscopy show subtle differences light emission properties

  17. Co@Carbon and Co 3 O4@Carbon nanocomposites derived from a single MOF for supercapacitors.

    Science.gov (United States)

    Dai, Engao; Xu, Jiao; Qiu, Junjie; Liu, Shucheng; Chen, Ping; Liu, Yi

    2017-10-03

    Developing a composite electrode containing both carbon and transition metal/metal oxide as the supercapacitor electrode can combine the merits and mitigate the shortcomings of both the components. Herein, we report a simple strategy to prepare the hybrid nanostructure of Co@Carbon and Co 3 O 4 @Carbon by pyrolysis a single MOFs precursor. Co-based MOFs (Co-BDC) nanosheets with morphology of regular parallelogram slice have been prepared by a bottom-up synthesis strategy. One-step pyrolysis of Co-BDC, produces a porous carbon layer incorporating well-dispersed Co and Co 3 O 4 nanoparticles. The as-prepared cobalt-carbon composites exhibit the thin layer morphology and large specific surface area with hierarchical porosity. These features significantly improve the ion-accessible surface area for charge storage and shorten the ion transport length in thin dimension, thus contributing to a high specific capacitance. Improved capacitance performance was successfully realized for the asymmetric supercapacitors (ASCs) (Co@Carbon//Co 3 O 4 @Carbon), better than those of the symmetric supercapacitors (SSCs) based on Co@Carbon and Co 3 O 4 @Carbon materials (i.e., Co@Carbon//Co@Carbon and Co 3 O 4 @Carbon//Co 3 O 4 @Carbon). The working voltage of the ASCs can be extended to 1.5 V and show a remarkable high power capability in aqueous electrolyte. This work provides a controllable strategy for nanostructured carbon-metal and carbon-metal oxide composite electrodes from a single precursor.

  18. Hydrogen adsorption strength and sites in the metal organic framework MOF5: Comparing experiment and model calculations

    Science.gov (United States)

    Mulder, F. M.; Dingemans, T. J.; Schimmel, H. G.; Ramirez-Cuesta, A. J.; Kearley, G. J.

    2008-07-01

    Hydrogen adsorption in porous, high surface area, and stable metal organic frameworks (MOF's) appears a novel route towards hydrogen storage materials [N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O'Keeffe, O.M. Yaghi, Science 300 (2003) 1127; J.L.C. Rowsell, A.R. Millward, K. Sung Park, O.M. Yaghi, J. Am. Chem. Soc. 126 (2004) 5666; G. Ferey, M. Latroche, C. Serre, F. Millange, T. Loiseau, A. Percheron-Guegan, Chem. Commun. (2003) 2976; T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille, G. Férey, Chem. Eur. J. 10 (2004) 1373]. A prerequisite for such materials is sufficient adsorption interaction strength for hydrogen adsorbed on the adsorption sites of the material because this facilitates successful operation under moderate temperature and pressure conditions. Here we report detailed information on the geometry of the hydrogen adsorption sites, based on the analysis of inelastic neutron spectroscopy (INS). The adsorption energies for the metal organic framework MOF5 equal about 800 K for part of the different sites, which is significantly higher than for nanoporous carbon materials (˜550 K) [H.G. Schimmel, G.J. Kearley, M.G. Nijkamp, C.T. Visser, K.P. de Jong, F.M. Mulder, Chem. Eur. J. 9 (2003) 4764], and is in agreement with what is found in first principles calculations [T. Sagara, J. Klassen, E. Ganz, J. Chem. Phys. 121 (2004) 12543; F.M. Mulder, T.J. Dingemans, M. Wagemaker, G.J. Kearley, Chem. Phys. 317 (2005) 113]. Assignments of the INS spectra is realized using comparison with independently published model calculations [F.M. Mulder, T.J. Dingemans, M. Wagemaker, G.J. Kearley, Chem. Phys. 317 (2005) 113] and structural data [T. Yildirim, M.R. Hartman, Phys. Rev. Lett. 95 (2005) 215504].

  19. Forming MOFs into spheres by use of molecular gastronomy methods.

    Science.gov (United States)

    Spjelkavik, Aud I; Aarti; Divekar, Swapnil; Didriksen, Terje; Blom, Richard

    2014-07-14

    A novel method utilizing hydrocolloids to prepare nicely shaped spheres of metal-organic frameworks (MOFs) has been developed. Microcrystalline CPO-27-Ni particles are dispersed in either alginate or chitosan solutions, which are added dropwise to solutions containing, respectively, either divalent group 2 cations or base that act as gelling agents. Well-shaped spheres are immediately formed, which can be dried into spheres containing mainly MOF (>95 wt %). The spheronizing procedures have been optimized with respect to maximum specific surface area, shape, and particle density of the final sphere. At optimal conditions, well-shaped 2.5-3.5 mm diameter CPO-27-Ni spheres with weight-specific surface areas <10 % lower than the nonformulated CPO-27-Ni precursor, and having sphere densities in the range 0.8 to 0.9 g cm(-3) and particle crushing strengths above 20 N, can be obtained. The spheres are well suited for use in fixed-bed catalytic or adsorption processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Reduced Magnetism in Core–Shell Magnetite@MOF Composites

    Energy Technology Data Exchange (ETDEWEB)

    Elsaidi, Sameh K.; Sinnwell, Michael A.; Banerjee, Debasis; Devaraj, Arun; Kukkadapu, Ravi K.; Droubay, Timothy C.; Nie, Zimin; Kovarik, Libor; Murugesan, Vijayakumar; Manandhar, Sandeep; Nandasiri, Manjula I.; McGrail, Bernard P.; Thallapally, Praveen K.

    2017-10-17

    Rare-earth elements (REEs) have significant commercial and military uses.1-3 However, REE extraction through conventional mining processes is expensive and feasible at only a few locations worldwide. Alternative methods are needed to produce REEs from more geographically disperse resources and in a cost effective, environmental friendly manner.4,5 Among various sources, geothermal brine, used for generating geothermal energy can possess attractive concentrations (ppb to ppm level) of REEs along with other dissolved metal ions.6 A system that can selectively trap the REEs using an existing geothermal power plant infrastructure would be an attractive additional revenue stream for the plant operator that could accelerate the development and deployment of geothermal plants in the United States and rest of the world.7,8 Here, we demonstrate a magnetic core-shell approach that can effectively extract REEs in their ionic form from aqueous solution with up to 99.99% removal efficiency. The shell, composed of thermally and chemically stable functionalized metal-organic framework (MOF), is grown over a synthesized Fe3O4 magnetic core. Magnetic susceptibility of the particles was found to decline significantly after in situ growth of a MOF shell, which resulted from oxidation of Fe2+ species of the magnetite (Fe3O4) to Fe3+ species (maghemite). The core-shell particles can be completely removed from the mixture under an applied magnetic field, offering a practical, economic, and efficient REE-removal process.

  1. Understanding the H 2 Sorption Trends in the M-MOF-74 Series (M = Mg, Ni, Co, Zn)

    KAUST Repository

    Pham, Tony; Forrest, Katherine A.; Banerjee, Rahul; Orcajo, Gisela; Eckert, Juergen; Space, Brian

    2015-01-01

    © 2014 American Chemical Society. Electronic structure calculations and simulations of H2 sorption were performed in four members of the M-MOF-74 series: Mg-MOF-74, Ni-MOF-74, Co-MOF-74, and Zn-MOF-74. Notable differences were observed in the partial charge and polarizability of the metal ions derived from the electronic structure calculations. The modeling parameters obtained from the electronic structure calculations were found to influence certain features in the experimentally observed H2 sorption trends in the M-MOF-74 series. The simulations were performed with the inclusion of explicit many-body polarization, which was required to reproduce the experimental H2 sorption observables (i.e., sorption isotherms and isosteric heats of adsorption (Qst)) and the H2-metal interaction in all four MOFs using classical molecular simulation. Consistent with experimental measurements, the simulations captured the following trend for the H2-metal interaction strength: Ni-MOF-74 > Co-MOF-74 > Mg-MOF-74 > Zn-MOF-74. The calculations revealed that stronger H2-metal interactions within the M-MOF-74 series corresponded to shorter H2-metal distances and higher induced dipoles on the metal-sorbed H2 molecules. In addition, it was observed that there was a strong correlation between the H2-metal interaction and the polarization contribution. Although Mg-MOF-74 has the highest calculated partial charge for the metal ion within the series, the Mg2+ ion has a very low polarizability compared to the other M2+ ions; this explains why the H2-metal interaction in this MOF is weaker compared to those for Ni-MOF-74 and Co-MOF-74. The sterics interactions, reflected in the crystal structure for all four MOFs, also played a role for the observed H2 sorption trends. Zn-MOF-74 has the lowest H2 uptakes and Qst within the series due to an unfavorable geometric environment for the Zn2+ ions within the ZnO5 clusters. Lastly, the two-dimensional quantum rotational levels were calculated for the H

  2. Understanding the H 2 Sorption Trends in the M-MOF-74 Series (M = Mg, Ni, Co, Zn)

    KAUST Repository

    Pham, Tony

    2015-01-15

    © 2014 American Chemical Society. Electronic structure calculations and simulations of H2 sorption were performed in four members of the M-MOF-74 series: Mg-MOF-74, Ni-MOF-74, Co-MOF-74, and Zn-MOF-74. Notable differences were observed in the partial charge and polarizability of the metal ions derived from the electronic structure calculations. The modeling parameters obtained from the electronic structure calculations were found to influence certain features in the experimentally observed H2 sorption trends in the M-MOF-74 series. The simulations were performed with the inclusion of explicit many-body polarization, which was required to reproduce the experimental H2 sorption observables (i.e., sorption isotherms and isosteric heats of adsorption (Qst)) and the H2-metal interaction in all four MOFs using classical molecular simulation. Consistent with experimental measurements, the simulations captured the following trend for the H2-metal interaction strength: Ni-MOF-74 > Co-MOF-74 > Mg-MOF-74 > Zn-MOF-74. The calculations revealed that stronger H2-metal interactions within the M-MOF-74 series corresponded to shorter H2-metal distances and higher induced dipoles on the metal-sorbed H2 molecules. In addition, it was observed that there was a strong correlation between the H2-metal interaction and the polarization contribution. Although Mg-MOF-74 has the highest calculated partial charge for the metal ion within the series, the Mg2+ ion has a very low polarizability compared to the other M2+ ions; this explains why the H2-metal interaction in this MOF is weaker compared to those for Ni-MOF-74 and Co-MOF-74. The sterics interactions, reflected in the crystal structure for all four MOFs, also played a role for the observed H2 sorption trends. Zn-MOF-74 has the lowest H2 uptakes and Qst within the series due to an unfavorable geometric environment for the Zn2+ ions within the ZnO5 clusters. Lastly, the two-dimensional quantum rotational levels were calculated for the H

  3. Strategies for the design of functional MOFs: addressing energy-intensive separations

    KAUST Repository

    Eddaoudi, Mohamed

    2017-12-19

    Metal Organic Frameworks (MOFs) are a promising class of crystalline solid-state materials amenable to tailoring their porosity and functionality towards various applications. MOF reticular chemistry using the Molecular Building Block (MBB) approach offers potential to construct robust made-to-order MOFs, where desired structural and geometrical information are incorporated into the building blocks prior to the assembly process. We will discuss two recently implemented conceptual approaches facilitating the design and deliberate construction of metal–organic frameworks (MOFs), namely supermolecular building block (SBB) and supermolecular building layer (SBL) approaches. Additionally, the concept of net-coded building units (net-cBUs), where precise embedded geometrical information codes uniquely and matchlessly a selected net, as a compelling route for the rational design of MOFs will be presented. Our progress in the development of functional metal-organic frameworks (MOFs) to address some energy-intensive separations will be discussed. Namely, the successful practice of reticular chemistry affording the fabrication of various stable MOFs with controlled pore-aperture size and allowing effective separation of various gas or vapors pairs.

  4. Ultra-Fast Degradation of Chemical Warfare Agents Using MOF-Nanofiber Kebabs.

    Science.gov (United States)

    Zhao, Junjie; Lee, Dennis T; Yaga, Robert W; Hall, Morgan G; Barton, Heather F; Woodward, Ian R; Oldham, Christopher J; Walls, Howard J; Peterson, Gregory W; Parsons, Gregory N

    2016-10-10

    The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal-organic frame-works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF-nanofiber kebab structures for fast degradation of CWAs. We found TiO 2 coatings deposited via atomic layer deposition (ALD) onto polyamide-6 nanofibers enable the formation of conformal Zr-based MOF thin films including UiO-66, UiO-66-NH 2 , and UiO-67. Cross-sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF-functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half-lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF-nanofiber textile composites capable of ultra-fast degradation of CWAs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Chemically intuited, large-scale screening of MOFs by machine learning techniques

    Science.gov (United States)

    Borboudakis, Giorgos; Stergiannakos, Taxiarchis; Frysali, Maria; Klontzas, Emmanuel; Tsamardinos, Ioannis; Froudakis, George E.

    2017-10-01

    A novel computational methodology for large-scale screening of MOFs is applied to gas storage with the use of machine learning technologies. This approach is a promising trade-off between the accuracy of ab initio methods and the speed of classical approaches, strategically combined with chemical intuition. The results demonstrate that the chemical properties of MOFs are indeed predictable (stochastically, not deterministically) using machine learning methods and automated analysis protocols, with the accuracy of predictions increasing with sample size. Our initial results indicate that this methodology is promising to apply not only to gas storage in MOFs but in many other material science projects.

  6. A database for CO2 Separation Performances of MOFs based on Computational Materials Screening.

    Science.gov (United States)

    Altintas, Cigdem; Avci, Gokay; Daglar, Hilal; Nemati Vesali Azar, Ayda; Velioglu, Sadiye; Erucar, Ilknur; Keskin, Seda

    2018-05-03

    Metal organic frameworks (MOFs) have been considered as great candidates for CO2 capture. Considering the very large number of available MOFs, high-throughput computational screening plays a critical role in identifying the top performing materials for target applications in a time-effective manner. In this work, we used molecular simulations to screen the most recent and complete MOF database for identifying the most promising materials for CO2 separation from flue gas (CO2/N2) and landfill gas (CO2/CH4) under realistic operating conditions. We first validated our approach by comparing the results of our molecular simulations for the CO2 uptakes, CO2/N2 and CO2/CH4 selectivities of various types of MOFs with the available experimental data. We then computed binary CO2/N2 and CO2/CH4 mixture adsorption data for the entire MOF database and used these results to calculate several adsorbent selection metrics such as selectivity, working capacity, adsorbent performance score, regenerability, and separation potential. MOFs were ranked based on the combination of these metrics and the top performing MOF adsorbents that can achieve CO2/N2 and CO2/CH4 separations with high performance were identified. Molecular simulations for the adsorption of a ternary CO2/N2/CH4 mixture were performed for these top materials in order to provide a more realistic performance assessment of MOF adsorbents. Structure-performance analysis showed that MOFs with ΔQ>30 kJ/mol, 3.8 A≤PLD≤5 A, 5 A≤LCD≤7.5 A, 0.5≤ϕ≤0.75, SA≤1,000 m2/g, ρ>1 g/cm 3 are the best candidates for selective separation of CO2 from flue gas and landfill gas. This information will be very useful to design novel MOFs with the desired structural features that can lead to high CO2 separation potentials. Finally, an online, freely accessible database https://cosmoserc.ku.edu.tr was established, for the first time in the literature, which reports all computed adsorbent metrics of 3,816 MOFs for CO2/N2, CO2/CH4

  7. Revisiting the Aluminum Trimesate-based MOF (MIL-96): from Structure Determination to the Processing of Mixed Matrix Membranes for CO2 Capture.

    KAUST Repository

    Benzaqui, Marvin; S. Pillai, Renjith; Sabetghadam, Anahid; Benoit, Virginie; Normand, Pé rine; Marrot, Jerome; Menguy, Nicolas; Montero, David; Shepard, William; Tissot, Antoine; Martineau-Corcos, Charlotte; Sicard, Clé mence; Mihaylov, Mihail; Carn, Florent; Beurroeis, Isabelle; Llewellyn, Philip L.; De Weireld, Guy; Hadjiivanov, Konstantin; Gascon, Jorge; Kapteijn, Freek; Maurin, Guillaume; Steunou, Nathalie; Serre, Christian

    2017-01-01

    A microporous Al trimesate-based metal-organic framework (MOF), denoted MIL-96-(Al), was selected as a porous hybrid filler for the processing of mixed matrix membranes (MMMs) for CO2/N-2 postcombustion separation. First, the structural model of MIL-96-(Al) initially reported was revisited using a combination of synchrotron-based single-crystal X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory (DFT) calculations. In a second step, pure MIL-96-(Al) crystals differing by their size and aspect ratio, including anisotropic hexagonal platelets and nanoparticles of about 70 nm in diameter, were prepared. Then, a combination of in situ IR spectroscopy, single-gas, and CO2/N-2 coadsorption experiments, calorimetry, and molecular simulations revealed that MIL-96-(Al) nanoparticles show a relatively high CO2 affinity over N-2 owing to strong interactions between CO2 molecules and several adsorption sites such as Al3+ Lewis centers, coordinated water, and hydroxyl groups. Finally, the high compatibility between MIL-96-(Al) nanoparticles and the 6FDA-DAM polymer allowed the processing of homogeneous and defect-free MMMs with a high MOF loading (up to 25 wt %) that outperform pure polymer membranes for CO2/N-2 separation.

  8. Preparation of mesoporous Cs-POM@MOF-199@MCM-41 under two different synthetic methods for a highly oxidesulfurization of dibenzothiophene.

    Science.gov (United States)

    Li, Si-Wen; Li, Jia-Rong; Jin, Qi-Ping; Yang, Zhi; Zhang, Rong-Lan; Gao, Rui-Min; Zhao, Jian-She

    2017-09-05

    Two different synthetic methods, the direct method and the substitution method, were used to synthesize the Cs-POM@MOF-199@MCM-41 (Cs-PMM), in which the modified heteropolyacid with cesium salt has been encapsulated into the pores with the mixture of MOF and MCM-41. The structural properties of the as-prepared catalysts were characterized using various analytical techniques: powder X-ray diffraction, FT-IR, SEM, TEM, XPS and BET, confirming that the Cs-POM active species retained its Keggin structure after immobilization. The substitution method of Cs-PMM exhibited more excellent catalytic performance for oxidative desulfurization of dibenzothiophene in the presence of oxygen. Under optimal conditions, the DBT conversion rate reached up to 99.6% and could be recycled 10 times without significant loss of catalytic activity, which is mainly attributed to the slow leaching of the active heteropolyacid species from the strong fixed effect of the mixture porous materials. Copyright © 2017. Published by Elsevier B.V.

  9. Revisiting the Aluminum Trimesate-based MOF (MIL-96): from Structure Determination to the Processing of Mixed Matrix Membranes for CO2 Capture.

    KAUST Repository

    Benzaqui, Marvin

    2017-11-08

    A microporous Al trimesate-based metal-organic framework (MOF), denoted MIL-96-(Al), was selected as a porous hybrid filler for the processing of mixed matrix membranes (MMMs) for CO2/N-2 postcombustion separation. First, the structural model of MIL-96-(Al) initially reported was revisited using a combination of synchrotron-based single-crystal X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory (DFT) calculations. In a second step, pure MIL-96-(Al) crystals differing by their size and aspect ratio, including anisotropic hexagonal platelets and nanoparticles of about 70 nm in diameter, were prepared. Then, a combination of in situ IR spectroscopy, single-gas, and CO2/N-2 coadsorption experiments, calorimetry, and molecular simulations revealed that MIL-96-(Al) nanoparticles show a relatively high CO2 affinity over N-2 owing to strong interactions between CO2 molecules and several adsorption sites such as Al3+ Lewis centers, coordinated water, and hydroxyl groups. Finally, the high compatibility between MIL-96-(Al) nanoparticles and the 6FDA-DAM polymer allowed the processing of homogeneous and defect-free MMMs with a high MOF loading (up to 25 wt %) that outperform pure polymer membranes for CO2/N-2 separation.

  10. Bio-inspired MOF-based Catalysts for Lignin Valorization.

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Stavila, Vitalie; Ramakrishnan, Parthasarathi; Davis, Ryan Wesley

    2014-09-01

    Lignin is a potentially plentiful source of renewable organics, with %7E50Mtons/yr produced by the pulp/paper industry and 200-300 Mtons/yr projected production by a US biofuels industry. This industry must process approximately 1 billion tons of biomass to meet the US Renewable Fuel goals. However, there are currently no efficient processes for converting lignin to value-added chemicals and drop-in fuels. Lignin is therefore an opportunity for production of valuable renewable chemicals, but presents staggering technical and economic challenges due to the quantities of material involved and the strong chemical bonds comprising this polymer. Aggressive chemistries and high temperatures are required to degrade lignin without catalysts. Moreover, chemical non-uniformity among lignins leads to complex product mixtures that tend to repolymerize. Conventional petrochemical approaches (pyrolysis, catalytic cracking, gasification) are energy intensive (400-800 degC), require complicated separations, and remove valuable chemical functionality. Low-temperature (25-200 degC) alternatives are clearly desirable, but enzymes are thermally fragile and incompatible with liquid organic compounds, making them impractical for large-scale biorefining. Alternatively, homogeneous catalysts, such as recently developed vanadium complexes, must be separated from product mixtures, while many heterogenous catalysts involve costly noble metals. The objective of this project is to demonstrate proof of concept that an entirely new class of biomimetic, efficient, and industrially robust synthetic catalysts based on nanoporous Metal- Organic Frameworks (MOFs) can be developed. Although catalytic MOFs are known, catalysis of bond cleavage reactions needed for lignin degradation is completely unexplored. Thus, fundamental research is required that industry and most sponsoring agencies are currently unwilling to undertake. We introduce MOFs infiltrated with titanium and nickel species as catalysts

  11. Synthesis and CO{sub 2} adsorption study of modified MOF-5 with multi-wall carbon nanotubes and expandable graphite

    Energy Technology Data Exchange (ETDEWEB)

    Ullah, Sami, E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Bustam, M. A., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Shariff, A. M., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Elkhalifah, Ali E. I., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Murshid, G., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Riaz, Nadia, E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com [Research Center for Carbon Dioxide Capture, Dept. of Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Sri Iskandar, Tronoh 31750 Perak (Malaysia)

    2014-10-24

    MOF-5 was synthesized by solvothermal method and its reactivation under anhydrous conditions. This research is conducted to investigate the effect of MOF-5 and MOF-5 modified with multi-wall carbon nanotubes (MWCNTs) and expandable graphite (EG) on the performance of CO{sub 2} adsorption. The synthesized MOFs were characterized using Field emission scanning electron microscopy (FESEM) for surface morphology, Thermogravimetric analysis (TGA) for thermal stability, X-ray diffraction (XRD) for crystals plane, Brunauer-Emmet-Teller (BET) for surface area and CO{sub 2} adsorption. The result had showed that the modified MOF-5 enhanced the CO{sub 2} adsorption compared to the pure MOF-5. The increment in the CO{sub 2} uptake capacities of MOF materials was attributed to the decrease in the pore size and enhancement of micropore volume of MOF-5 by multi-walled carbon nanotube and EG incorporation. The BET surface area of the synthesized MOF-5@MWCNTs is more than MOF-5. The CO{sub 2} sorption capacities of MOF-5 and MOF-5@MWCNTs were observed to increase from 0.00008 to 0.00048 mol g-1 at 298 K and 1 bar. The modified MOF-5@MWCNTs resulted in the highest CO{sub 2} adsorption followed by the modified MOF-5@ EG and lastly, MOF-5.

  12. Metal-adeninate vertices for the construction of an exceptionally porous metal-organic framework.

    Science.gov (United States)

    An, Jihyun; Farha, Omar K; Hupp, Joseph T; Pohl, Ehmke; Yeh, Joanne I; Rosi, Nathaniel L

    2012-01-03

    Metal-organic frameworks comprising metal-carboxylate cluster vertices and long, branched organic linkers are the most porous materials known, and therefore have attracted tremendous attention for many applications, including gas storage, separations, catalysis and drug delivery. To increase metal-organic framework porosity, the size and complexity of linkers has increased. Here we present a promising alternative strategy for constructing mesoporous metal-organic frameworks that addresses the size of the vertex rather than the length of the organic linker. This approach uses large metal-biomolecule clusters, in particular zinc-adeninate building units, as vertices to construct bio-MOF-100, an exclusively mesoporous metal-organic framework. Bio-MOF-100 exhibits a high surface area (4,300 m(2) g(-1)), one of the lowest crystal densities (0.302 g cm(-3)) and the largest metal-organic framework pore volume reported to date (4.3 cm(3) g(-1)).

  13. Recent advances in visible-light-responsive photocatalysts for hydrogen production and solar energy conversion--from semiconducting TiO2 to MOF/PCP photocatalysts.

    Science.gov (United States)

    Horiuchi, Yu; Toyao, Takashi; Takeuchi, Masato; Matsuoka, Masaya; Anpo, Masakazu

    2013-08-28

    The present perspective describes recent advances in visible-light-responsive photocatalysts intended to develop novel and efficient solar energy conversion technologies, including water splitting and photofuel cells. Water splitting is recognized as one of the most promising techniques to convert solar energy as a clean and abundant energy resource into chemical energy in the form of hydrogen. In recent years, increasing concern is directed to not only the development of new photocatalytic materials but also the importance of technologies to produce hydrogen and oxygen separately. Photofuel cells can convert solar energy into electrical energy by decomposing bio-related compounds and livestock waste as fuels. The advances of photocatalysts enabling these solar energy conversion technologies have been going on since the discovery of semiconducting titanium dioxide materials and have extended to organic-inorganic hybrid materials, such as metal-organic frameworks and porous coordination polymers (MOF/PCP).

  14. Metal-Organic Frameworks: Building Block Design Strategies for the Synthesis of MOFs.

    KAUST Repository

    Luebke, Ryan

    2014-01-01

    A significant and ongoing challenge in materials chemistry and furthermore solid state chemistry is to design materials with the desired properties and characteristics. The field of Metal-Organic Frameworks (MOFs) offers several strategies

  15. Gas adsorption and gas mixture separations using mixed-ligand MOF material

    Science.gov (United States)

    Hupp, Joseph T [Northfield, IL; Mulfort, Karen L [Chicago, IL; Snurr, Randall Q [Evanston, IL; Bae, Youn-Sang [Evanston, IL

    2011-01-04

    A method of separating a mixture of carbon dioxiode and hydrocarbon gas using a mixed-ligand, metal-organic framework (MOF) material having metal ions coordinated to carboxylate ligands and pyridyl ligands.

  16. Highly porous ionic rht metal-organic framework for H2 and CO2 storage and separation: A molecular simulation study

    KAUST Repository

    Babarao, Ravichandar

    2010-07-06

    The storage and separation of H2 and CO2 are investigated in a highly porous ionic rht metal-organic framework (rht-MOF) using molecular simulation. The rht-MOF possesses a cationic framework and charge-balancing extraframework NO3 - ions. Three types of unique open cages exist in the framework: rhombicuboctahedral, tetrahedral, and cuboctahedral cages. The NO3 - ions exhibit small mobility and are located at the windows connecting the tetrahedral and cuboctahedral cages. At low pressures, H2 adsorption occurs near the NO 3 - ions that act as preferential sites. With increasing pressure, H2 molecules occupy the tetrahedral and cuboctahedral cages and the intersection regions. The predicted isotherm of H2 at 77 K agrees well with the experimental data. The H2 capacity is estimated to be 2.4 wt % at 1 bar and 6.2 wt % at 50 bar, among the highest in reported MOFs. In a four-component mixture (15:75:5:5 CO2/H 2/CO/CH4) representing a typical effluent gas of H 2 production, the selectivity of CO2/H2 in rht-MOF decreases slightly with increasing pressure, then increases because of cooperative interactions, and finally decreases as a consequence of entropy effect. By comparing three ionic MOFs (rht-MOF, soc-MOF, and rho-ZMOF), we find that the selectivity increases with increasing charge density or decreasing free volume. In the presence of a trace amount of H2O, the interactions between CO2 and NO3 - ions are significantly shielded by H2O; consequently, the selectivity of CO 2/H2 decreases substantially. © 2010 American Chemical Society.

  17. Amine Functionalized Porous Network

    KAUST Repository

    Eddaoudi, Mohamed; Guillerm, Vincent; Weselinski, Lukasz Jan; Alkordi, Mohamed H.; Mohideen, Mohamed Infas Haja; Belmabkhout, Youssef

    2015-01-01

    Amine groups can be introduced in porous materials by a direct (one pot) or post-synthetic modification (PSM) process on aldehyde groups, and the resulting porous materials have increased gas affinity.

  18. Amine Functionalized Porous Network

    KAUST Repository

    Eddaoudi, Mohamed

    2015-05-28

    Amine groups can be introduced in porous materials by a direct (one pot) or post-synthetic modification (PSM) process on aldehyde groups, and the resulting porous materials have increased gas affinity.

  19. 3D hybrid-porous carbon derived from carbonization of metal organic frameworks for high performance supercapacitors

    Science.gov (United States)

    Bao, Weizhai; Mondal, Anjon Kumar; Xu, Jing; Wang, Chengyin; Su, Dawei; Wang, Guoxiu

    2016-09-01

    We report a rational design and synthesis of 3D hybrid-porous carbon with a hierarchical pore architecture for high performance supercapacitors. It contains micropores (<2 nm diameter) and mesopores (2-4 nm), derived from carbonization of unique porous metal organic frameworks (MOFs). Owning to the synergistic effect of micropores and mesopores, the hybrid-porous carbon has exceptionally high ion-accessible surface area and low ion diffusion resistance, which is desired for supercapacitor applications. When applied as electrode materials in supercapacitors, 3D hybrid-porous carbon demonstrates a specific capacitance of 332 F g-1 at a constant charge/discharge current of 500 mA g-1. The supercapacitors can endure more than 10,000 cycles without degradation of capacitance.

  20. Using MOF-74 for Hg{sup 2+} removal from ultra-low concentration aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Yang Yang; Li, Jian Qiang; Gong, Le Le; Feng, Xue Feng; Meng, Li Na; Zhang, Le; Meng, Pan Pan; Luo, Ming Biao; Luo, Feng, E-mail: ecitluofeng@163.com

    2017-02-15

    Mercury (Hg{sup 2+}) ions have very high toxicity and widely spread as environmental pollutants. At present, many efforts have been taken to remove the hazardous materials of mercury(II) by adsorption, and it is highly desirable to develop a novel adsorbent with high adsorptive capacities. However it is still a big challenge to remove the ultra-low-concentration mercury ions from water. In this paper, MOF-74-Zn is explored for such function, showing high removal rate of Hg(II) from water without any pretreatment, especially for the ultra-trace Hg(II) ions in the ppb magnitude with the removal rate reaching to 54.48%, 69.71%, 72.26% when the initial concentration of Hg(II) is 20ppb, 40ppb, 50ppb, respectively. - Graphical abstract: The absorption of mercury ions on MOF-74-Zn is due to somewhat weak interactions between MOF skeleton that is composed of carboxylate and hydroxy group and Hg2+ ions. - Highlights: • MOF-74-Zn shows high removal rate of Hg(II) from water without any pretreatment. • The MOF-74-Zn has a notable performance at ultra-low concentration of Hg(II). • MOF-74-Zn shows the potential for Hg(II) removal from industrial waste water.

  1. Using MOF-74 for Hg2+ removal from ultra-low concentration aqueous solution

    International Nuclear Information System (INIS)

    Xiong, Yang Yang; Li, Jian Qiang; Gong, Le Le; Feng, Xue Feng; Meng, Li Na; Zhang, Le; Meng, Pan Pan; Luo, Ming Biao; Luo, Feng

    2017-01-01

    Mercury (Hg 2+ ) ions have very high toxicity and widely spread as environmental pollutants. At present, many efforts have been taken to remove the hazardous materials of mercury(II) by adsorption, and it is highly desirable to develop a novel adsorbent with high adsorptive capacities. However it is still a big challenge to remove the ultra-low-concentration mercury ions from water. In this paper, MOF-74-Zn is explored for such function, showing high removal rate of Hg(II) from water without any pretreatment, especially for the ultra-trace Hg(II) ions in the ppb magnitude with the removal rate reaching to 54.48%, 69.71%, 72.26% when the initial concentration of Hg(II) is 20ppb, 40ppb, 50ppb, respectively. - Graphical abstract: The absorption of mercury ions on MOF-74-Zn is due to somewhat weak interactions between MOF skeleton that is composed of carboxylate and hydroxy group and Hg2+ ions. - Highlights: • MOF-74-Zn shows high removal rate of Hg(II) from water without any pretreatment. • The MOF-74-Zn has a notable performance at ultra-low concentration of Hg(II). • MOF-74-Zn shows the potential for Hg(II) removal from industrial waste water.

  2. Highly sensitive and selective SO2 MOF sensor: the integration of MFM-300 MOF as a sensitive layer on a capacitive interdigitated electrode

    KAUST Repository

    Chernikova, Valeriya; Yassine, Omar; Shekhah, Osama; Eddaoudi, Mohamed; Salama, Khaled N.

    2018-01-01

    We report on the fabrication of an advanced chemical capacitive sensor for the detection of sulfur dioxide (SO2) at room temperature. The sensing layer based on an indium metal–organic framework (MOF), namely MFM-300, is coated solvothermally on a functionalized capacitive interdigitated electrode. The fabricated sensor exhibits significant detection sensitivity to SO2 at concentrations down to 75 ppb, with the lower detection limit estimated to be around 5 ppb. The MFM-300 MOF sensor demonstrates highly desirable detection selectivity towards SO2 vs. CH4, CO2, NO2 and H2, as well as an outstanding SO2 sensing stability.

  3. Highly sensitive and selective SO2 MOF sensor: the integration of MFM-300 MOF as a sensitive layer on a capacitive interdigitated electrode

    KAUST Repository

    Chernikova, Valeriya

    2018-03-05

    We report on the fabrication of an advanced chemical capacitive sensor for the detection of sulfur dioxide (SO2) at room temperature. The sensing layer based on an indium metal–organic framework (MOF), namely MFM-300, is coated solvothermally on a functionalized capacitive interdigitated electrode. The fabricated sensor exhibits significant detection sensitivity to SO2 at concentrations down to 75 ppb, with the lower detection limit estimated to be around 5 ppb. The MFM-300 MOF sensor demonstrates highly desirable detection selectivity towards SO2 vs. CH4, CO2, NO2 and H2, as well as an outstanding SO2 sensing stability.

  4. Synthesis and characterization of polymorphs of photoluminescent Eu(III)-(2,5-furandicarboxylic acid, oxalic acid) MOFs

    Science.gov (United States)

    Shi, Fa-Nian; Ananias, Duarte; Yang, Ting-Hai; Rocha, João

    2013-08-01

    A novel metal organic framework (MOF) formulated as [Eu(H2O)2(fdc)(ox)0.5·(H2O)]n (1, fdc2-=2,5-furandicarboxylate, ox2-=oxalate), was hydrothermally synthesized via in situ ox2- generation from the partial decomposition of the fdc2- ligand. This material crystallizes in the monoclinic space group C2/c, unit cell parameters of 1: a=16.7570(10), b=10.5708(7), c=13.5348(14) Å, β=116.917(2)° (Z=8), and exhibits a three-dimensional (3D)-porous framework, with guest water molecules residing in the channel linking all other ligands (H2O, ox2-and fdc2-) via hydrogen bonding interactions. Compound 2 is a polymorph of 1 crystallizing in monoclinic P21/c space group. The photoluminescence properties of 1 and 2 were studied at room temperature. The spectra show the typical Eu3+ red emission and the differences observed reflects the slightly different structures of these polymorphs.

  5. Tailored Porous Materials

    Energy Technology Data Exchange (ETDEWEB)

    BARTON,THOMAS J.; BULL,LUCY M.; KLEMPERER,WALTER G.; LOY,DOUGLAS A.; MCENANEY,BRIAN; MISONO,MAKOTO; MONSON,PETER A.; PEZ,GUIDO; SCHERER,GEORGE W.; VARTULI,JAMES C.; YAGHI,OMAR M.

    1999-11-09

    Tailoring of porous materials involves not only chemical synthetic techniques for tailoring microscopic properties such as pore size, pore shape, pore connectivity, and pore surface reactivity, but also materials processing techniques for tailoring the meso- and the macroscopic properties of bulk materials in the form of fibers, thin films and monoliths. These issues are addressed in the context of five specific classes of porous materials: oxide molecular sieves, porous coordination solids, porous carbons, sol-gel derived oxides, and porous heteropolyanion salts. Reviews of these specific areas are preceded by a presentation of background material and review of current theoretical approaches to adsorption phenomena. A concluding section outlines current research needs and opportunities.

  6. Advances in hollow MOFs%中空MOFs的研究进展

    Institute of Scientific and Technical Information of China (English)

    张春花; 陈日志; 邢卫红

    2017-01-01

    中空金属有机骨架材料MOFs因其具有高的比表面积、密度低、中空结构等优点受到人们广泛的关注,是近年来MOFs材料的一个重要研究方向.本文概括了中空结构MOFs(H-MOFs)制备方法的研究进展,重点介绍了聚苯乙烯牺牲剂和Cu2O自我牺牲剂模板法、乳液型液-液和液-气界面的软模板法、Ostwald Ripening、Kirkendall效应等自组装方法的无模板法,并对其优缺点进行了讨论;探讨了中空MOFs在气体吸附和分离、催化方面的应用性能及在生物医药、磁性分离及环境保护方面的潜在应用;并提出今后H_MOFs研究的主要方向是合成新型H_MOFs、制备形貌多样、结晶性能好的新型高稳定性材料、精确控制壳层厚度以及开发新的H_MOFs制备方法.%H_MOFs have attracted considerable interest and found potential applications in many fields due to their special properties such as high surface area,low density and hollow structure,and the related reseach has been an important direction of MOFs materials. This article mainly featured recent research progress towards various preparation methods of H_MOFs,with the focus on the hard-template routes including polystyrene and Cu2O,the soft-template routes including emulsion-based interfacial synthesis and gas-liquid interfacial,and the template-free routes including Ostwald Ripening and Kirkendall effect were analyzed in detail. And the advantages and disadvantages of these methods,were discussed respectively. Applications of H_MOFs in gas adsorption and separation,catalysis,and potential applications of H_MOFs in biomedical,magnetic separation and environment protection were also discussed. The preparation of novel and highly stable H_MOFs materials with versatile morphology and good crystallinity,the precise control of shell thickness and the development of preparation methods of H_MOFs were proposed as the main future research and development directions of H_MOFs.

  7. Porous organic cages

    Science.gov (United States)

    Tozawa, Tomokazu; Jones, James T. A.; Swamy, Shashikala I.; Jiang, Shan; Adams, Dave J.; Shakespeare, Stephen; Clowes, Rob; Bradshaw, Darren; Hasell, Tom; Chong, Samantha Y.; Tang, Chiu; Thompson, Stephen; Parker, Julia; Trewin, Abbie; Bacsa, John; Slawin, Alexandra M. Z.; Steiner, Alexander; Cooper, Andrew I.

    2009-12-01

    Porous materials are important in a wide range of applications including molecular separations and catalysis. We demonstrate that covalently bonded organic cages can assemble into crystalline microporous materials. The porosity is prefabricated and intrinsic to the molecular cage structure, as opposed to being formed by non-covalent self-assembly of non-porous sub-units. The three-dimensional connectivity between the cage windows is controlled by varying the chemical functionality such that either non-porous or permanently porous assemblies can be produced. Surface areas and gas uptakes for the latter exceed comparable molecular solids. One of the cages can be converted by recrystallization to produce either porous or non-porous polymorphs with apparent Brunauer-Emmett-Teller surface areas of 550 and 23m2g-1, respectively. These results suggest design principles for responsive porous organic solids and for the modular construction of extended materials from prefabricated molecular pores.

  8. Synthesis and Electrospraying of Nanoscale MOF (Metal Organic Framework) for High-Performance CO2 Adsorption Membrane

    Science.gov (United States)

    Wahiduzzaman; Allmond, Kelsey; Stone, John; Harp, Spencer; Mujibur, Khan

    2017-01-01

    We report the sonochemical synthesis of MOF (metal organic framework) nanoparticles of 30-200 nm in size and electrospraying of those particles on electrospun nanofibers to process a MOF-attached nanofibrous membrane. This membrane displayed significant selectivity towards CO2 and capacity of adsorbing with 4000-5000 ppm difference from a mixed gas flow of 1% CO2 and 99% N2. Applying ultrasonic waves during the MOF synthesis offered rapid dispersion and formation of crystalline MOF nanoparticles in room temperature. The MOF nanoparticles of 100-200 nm in size displayed higher surface area and adsorption capacity comparing to that of 30-60 nm in size. Nanofibrous membrane was produced by electrospinning of MOF blended PAN solution followed by electrospraying of additional MOF nanoparticles. This yielded uniform MOF deposition on nanofibers, occurred due to electrostatic attraction between highly charged nanoparticles and conductive nanofibers. A test bench for real-time CO2 adsorption at room temperature was built with non-dispersive Infrared (NDIR) CO2 sensors. Comparative tests were performed on the membrane to investigate its enhanced adsorption capacity. Three layers of the as-produced membranes displayed CO2 adsorption for approximately 2 h. Thermogravimetric analysis (TGA) of the membrane showed the thermal stability of the MOF and PAN up to 290 and 425 °C, respectively.

  9. Thermodynamics of solvent interaction with the metal-organic framework MOF-5.

    Science.gov (United States)

    Akimbekov, Zamirbek; Wu, Di; Brozek, Carl K; Dincă, Mircea; Navrotsky, Alexandra

    2016-01-14

    The inclusion of solvent in metal-organic framework (MOF) materials is a highly specific form of guest-host interaction. In this work, the energetics of solvent MOF-5 interactions has been investigated by solution calorimetry in 5 M sodium hydroxide (NaOH) at room temperature. Solution calorimetric measurement of enthalpy of formation (ΔH(f)) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)(-1), respectively. The enthalpies of interaction (ΔH(int)) for DMF and DEF with MOF-5 are -82.78 ± 4.84 kJ (mol DMF)(-1) and -89.28 ± 3.05 kJ (mol DEF)(-1), respectively. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quantitative thermodynamic basis to investigate transmetallation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs.

  10. An -OH group functionalized MOF for ratiometric Fe3+ sensing

    Science.gov (United States)

    Xu, Hui; Dong, Yingying; Wu, Yuhang; Ren, Wenjing; Zhao, Tao; Wang, Shunli; Gao, Junkuo

    2018-02-01

    Iron is one of the most important elements in the biochemical processes in all living system, both deficiency or excess of iron will lead to metabolism disorder diseases. However, Fe3+ is one of the most efficient fluorescence quenchers among the transition-metal ions because of its paramagnetic nature. The realization of Fe3+ ratiometric and self-calibrated fluorescent sensor is highly-challenging. We synthesized a novel luminescent -OH functionalized EuOHBDC (Eu2(OH-BDC)3, OH-BDC=2-hydroxyterephthalic acid) by hydrothermal reaction and in situ ligand synthesis, and used it as a rare ratiomatric luminescent sensor for Fe3+ ions. The -OH functional group facilitates both electron transfer and binding interaction between EuOHBDC and Fe3+, which lead to luminescent quenching of ligand-based emission while enhancement of a new peak emission, and thus enables ratiometric detection of Fe3+. The relative fluorescent intensity ratio (I375/I427) increased linearly with increasing Fe3+ concentration in the 10-50 μM range with 1.17 μM (65 ppb) detection limit. The EuOHBDC also shows excellent selectivity towards different metal ions, particularly can discriminate Fe3+ and Fe2+ through different luminescent responses. This result clearly demonstrates the superiority of -OH functionalized MOF for Fe3+ detection, which can contribute to develop high performance luminescent probe for detection of metal ions in environmental and biomedical applications.

  11. Hydrogen selective NH{sub 2}-MIL-53(Al) MOF membranes with high permeability

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Feng; Zou, Xiaoqin; Gao, Xue; Fan, Songjie; Sun, Fuxing; Ren, Hao; Zhu, Guangshan [State Key Laboratory of Inorganic, Synthesis and Preparative Chemistry, Jilin University, Changchun (China)

    2012-09-11

    Hydrogen-based energy is a promising renewable and clean resource. Thus, hydrogen selective microporous membranes with high performance and high stability are demanded. Novel NH{sub 2}-MIL-53(Al) membranes are evaluated for hydrogen separation for this goal. Continuous NH{sub 2}-MIL-53(Al) membranes have been prepared successfully on macroporous glass frit discs assisted with colloidal seeds. The gas sorption ability of NH{sub 2}-MIL-53(Al) materials is studied by gas adsorption measurement. The isosteric heats of adsorption in a sequence of CO{sub 2}> N{sub 2}> CH{sub 4}{approx} H{sub 2} indicates different interactions between NH{sub 2}-MIL-53(Al) framework and these gases. As-prepared membranes are measured by single and binary gas permeation at different temperatures. The results of singe gas permeation show a decreasing permeance in an order of H{sub 2}> CH{sub 4}> N{sub 2}> CO{sub 2}, suggesting that the diffusion and adsorption properties make significant contributions in the gas permeation through the membrane. In binary gas permeation, the NH{sub 2}-MIL-53(Al) membrane shows high selectivity for H{sub 2} with separation factors of 20.7, 23.9 and 30.9 at room temperature (288 K) for H{sub 2} over CH{sub 4}, N{sub 2} and CO{sub 2}, respectively. In comparison to single gas permeation, a slightly higher separation factor is obtained due to the competitive adsorption effect between the gases in the porous MOF membrane. Additionally, the NH{sub 2}-MIL-53(Al) membrane exhibits very high permeance for H{sub 2} in the mixtures separation (above 1.5 x 10{sup -6} mol m{sup -2} s{sup -1} Pa{sup -1}) due to its large cavity, resulting in a very high separation power. The details of the temperature effect on the permeances of H{sub 2} over other gases are investigated from 288 to 353 K. The supported NH{sub 2}-MIL-53(Al) membranes with high hydrogen separation power possess high stability, resistance to cracking, temperature cycling and show high reproducibility

  12. Computational materials chemistry for carbon capture using porous materials

    International Nuclear Information System (INIS)

    Sharma, Abhishek; Malani, Ateeque; Huang, Runhong; Babarao, Ravichandar

    2017-01-01

    Control over carbon dioxide (CO 2 ) release is extremely important to decrease its hazardous effects on the environment such as global warming, ocean acidification, etc. For CO 2 capture and storage at industrial point sources, nanoporous materials offer an energetically viable and economically feasible approach compared to chemisorption in amines. There is a growing need to design and synthesize new nanoporous materials with enhanced capability for carbon capture. Computational materials chemistry offers tools to screen and design cost-effective materials for CO 2 separation and storage, and it is less time consuming compared to trial and error experimental synthesis. It also provides a guide to synthesize new materials with better properties for real world applications. In this review, we briefly highlight the various carbon capture technologies and the need of computational materials design for carbon capture. This review discusses the commonly used computational chemistry-based simulation methods for structural characterization and prediction of thermodynamic properties of adsorbed gases in porous materials. Finally, simulation studies reported on various potential porous materials, such as zeolites, porous carbon, metal organic frameworks (MOFs) and covalent organic frameworks (COFs), for CO 2 capture are discussed. (topical review)

  13. Capturing the H 2 –Metal Interaction in Mg-MOF-74 Using Classical Polarization

    KAUST Repository

    Pham, Tony; Forrest, Katherine A.; McLaughlin, Keith; Eckert, Juergen; Space, Brian

    2014-01-01

    © 2014 American Chemical Society. Grand canonical Monte Carlo (GCMC) simulations of H2 sorption were performed in Mg-MOF-74, a metal-organic framework (MOF) that displays very high H2 sorption affinity. Experimental H2 sorption isotherms and isosteric heats of adsorption (Qst) values were reproduced using a general purpose materials sorption potential that includes many-body polarization interactions. In contrast, using two models that include only charge-quadrupole interactions failed to reproduce such experimental measurements even though they are the type normally employed in such classical force field calculations. Utilizing the present explicit polarizable model in GCMC simulation resulted in a Mg2+-H2 distance of 2.60 Å, which is close to a previously reported value that was obtained using electronic structure methods and comparable to similar experimental measurements. The induced dipole distribution obtained from simulation assisted in the characterization of two previously identified sorption sites in the MOF: the Mg2+ ions and the oxido group of the linkers. The calculated two-dimensional quantum rotational levels for a H2 molecule sorbed onto the Mg2+ ion were in good agreement with experimental inelastic neutron scattering (INS) data. Although the H2-metal interaction in MOFs may be thought of as a quantum mechanical effect, this study demonstrates how the interaction between the sorbate molecules and the open-metal sites in a particular highly sorbing MOF can be captured using classical simulation techniques that involve a polarizable potential.

  14. Capturing the H 2 –Metal Interaction in Mg-MOF-74 Using Classical Polarization

    KAUST Repository

    Pham, Tony

    2014-10-02

    © 2014 American Chemical Society. Grand canonical Monte Carlo (GCMC) simulations of H2 sorption were performed in Mg-MOF-74, a metal-organic framework (MOF) that displays very high H2 sorption affinity. Experimental H2 sorption isotherms and isosteric heats of adsorption (Qst) values were reproduced using a general purpose materials sorption potential that includes many-body polarization interactions. In contrast, using two models that include only charge-quadrupole interactions failed to reproduce such experimental measurements even though they are the type normally employed in such classical force field calculations. Utilizing the present explicit polarizable model in GCMC simulation resulted in a Mg2+-H2 distance of 2.60 Å, which is close to a previously reported value that was obtained using electronic structure methods and comparable to similar experimental measurements. The induced dipole distribution obtained from simulation assisted in the characterization of two previously identified sorption sites in the MOF: the Mg2+ ions and the oxido group of the linkers. The calculated two-dimensional quantum rotational levels for a H2 molecule sorbed onto the Mg2+ ion were in good agreement with experimental inelastic neutron scattering (INS) data. Although the H2-metal interaction in MOFs may be thought of as a quantum mechanical effect, this study demonstrates how the interaction between the sorbate molecules and the open-metal sites in a particular highly sorbing MOF can be captured using classical simulation techniques that involve a polarizable potential.

  15. Hydrogen adsorption on metal-organic frameworks (MOFs) and single-walled carbon nanotubes (SWNTs)

    Energy Technology Data Exchange (ETDEWEB)

    Poirier, E.; Chahine, R.; Benard, P.; Lafi, L.; Dorval-Douville, G.; Chandonia, P.-A. [Univ. du Quebec a Trois-Rivieres, Inst. de recherche sur l' hydrogene, Trois-Rivieres, Quebec (Canada)]. E-mail: Lyubov.Lafi@uqtr.ca

    2006-07-01

    'Full text:' In recent years, several novel carbon-based microporous materials such as single-walled carbon nanotubes (SWNTs) and metal-organic frameworks (MOFs) have been proposed as promising adsorbents for hydrogen. Hydrogen adsorption measurements on Al-, Cr- and Zn-based metal-organic frameworks (MOFs) and single-walled carbon nanotubes (SWNTs) are presented. The measurements were performed at temperatures ranging from 77 to 300K and pressures up to 50 atm using a volumetric approach. The maximum excess adsorption at 77K ranges from 2,8 to 3,9 wt % for the MOFs and from 1,5 to 2,5 wt % for the SWNTs. These values are reached at pressures below 40 atm. At room temperature and 40 atm, modest amounts of hydrogen are adsorbed (< 0,4 wt %). A Dubinin-Astakhov (DA) approach is used to investigate the measured adsorption isotherms and retrieve energetic and structural parameters. The adsorption enthalpy averaged over filling is found to be about 2,9 kJ/mol for the MOF-5 and about 3,6 - 4,2 kJ/mol for SWNTs. The uptake of hydrogen on SWNTs and MOF-5 appears to be due to physisorption and can be described, through the DA-model, by a traditional theory of micropore filling. (author)

  16. Fe/Fe3C decorated 3-D porous nitrogen-doped graphene as a cathode material for rechargeable Li–O2 batteries

    International Nuclear Information System (INIS)

    Lai, Yanqing; Chen, Wei; Zhang, Zhian; Qu, Yaohui; Gan, Yongqing; Li, Jie

    2016-01-01

    Graphical abstract: Fe/Fe 3 C decorated 3-D porous N-doped graphene are prepaed by a one-step carbonization process, with MOF as the structure-directing agent. The method provides a simple and scalable route for preparing 3-D porous graphene materials.The as-prepared material possesses an excellent bi-functional electrocatalytic activity. While applied as the cathode materials of Li–O 2 batteries, the cell exihibits high capacity and considerable rate capability. - Highlights: • A facile simple strategy is employed to in-situ fabricate Fe/Fe 3 C decorated 3-D porous nitrogen-doped graphene. • MIL-100(Fe), a kind of metal-organic framework, is proved playing a structure-directing role in this advanced synthesis route. • This material possesses excellent bi-functional electro-catalytic activity for ORR and OER and shows good electrochemical performance while used as cathode material for Li–O 2 batteries. • The MOF-assisted synthesis method would be a promising new strategy for the synthesis of 3-D porous graphene materials. - Abstract: Fe/Fe 3 C decorated 3-D porous N-doped graphene (F-PNG) is designed and synthesized via a one-step carbonization route. During the process, MIL-100(Fe), a kind of metal organic frameworks (MOFs) plays a structure-directing role. It is found that F-PNG with 3-D porous structure is constituted by N-doped graphene and extremely small Fe/Fe 3 C particles uniformly distribute on the surface of graphene. This rationally designed F-PNG possesses excellent oxygen reduction reaction and oxygen evolution reaction bifunctional electrocatalytic activity. While the material is explored as a cathode of Li–O 2 batteries, it exhibits excellent electrochemical performances, delivering a discharge voltage platform of ∼2.91 V and a charge voltage platform of ∼3.52 V at 0.1 mA cm −2 , showing a good cycle performance and having a discharge capacity of ∼7150 mAh g −1 carbon+catalyst at 0.1 mA cm −2 . The excellent performance of

  17. Immobilization of Bacillus subtilis lipase on a Cu-BTC based hierarchically porous metal-organic framework material: a biocatalyst for esterification.

    Science.gov (United States)

    Cao, Yu; Wu, Zhuofu; Wang, Tao; Xiao, Yu; Huo, Qisheng; Liu, Yunling

    2016-04-28

    Bacillus subtilis lipase (BSL2) has been successfully immobilized into a Cu-BTC based hierarchically porous metal-organic framework material for the first time. The Cu-BTC hierarchically porous MOF material with large mesopore apertures is prepared conveniently by using a template-free strategy under mild conditions. The immobilized BSL2 presents high enzymatic activity and perfect reusability during the esterification reaction. After 10 cycles, the immobilized BSL2 still exhibits 90.7% of its initial enzymatic activity and 99.6% of its initial conversion.

  18. Review on the current practices and efforts towards pilot-scale production of metal-organic frameworks (MOFs)

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2017-12-01

    Full Text Available -effective production technologies account for the slow progression towards the development of envisioned MOF products at pilot-scale level. This short review brings together the scattered literature that addresses pilot-scale production of MOF materials. An additional...

  19. Facile synthesis of hydroxy-modified MOF-5 for improving the adsorption capacity of hydrogen by lithium doping.

    Science.gov (United States)

    Kubo, Masaru; Hagi, Hayato; Shimojima, Atsushi; Okubo, Tatsuya

    2013-11-01

    A facile synthesis of partially hydroxy-modified MOF-5 and its improved H2-adsorption capacity by lithium doping are reported. The reaction of Zn(NO3)2·6H2O with a mixture of terephthalic acid (H2BDC) and 2-hydroxyterephthalic acid (H2BDC-OH) in DMF gave hydroxy-modified MOF-5 (MOF-5-OH-x), in which the molar fraction (x) of BDC-OH(2-) was up to 0.54 of the whole ligand. The MOF-5-OH-x frameworks had high BET surface areas (about 3300 m(2) g(-1)), which were comparable to that of MOF-5. We suggest that the MOF-5-OH-x frameworks are formed by the secondary growth of BDC(2-)-rich MOF-5 seed crystals, which are nucleated during the early stage of the reaction. Subsequent Li doping into MOF-5-OH-x results in increased H2 uptake at 77 K and 0.1 MPa from 1.23 to 1.39 wt.% and an increased isosteric heat of H2 adsorption from 5.1-4.2 kJ mol(-1) to 5.5-4.4 kJ mol(-1). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Effects of ammonium hydroxide on the structure and gas adsorption of nanosized Zr-MOFs (UiO-66).

    Science.gov (United States)

    Abid, Hussein Rasool; Ang, Ha Ming; Wang, Shaobin

    2012-05-21

    Several zirconium-based metal-organic frameworks (Zr-MOFs) have been synthesized using ammonium hydroxide as an additive in the synthesis process. Their physicochemical properties have been characterized by N(2) adsorption/desorption, XRD, SEM, FTIR, and TGA, and their application in CO(2) adsorption was evaluated. It was found that addition of ammonium hydroxide produced some effects on the structure and adsorption behavior of Zr-MOFs. The pore size and pore volume of Zr-MOFs were enhanced with the additive, however, specific surface area of Zr-MOFs was reduced. Using an ammonium hydroxide additive, the crystal size of Zr-MOF was reduced with increasing amount of the additive. All the samples presented strong thermal stability. Adsorption tests showed that capacity of CO(2) adsorption on the Zr-MOFs under standard conditions was reduced due to decreased micropore fractions. However, modified Zr-MOFs had significantly lower adsorption heat. The adsorption capacity of carbon dioxide was increased at high pressure, reaching 8.63 mmol g(-1) at 987 kPa for Zr-MOF-NH(4)-2.

  1. Microwave-assisted modulated synthesis of zirconium-based metal–organic framework (Zr-MOF) for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2014-05-01

    Full Text Available Zirconium-based metal–organic framework (Zr-MOF) was synthesized using a microwave-assisted modulated method in a short reaction time of 5 min. The Zr-MOF material was highly crystalline with well-defined octahedral shaped crystals, and it exhibited...

  2. Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

    Science.gov (United States)

    Benson, Oguarabau; da Silva, Ivan; Argent, Stephen P; Cabot, Rafel; Savage, Mathew; Godfrey, Harry G W; Yan, Yong; Parker, Stewart F; Manuel, Pascal; Lennox, Matthew J; Mitra, Tamoghna; Easun, Timothy L; Lewis, William; Blake, Alexander J; Besley, Elena; Yang, Sihai; Schröder, Martin

    2016-11-16

    An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO 2 uptake of 12.6 mmol g -1 at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffraction reveals that, surprisingly, there is no direct binding between the adsorbed CO 2 /CH 4 molecules and the pendant amide group in the pore. This observation has been confirmed unambiguously by inelastic neutron spectroscopy. This suggests that introduction of functional groups solely may not necessarily induce specific guest-host binding in porous materials, but it is a combination of pore size, geometry, and functional group that leads to enhanced gas adsorption properties.

  3. Stability of MOF-5 in a hydrogen gas environment containing fueling station impurities

    DEFF Research Database (Denmark)

    Ming, Yang; Purewal, Justin; Yang, Jun

    2016-01-01

    , HCl, H2O, CO, CO2, CH4, O2, N2, and He) to pure hydrogen gas. Subsequently, MOF-5 was exposed to these mixtures over hundreds of adsorption/desorption pressure-swing cycles and for extended periods of static exposure. The impact of exposure was assessed by periodically measuring the hydrogen storage...... of these contaminants on MOFs is mostly unknown. In the present study MOF-5 is adopted as a prototypical moisture-sensitive hydrogen storage material. Five “impure” gas mixtures were prepared by introducing low-to-moderate levels (i.e., up to ∼200 times greater than the J2719 limit) of selected contaminants (NH3, H2S...

  4. MOF-5 decorated hierarchical ZnO nanorod arrays and its photoluminescence

    Science.gov (United States)

    Zhang, Yinmin; Lan, Ding; Wang, Yuren; Cao, He; Jiang, Heng

    2011-04-01

    The strategy to manipulate nanoscale materials into well-organized hierarchical architectures is very important to both material synthesis and nanodevice applications. Here, nanoscale MOF-5 crystallites were successfully fabricated onto ordered hierarchical ZnO arrays based on aqueous chemical synthesis and molecule self-assembly technology guided room temperature diffusion method, which has the advantages of energy saving and simple operation. The structures and morphologies of the samples were performed by X-ray powder diffraction and field emission scanning electronic microscopy. The MOF-5 crystallites have good quality and bind well to the hexagonal-patterned ZnO arrays. The photoluminescence spectrum shows that the emission of hybrid MOF-5-ZnO films displays a blue shift in green emission and intensity reduction in UV emission. This ordered hybrid semiconductor material is expected to exploit the great potentiality in sensors, micro/nanodevices, and screen displays.

  5. Post-assembly transformations of porphyrin-containing metal-organic framework (MOF) films fabricated via automated layer-by-layer coordination

    KAUST Repository

    So, Monica; Beyzavi, M. Hassan; Sawhney, Rohan; Shekhah, Osama; Eddaoudi, Mohamed; Al-Juaid, Salih Salem; Hupp, Joseph T.; Farha, Omar K.

    2015-01-01

    Herein, we demonstrate the robustness of layer-by-layer (LbL)-assembled, pillared-paddlewheel-type MOF films toward conversion to new or modified MOFs via solvent-assisted linker exchange (SALE) and post-assembly linker metalation. Further, we show that LbL synthesis can afford MOFs that have proven inaccessible through other de novo strategies.

  6. Reticular synthesis of HKUST-like tbo MOFs with enhanced CH4 storage

    KAUST Repository

    Spanopoulos, Ioannis

    2015-12-22

    Successful implementation of reticular chemistry using a judiciously designed rigid octatopic carboxylate organic linker allowed the construction of expanded HKUST-1-like tbo-MOF series with intrinsic strong CH4 adsorption sites. The Cu-analogue displayed a concomitant enhancement of the gravimetric and volumetric surface area with the highest reported CH4 uptake among the tbo family, comparable to the best performing MOFs for CH4 storage. The corresponding gravimetric (BET) and volumetric surface area of 3971 m2 g-1 and 2363 m2 cm-3 represent an increase of respectively 115 % and 47 % in comparison to the corresponding values for the prototypical HKUST-1 (tbo-MOF-1), and 42 % and 20 % higher than tbo-MOF-2. High pressure methane adsorption isotherms revealed a high total gravimetric and volumetric CH4 uptakes, reaching 372 cm3 (STP) g-1 and 221 cm3 (STP) cm-3 respectively at 85 bar and 298 K. The corresponding working capacities between 5-80 bar were found to be 294 cm3 (STP) g-1 and 175 cm3 (STP) cm-3 and are placed among the best performing MOFs for CH4 storage particularly at relatively low temperature (e.g. 326 cm3 (STP) g-1 and 194 cm3 (STP) cm-3 at 258 K). To better understand the structure-property relationship and gain insight on the mechanism accounting for the resultant enhanced CH4 storage capacity, molecular simulation study was performed and revealed the presence of very strong CH4 adsorption sites at the vicinity of the organic linker with similar adsorption energetics as the open metal sites. The present findings supports the potential of tbo-MOFs based on the supermolecular building layer (SBL) approach as an ideal platform to further enhance the CH4 storage capacity via expansion and functionalization of the quadrangular pillars.

  7. Metal-Organic Frameworks: Building Block Design Strategies for the Synthesis of MOFs.

    KAUST Repository

    Luebke, Ryan

    2014-09-01

    A significant and ongoing challenge in materials chemistry and furthermore solid state chemistry is to design materials with the desired properties and characteristics. The field of Metal-Organic Frameworks (MOFs) offers several strategies to address this challenge and has proven fruitful at allowing some degree of control over the resultant materials synthesized. Several methodologies for synthesis of MOFs have been developed which rely on use of predetermined building blocks. The work presented herein is focused on the utilization of two of these design principles, namely the use of molecular building blocks (MBBs) and supermolecular building blocks (SBBs) to target MOF materials having desired connectivities (topologies). These design strategies also permit the introduction of specific chemical moieties, allowing for modification of the MOFs properties. This research is predominantly focused on two platforms (rht-MOFs and ftw-MOFs) which topologically speaking are edge transitive binodal nets; ftw being a (4,12)-connected net and rht being a (3,24)-connected net. These highly connected nets (at least one node having connectivity greater than eight) have been purposefully targeted to increase the predictability of structural outcome. A general trend in topology is that there is an inverse relationship between the connectivity of the node(s) and the number of topological outcomes. Therefore the key to this research (and to effective use of the SBB and MBB approaches) is identification of conditions which allow for reliable formation of the targeted MBBs and SBBs. In the case of the research presented herein: a 12-connected Group IV or Rare Earth based hexanuclear MBB and a 24-connected transition metal based SBB were successfully targeted and synthesized. These two synthetic platforms will be presented and used as examples of how these design methods have been (and can be further) utilized to modify existing materials or develop new materials for gas storage and

  8. Reticular synthesis of HKUST-like tbo MOFs with enhanced CH4 storage

    KAUST Repository

    Spanopoulos, Ioannis; Tsangarakis, Constantinos; Klontzas, Emmanuel; Tylianakis, Emmanuel; Froudakis, George; Adil, Karim; Belmabkhout, Youssef; Eddaoudi, Mohamed; Trikalitis, Pantelis N.

    2015-01-01

    Successful implementation of reticular chemistry using a judiciously designed rigid octatopic carboxylate organic linker allowed the construction of expanded HKUST-1-like tbo-MOF series with intrinsic strong CH4 adsorption sites. The Cu-analogue displayed a concomitant enhancement of the gravimetric and volumetric surface area with the highest reported CH4 uptake among the tbo family, comparable to the best performing MOFs for CH4 storage. The corresponding gravimetric (BET) and volumetric surface area of 3971 m2 g-1 and 2363 m2 cm-3 represent an increase of respectively 115 % and 47 % in comparison to the corresponding values for the prototypical HKUST-1 (tbo-MOF-1), and 42 % and 20 % higher than tbo-MOF-2. High pressure methane adsorption isotherms revealed a high total gravimetric and volumetric CH4 uptakes, reaching 372 cm3 (STP) g-1 and 221 cm3 (STP) cm-3 respectively at 85 bar and 298 K. The corresponding working capacities between 5-80 bar were found to be 294 cm3 (STP) g-1 and 175 cm3 (STP) cm-3 and are placed among the best performing MOFs for CH4 storage particularly at relatively low temperature (e.g. 326 cm3 (STP) g-1 and 194 cm3 (STP) cm-3 at 258 K). To better understand the structure-property relationship and gain insight on the mechanism accounting for the resultant enhanced CH4 storage capacity, molecular simulation study was performed and revealed the presence of very strong CH4 adsorption sites at the vicinity of the organic linker with similar adsorption energetics as the open metal sites. The present findings supports the potential of tbo-MOFs based on the supermolecular building layer (SBL) approach as an ideal platform to further enhance the CH4 storage capacity via expansion and functionalization of the quadrangular pillars.

  9. Postmodification of MOF-5 using secondary complex formation using 8- hydroxyquinoline (HOQ) for the development of visible light active photocatalysts

    Science.gov (United States)

    Thakare, Sanjay R.; Ramteke, Shruti M.

    2018-05-01

    A novel HOQ@MOF-5 compound photocatalyst was successfully constructed by interacting 8- Hydroxyquinoline with MOF-5 synthesized through a room temperature method. The secondary complex formation between the Zn cluster with 8-Hydroxyquinoline harnessed visible light and acted as a mediator to transfer photoinduced electrons to MOF-5 for enhancing the photocatalytic reaction rate with visible light. HOQ@MOF-5 was characterized by various spectroscopic techniques, such as XRD showing the crystalline nature of compound, UV-Visible spectroscopy showing the 2.54 eV band gap of HOQ@MOF-5 and morphological analysis tools, such as the nanoparticle nature of the compound with 9.561 nm particle size. The photocatalytic effect was estimated using the photocatalytic degradation of phenol as a representative organic pollutant under visible light irradiation. This work provides a new compound acting as source of electrons transfer for the development of efficient photocatalysts for remediation of environmental pollution.

  10. Conductividad superprotónica en MOFs metaloporfirínicos bioinspirados

    OpenAIRE

    Fidalgo Marijuan, Arkaitz; Amayuelas López, Eder; Barandika Argoitia, Miren Gotzone; Bazán Blau, Begoña del Pilar; Urtiaga Greaves, Miren Karmele; Ruiz de Larramendi Villanueva, Idoia; Arriortua Marcaida, María Isabel

    2017-01-01

    Comunicacion oral a la X Reunión Científica de Bioinorgánica, BioBilbao 2017. Bilbao 9-12 de julio de 2017 - Bizkaia Aretoa - Paraninfo de la UPV/EHU Los materiales de tipo MOF muestran un gran potencial para una amplia gama de aplicaciones debido a su elevada porosidad, baja densidad y facilidad en la modificación estructural. En particular, los MOF basados en metaloporfirinas están adquiriendo gran importancia en muchos campos. Estos materiales se inspiran en las funciones bioló...

  11. The unique rht-MOF platform, ideal for pinpointing the functionalization and CO 2 adsorption relationship

    KAUST Repository

    Luebke, Ryan

    2012-01-01

    The uniqueness of the rht-MOF platform, based on the singular (3,24)-connected net, allows for the facile design and synthesis of functionalized materials for desired applications. Here we designed a nitrogen-rich trefoil hexacarboxylate (trigonal tri-isophthalate) ligand, which serves to act as the trigonal molecular building block while concurrently coding the formation of the targeted truncated cuboctahedral supermolecular building block (in situ), and enhancing the CO 2 uptake in the resultant rht-MOF. © 2012 The Royal Society of Chemistry.

  12. Functionalized ultra-porous titania nanofiber membranes as nuclear waste separation and sequestration scaffolds for nuclear fuels recycle.

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Haiqing; Bell, Nelson S; Cipiti, Benjamin B.; Lewis, Tom Goslee,; Sava, Dorina Florentina; Nenoff, Tina Maria

    2012-09-01

    Advanced nuclear fuel cycle concept is interested in reducing separations to a simplified, one-step process if possible. This will benefit from the development of a one-step universal getter and sequestration material so as a simplified, universal waste form was proposed in this project. We have developed a technique combining a modified sol-gel chemistry and electrospinning for producing ultra-porous ceramic nanofiber membranes with controllable diameters and porous structures as the separation/sequestration materials. These ceramic nanofiber materials have been determined to have high porosity, permeability, loading capacity, and stability in extreme conditions. These porous fiber membranes were functionalized with silver nanoparticles and nanocrystal metal organic frameworks (MOFs) to introduce specific sites to capture gas species that are released during spent nuclear fuel reprocessing. Encapsulation into a durable waste form of ceramic composition was also demonstrated.

  13. Hierarchical Porous Structures

    Energy Technology Data Exchange (ETDEWEB)

    Grote, Christopher John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-06-07

    Materials Design is often at the forefront of technological innovation. While there has always been a push to generate increasingly low density materials, such as aero or hydrogels, more recently the idea of bicontinuous structures has gone more into play. This review will cover some of the methods and applications for generating both porous, and hierarchically porous structures.

  14. Boiling in porous media

    International Nuclear Information System (INIS)

    1998-01-01

    This conference day of the French society of thermal engineers was devoted to the analysis of heat transfers and fluid flows during boiling phenomena in porous media. This book of proceedings comprises 8 communications entitled: 'boiling in porous medium: effect of natural convection in the liquid zone'; 'numerical modeling of boiling in porous media using a 'dual-fluid' approach: asymmetrical characteristic of the phenomenon'; 'boiling during fluid flow in an induction heated porous column'; 'cooling of corium fragment beds during a severe accident. State of the art and the SILFIDE experimental project'; 'state of knowledge about the cooling of a particulates bed during a reactor accident'; 'mass transfer analysis inside a concrete slab during fire resistance tests'; 'heat transfers and boiling in porous media. Experimental analysis and modeling'; 'concrete in accidental situation - influence of boundary conditions (thermal, hydric) - case studies'. (J.S.)

  15. Assembly of [Cu2(COO)4] and [M3(μ3-O)(COO)6] (M = Sc, Fe, Ga, and In) building blocks into porous frameworks towards ultra-high C2H2/CO2 and C2H2/CH4 separation performance.

    Science.gov (United States)

    Zhang, Jian-Wei; Hu, Man-Cheng; Li, Shu-Ni; Jiang, Yu-Cheng; Qu, Peng; Zhai, Quan-Guo

    2018-02-20

    A porous MOF platform (SNNU-65s) formed by creatively combining paddle-wheel-like [Cu 2 (COO) 4 ] and trigonal prismatic [M 3 (μ 3 -O)(COO) 6 ] building blocks was designed herein. The mixed and high-density open metal sites and the OH-functionalized pore surface promote SNNU-65s to exhibit ultra-high C 2 H 2 uptake and separation performance. Impressively, SNNU-65-Cu-Ga stands out for the highest C 2 H 2 /CO 2 (18.7) and C 2 H 2 /CH 4 (120.6) selectivity among all the reported MOFs at room temperature.

  16. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-08-22

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  17. Fabrication of Fe3O4@CuO core-shell from MOF based materials and its antibacterial activity

    International Nuclear Information System (INIS)

    Rajabi, S.K.; Sohrabnezhad, Sh.; Ghafourian, S.

    2016-01-01

    Magnetic Fe 3 O 4 @CuO nanocomposite with a core/shell structure was successfully synthesized via direct calcinations of magnetic Fe 3 O 4 @HKUST-1 in air atmosphere. The morphology, structure, magnetic and porous properties of the as-synthesized nano composites were characterized by using scanning electron microscope (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), and vibration sample magnetometer (VSM). The results showed that the nanocomposite material included a Fe 3 O 4 core and a CuO shell. The Fe 3 O 4 @CuO core-shell can be separated easily from the medium by a small magnet. The antibacterial activity of Fe 3 O 4 -CuO core-shell was investigated against gram-positive and gram-negative bacteria. A new mechanism was proposed for inactivation of bacteria over the prepared sample. It was demonstrated that the core-shell exhibit recyclable antibacterial activity, acting as an ideal long-acting antibacterial agent. - Graphical abstract: Fe 3 O 4 @CuO core-shell release of copper ions. These Cu 2+ ions were responsible for the exhibited antibacterial activity. - Highlights: • The Fe 3 O 4 @CuO core-shell was prepared by MOF method. • This is the first study of antibacterial activity of core-shell consist of CuO and Fe 3 O 4 . • The core-shell can be reused effectively. • Core-shell was separated from the reaction solution by external magnetic field.

  18. Review on processing of metal-organic framework (MOF) materials towards system integration for hydrogen storage

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2014-09-01

    Full Text Available materials to form part of a practical hydrogen storage system, knowledge of the ‘processing’ techniques to improve the properties of the powders is essential. However, the processing routes of MOF materials towards system integration are rarely reviewed...

  19. Mixed matrix formulations with MOF molecular sieving for key energy-intensive separations

    KAUST Repository

    Liu, Gongping

    2018-02-09

    Membrane-based separations can improve energy efficiency and reduce the environmental impacts associated with traditional approaches. Nevertheless, many challenges must be overcome to design membranes that can replace conventional gas separation processes. Here, we report on the incorporation of engineered submicrometre-sized metal–organic framework (MOF) crystals into polymers to form hybrid materials that successfully translate the excellent molecular sieving properties of face-centred cubic (fcu)-MOFs into the resultant membranes. We demonstrate, simultaneously, exceptionally enhanced separation performance in hybrid membranes for two challenging and economically important applications: the removal of CO2 and H2S from natural gas and the separation of butane isomers. Notably, the membrane molecular sieving properties demonstrate that the deliberately regulated and contracted MOF pore-aperture size can discriminate between molecular pairs. The improved performance results from precise control of the linkers delimiting the triangular window, which is the sole entrance to the fcu-MOF pore. This rational-design hybrid approach provides a general toolbox for enhancing the transport properties of advanced membranes bearing molecular sieve fillers with sub-nanometre-sized pore-apertures.

  20. Charge-transfer-based terbium MOF nanoparticles as fluorescent pH sensor for extreme acidity.

    Science.gov (United States)

    Qi, Zewan; Chen, Yang

    2017-01-15

    Newly emerged metal organic frameworks (MOFs) have aroused the great interest in designing functional materials by means of its flexible structure and component. In this study, we used lanthanide Tb 3+ ions and small molecular ligands to design and assemble a kind of pH-sensitive MOF nanoparticle based on intramolecular-charge-transfer effect. This kind of made-to-order MOF nanoparticle for H + is highly specific and sensitive and could be used to fluorescently indicate pH value of strong acidic solution via preset mechanism through luminescence of Tb 3+ . The long luminescence lifetime of Tb 3+ allows eliminating concomitant non-specific fluorescence by time-revised fluorescence techniques, processing an advantage in sensing H + in biological media with strong autofluorescence. Our method showed a great potential of MOF structures in designing and constructing sensitive sensing materials for specific analytes directly via the assembly of functional ions/ligands. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. MISTRAL : A Language for Model Transformations in the MOF Meta-modeling Architecture

    NARCIS (Netherlands)

    Kurtev, Ivan; van den Berg, Klaas; Aßmann, Uwe; Aksit, Mehmet; Rensink, Arend

    2005-01-01

    n the Meta Object Facility (MOF) meta-modeling architecture a number of model transformation scenarios can be identified. It could be expected that a meta-modeling architecture will be accompanied by a transformation technology supporting the model transformation scenarios in a uniform way. Despite

  2. Mixed matrix formulations with MOF molecular sieving for key energy-intensive separations

    KAUST Repository

    Liu, Gongping; Chernikova, Valeriya; Liu, Yang; Zhang, Kuang; Belmabkhout, Youssef; Shekhah, Osama; Zhang, Chen; Yi, Shouliang; Eddaoudi, Mohamed; Koros, William J.

    2018-01-01

    Membrane-based separations can improve energy efficiency and reduce the environmental impacts associated with traditional approaches. Nevertheless, many challenges must be overcome to design membranes that can replace conventional gas separation processes. Here, we report on the incorporation of engineered submicrometre-sized metal–organic framework (MOF) crystals into polymers to form hybrid materials that successfully translate the excellent molecular sieving properties of face-centred cubic (fcu)-MOFs into the resultant membranes. We demonstrate, simultaneously, exceptionally enhanced separation performance in hybrid membranes for two challenging and economically important applications: the removal of CO2 and H2S from natural gas and the separation of butane isomers. Notably, the membrane molecular sieving properties demonstrate that the deliberately regulated and contracted MOF pore-aperture size can discriminate between molecular pairs. The improved performance results from precise control of the linkers delimiting the triangular window, which is the sole entrance to the fcu-MOF pore. This rational-design hybrid approach provides a general toolbox for enhancing the transport properties of advanced membranes bearing molecular sieve fillers with sub-nanometre-sized pore-apertures.

  3. Metal organic framework synthesis in the presence of surfactants : Towards hierarchical MOFs?

    NARCIS (Netherlands)

    Seoane, B.; Dikhtiarenko, A.; Mayoral, A.; Tellez, C.; Coronas, J.; Kapteijn, F.; Gascon, J.

    2015-01-01

    The effect of synthesis pH and H2O/EtOH molar ratio on the textural properties of different aluminium trimesate metal organic frameworks (MOFs) prepared in the presence of the well-known cationic surfactant cetyltrimethylammonium bromide (CTAB) at 120 °C was studied with the purpose of obtaining a

  4. Mixed matrix formulations with MOF molecular sieving for key energy-intensive separations

    Science.gov (United States)

    Liu, Gongping; Chernikova, Valeriya; Liu, Yang; Zhang, Kuang; Belmabkhout, Youssef; Shekhah, Osama; Zhang, Chen; Yi, Shouliang; Eddaoudi, Mohamed; Koros, William J.

    2018-03-01

    Membrane-based separations can improve energy efficiency and reduce the environmental impacts associated with traditional approaches. Nevertheless, many challenges must be overcome to design membranes that can replace conventional gas separation processes. Here, we report on the incorporation of engineered submicrometre-sized metal-organic framework (MOF) crystals into polymers to form hybrid materials that successfully translate the excellent molecular sieving properties of face-centred cubic (fcu)-MOFs into the resultant membranes. We demonstrate, simultaneously, exceptionally enhanced separation performance in hybrid membranes for two challenging and economically important applications: the removal of CO2 and H2S from natural gas and the separation of butane isomers. Notably, the membrane molecular sieving properties demonstrate that the deliberately regulated and contracted MOF pore-aperture size can discriminate between molecular pairs. The improved performance results from precise control of the linkers delimiting the triangular window, which is the sole entrance to the fcu-MOF pore. This rational-design hybrid approach provides a general toolbox for enhancing the transport properties of advanced membranes bearing molecular sieve fillers with sub-nanometre-sized pore-apertures.

  5. A stable Alq3@MOF composite for white-light emission.

    Science.gov (United States)

    Xie, Wei; He, Wen-Wen; Du, Dong-Ying; Li, Shun-Li; Qin, Jun-Sheng; Su, Zhong-Min; Sun, Chun-Yi; Lan, Ya-Qian

    2016-02-25

    A stable mesoporous blue-emitting MOF NENU-521 was successfully constructed. NENU-521 can serve as a host for encapsulating Alq3 to obtain tunable and efficient white-light emission. The Alq3@NENU-521 composite possesses excellent stability and can be used as a promising white phosphor in WLEDs.

  6. Ethene/ethane separation by the MOF membrane ZIF-8: Molecular correlation of permeation, adsorption, diffusion

    NARCIS (Netherlands)

    Bux, H.; Chmelik, C.; Krishna, R.; Caro, J.

    2011-01-01

    The newly developed MOF membrane ZIF-8 separates an equimolar ethene/ethane mixture at room temperature for 1 and 6 bar feed pressure, respectively, with a selectivity of 2.8 and 2.4. Independent sorption uptake studies of an ethene/ethane mixture on a big ZIF-8 single crystal by IR microscopy

  7. The studies on gas adsorption properties of MIL-53 series MOFs materials

    Directory of Open Access Journals (Sweden)

    Yuqiu Jiao

    2017-08-01

    Full Text Available Molecular dynamics (MD, grand canonical Monte Carlo (GCMC and ideal adsorbed solution theory (IAST were used to study the structures and gas adsorption properties of MIL-53(M[M=Cr, Fe, Sc, Al] metal organic framework (MOF materials. The results show that the volumes of those MOF materials increase significantly at high temperature. By analyzing the adsorption isotherms, we found that the temperature had a paramount effect on the gas adsorption behaviors of these MOF materials. For MIL-53(Cr, the orders of the quantities of adsorbed gases were CH4>N2>CO2>H2S, CH4>H2S>CO2>N2 and CH4>CO2>H2S>N2 at 100K, 293K and 623K, respectively. We also calculated the adsorption of several combinations of two gases by MIL-53(Cr at 293K, the results indicate that the material had selective adsorption of CH4 over CO2, H2S and N2. Our calculations provide microscopic insights into the gas adsorption performances of these MOFs and may further guide the practice of gas separation.

  8. Synthesis of rGO/Zr-MOF composite for hydrogen storage application

    CSIR Research Space (South Africa)

    Musyoka, Nicholas M

    2017-11-01

    Full Text Available A composite material consisting of Zr-based metal organic framework (Zr-MOF) and reduced graphene oxide (rGO) was successfully synthesized by an in situ method. The aim of the study was to transfer some of the graphene's attractive properties...

  9. The studies on gas adsorption properties of MIL-53 series MOFs materials

    Science.gov (United States)

    Jiao, Yuqiu; Li, Zhenyu; Ma, Yue; Zhou, Guanggang; Wang, Shuangxi; Lu, Guiwu

    2017-08-01

    Molecular dynamics (MD), grand canonical Monte Carlo (GCMC) and ideal adsorbed solution theory (IAST) were used to study the structures and gas adsorption properties of MIL-53(M)[M=Cr, Fe, Sc, Al] metal organic framework (MOF) materials. The results show that the volumes of those MOF materials increase significantly at high temperature. By analyzing the adsorption isotherms, we found that the temperature had a paramount effect on the gas adsorption behaviors of these MOF materials. For MIL-53(Cr), the orders of the quantities of adsorbed gases were CH4>N2>CO2>H2S, CH4>H2S>CO2>N2 and CH4>CO2>H2S>N2 at 100K, 293K and 623K, respectively. We also calculated the adsorption of several combinations of two gases by MIL-53(Cr) at 293K, the results indicate that the material had selective adsorption of CH4 over CO2, H2S and N2. Our calculations provide microscopic insights into the gas adsorption performances of these MOFs and may further guide the practice of gas separation.

  10. 5-fold increase of hydrogen uptake in MOF74 through linker decorations

    Science.gov (United States)

    Thonhauser, T.; Zuluaga, S.; Harrison, D.; Welchman, E.; Arter, C.

    We present ab initio results for linker decorations in Mg-MOF74-i.e. attaching various metals  = Li, Na, K, Sc, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Pd, Ag, and Pt near the ring of the linker-creating new strong adsorption sites and thus maximizing small molecule uptake. We find that in most cases these decorations influence the overall form and structure of Mg-MOF74 only marginally. After the initial screening we chose metals that bind favorably to the linker and further investigate adsorption of H2, CO2, and H2O for  = Li, Na, K, and Sc. For the case of H2 we show that up to 24 additional guest molecules can be adsorbed in the MOF unit cell, with binding energies comparable to the original open-metal sites at the six corners of the channel. This leads to a 5-fold increase of the molecule uptake in Mg-MOF74, with tremendous impact on many applications in general and hydrogen storage in particular-where the gravimetric hydrogen density increases from 1 . 63 mass% to 7 . 28 mass% and the volumetric density from 15.10 g H2 L-1 to 75.50 g H2 L-1. This work was supported by NSF Grant No. DMR-1145968.

  11. Fivefold increase of hydrogen uptake in MOF74 through linker decorations

    Science.gov (United States)

    Arter, C. A.; Zuluaga, S.; Harrison, D.; Welchman, E.; Thonhauser, T.

    2016-10-01

    We present ab initio results for linker decorations in Mg-MOF74, i.e., attaching various metals M =Li, Na, K, Sc, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Pd, Ag, and Pt near the ring of the linker, creating new strong adsorption sites and thus maximizing small-molecule uptake. We find that in most cases these decorations influence the overall form and structure of Mg-MOF74 only marginally. After the initial screening, we chose metals that bind favorably to the linker and further investigated adsorption of H2,CO2, and H2O for M =Li , Na, K, and Sc. For the case of H2 we show that up to 24 additional guest molecules can be adsorbed in the metal-organic framework (MOF) unit cell, with binding energies comparable to the original open-metal sites at the six corners of the channel. This leads to a fivefold increase of the molecule uptake in Mg-MOF74, with tremendous impact on many applications in general and hydrogen storage in particular, where the gravimetric hydrogen density increases from 1.63 to 7.28 mass % and the volumetric density increases from 15.10 to 75.50 g H2L-1 .

  12. Fabricating porous silicon carbide

    Science.gov (United States)

    Shor, Joseph S. (Inventor); Kurtz, Anthony D. (Inventor)

    1994-01-01

    The formation of porous SiC occurs under electrochemical anodization. A sample of SiC is contacted electrically with nickel and placed into an electrochemical cell which cell includes a counter electrode and a reference electrode. The sample is encapsulated so that only a bare semiconductor surface is exposed. The electrochemical cell is filled with an HF electrolyte which dissolves the SiC electrochemically. A potential is applied to the semiconductor and UV light illuminates the surface of the semiconductor. By controlling the light intensity, the potential and the doping level, a porous layer is formed in the semiconductor and thus one produces porous SiC.

  13. Gaining Insights on the H2–Sorbent Interactions: Robust soc-MOF Platform as a Case Study

    KAUST Repository

    Cairns, Amy

    2016-09-18

    We report on the synthesis and gas adsorption properties (i.e., Ar and H2) of four robust 3-periodic metal–organic frameworks (MOFs) having the targeted soc topology. These cationic MOFs are isostructural to the parent indium-based MOF, In-soc-MOF-1a (for NO3–), previously reported by us, and likewise are constructed from the assembly of rigid μ3-oxygen-centered trinuclear metal carboxylate clusters, [M3O(O2C−)6], where M = In3+ or Fe3+. Each inorganic trinuclear molecular building block (MBB), generated in situ, is bridged by six 3,3′,5,5′-azobenzenetetracarboxylate (ABTC4–) ligands to give the extended (4,6)-connected MOF, soc-MOF. In our previous work, we confirmed that the parent soc-MOF, i.e., In-soc-MOF-1a, possesses unique structural characteristics (e.g., vacant In binding sites and narrow pores with higher localized charge density), which led to exceptional hydrogen (H2) storage capabilities. Therefore, charged MOFs with soc topology can be viewed collectively as an ideal prototypical platform to examine the impact of specific structural parameters on H2–MOF interactions via systematic gas adsorption studies. We infer that enhanced binding of molecular H2 is primarily governed by the presence and type of vacant metal centers (i.e., Fe was shown to exhibit stronger H2–MOF interactions at low H2 loading compared to the In analogues). These findings are evident from the associated isosteric heat of adsorption (Qst) at low loadings and inelastic neutron scattering (INS) experiments of the rotational transitions of sorbed H2, as well as, temperature-programmed desorption (TPD) studies (for a select compound). The importance of localized charge density is also highlighted, where the extra-framework nitrate anions in the Fe-soc-MOF-1a (for NO3–) facilitate enhanced binding affinities as compared to the chloride analogue.

  14. Investigation of prototypal MOFs consisting of polyhedral cages with accessible Lewis-acid sites for quinoline synthesis.

    Science.gov (United States)

    Gao, Wen-Yang; Leng, Kunyue; Cash, Lindsay; Chrzanowski, Matthew; Stackhouse, Chavis A; Sun, Yinyong; Ma, Shengqian

    2015-03-21

    A series of prototypal metal-organic frameworks (MOFs) consisting of polyhedral cages with accessible Lewis-acid sites, have been systematically investigated for Friedländer annulation reaction, a straightforward approach to synthesizing quinoline and its derivatives. Amongst them MMCF-2 demonstrates significantly enhanced catalytic activity compared with the benchmark MOFs, HKUST-1 and MOF-505, as a result of a high-density of accessible Cu(II) Lewis acid sites and large window size in the cuboctahedral cage-based nanoreactor of MMCF-2.

  15. Stochastic porous media equations

    CERN Document Server

    Barbu, Viorel; Röckner, Michael

    2016-01-01

    Focusing on stochastic porous media equations, this book places an emphasis on existence theorems, asymptotic behavior and ergodic properties of the associated transition semigroup. Stochastic perturbations of the porous media equation have reviously been considered by physicists, but rigorous mathematical existence results have only recently been found. The porous media equation models a number of different physical phenomena, including the flow of an ideal gas and the diffusion of a compressible fluid through porous media, and also thermal propagation in plasma and plasma radiation. Another important application is to a model of the standard self-organized criticality process, called the "sand-pile model" or the "Bak-Tang-Wiesenfeld model". The book will be of interest to PhD students and researchers in mathematics, physics and biology.

  16. Positronium formation in porous materials for antihydrogen production

    International Nuclear Information System (INIS)

    Ferragut, R; Calloni, A; Dupasquier, A; Consolati, G; Giammarchi, M G; Quasso, F; Trezzi, D; Egger, W; Ravelli, L; Petkov, M P; Jones, S M; Wang, B; Yaghi, O M; Jasinska, B; Chiodini, N; Paleari, A

    2010-01-01

    Positronium (Ps) formation measurements in several porous materials as: Vycor, germanate Xerogel, Metal-Organic Frameworks MOF-177 and Aerogel with two densities (20 and 150 mg/cm 3 ), were performed by means of a variable energy positron beam provided with a Ge detector and a positron lifetime spectrometer. An efficient formation of cooled Ps atoms is a requisite for the production of antihydrogen, with the aim of a direct measurement of the Earth gravitational acceleration g of antimatter, which is a primary scientific goal of AEGIS (Antimatter Experiment: Gravity, Interferometry, Spectroscopy). Porous materials are necessary to form a high yield of Ps atoms as well as to cool Ps through collisions with the inner walls of the pores. The different materials were characterized and produce Ps into the pores. Lifetime measurements give an estimation of the typical pores dimension of the substances. A comparative study of the positron lifetime and the Ps fraction values in the above mentioned materials indicates that silica Aerogel, with the appropriate density, is an excellent candidate for an efficient formation of cold Ps atoms for the AEGIS project.

  17. Synthesis and Characterization of Metal-Organic Frameworks (MOFs) for Photon Collection and Energy Transfer

    Science.gov (United States)

    So, Monica C.

    . To address problem (a), we incorporated antenna molecules (i.e. perylene diimides) to expand light collection and then transfer energy to the primary chromophores. To address problem (b), we observed that excitons can achieve up to 2,025 hops in a porphyrin-based metal-organic framework (MOF) single crystal within its 3 ns lifetime. By precisely aligning the chromophores in the MOF, we showed that long-distance exciton transport (i.e. ultra-fast, sequential hopping) was consistent with the well-established Forster theory. To address problems (c) and (d), we introduced MOF components one step at a time to optimize optical path length and crystal-thickness. This allowed us to incorporate MOFs (normally bulk crystals) into a MOF film. The approach exploited both MOF chemistry and layer-by-layer (LbL) assembly of crystalline MOFs in a highly controlled fashion on functional surfaces. We also incorporated good light-harvesting molecules as struts in MOFs to increase the visible absorption. Designing MOF-based OPVs can provide insight into solar energy conversion. This can potentially lead to much higher efficiencies, based on the simultaneous resolution of the four challenges hindering OPV performance.

  18. Synthesis of a 3D lanthanum(III) MOFs as a multi-chemosensor to Cr(VI)-containing anion and Fe(III) cation based on a flexible ligand

    Science.gov (United States)

    Ma, Yang-Min; Liu, Tong; Huang, Wen-Huan

    2018-02-01

    Based on La(NO3)3·6H2O and 4,4‧-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid (H3cpbda), a 3D porous MOFs, [La(cpbda)(H2O)1.5]n (1), was synthesized by hydrothermal method and further characterized by single-crystal X-ray diffraction, power X-ray diffraction, IR spectroscopy, thermal-gravimetric analysis and fluorescence spectroscopy. Owing to its good stabilities and fluorescence property, the sensing experiments on sixteen cations and eleven anions were implemented. Moreover, the further titration processes show 1 can sensitively detect the Fe(III) cation and Cr(VI)-containing anions by quenching responses.

  19. Molecular simulations of MOF membranes for separation of ethane/ethene and ethane/methane mixtures† †Electronic supplementary information (ESI) available: List of the MOFs studied in this work and their structural properties. Potential parameters of gas molecules used in the simulations. See DOI: 10.1039/c7ra11562h

    Science.gov (United States)

    Altintas, Cigdem

    2017-01-01

    Metal organic framework (MOF) membranes have been widely investigated for gas separation applications. Several MOFs have been recently examined for selective separation of C2H6. Considering the large number of available MOFs, it is not possible to fabricate and test the C2H6 separation performance of every single MOF membrane using purely experimental methods. In this study, we used molecular simulations to assess the membrane-based C2H6/C2H4 and C2H6/CH4 separation performances of 175 different MOF structures. This is the largest number of MOF membranes studied to date for C2H6 separation. We computed adsorption selectivity, diffusion selectivity, membrane selectivity and gas permeability of MOFs for C2H6/C2H4 and C2H6/CH4 mixtures. Our results show that a significant number of MOF membranes are C2H6 selective for C2H6/C2H4 separation in contrast to traditional nanoporous materials. Selectivity and permeability of MOF membranes were compared with other membrane materials, such as polymers, zeolites, and carbon molecular sieves. Several MOFs were identified to exceed the upper bound established for polymeric membranes and many MOF membranes exhibited higher gas permeabilities than zeolites and carbon molecular sieves. Examining the structure–performance relations of MOF membranes revealed that MOFs with cavity diameters between 6 and 9 Å, porosities lower than 0.50, and surface areas between 500–1000 m2 g–1 have high C2H6 selectivities. The results of this study will be useful to guide the experiments to the most promising MOF membranes for efficient separation of C2H6 and to accelerate the development of new MOFs with high C2H6 selectivities. PMID:29308193

  20. Ultra-Tuning of the Rare-Earth fcu-MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins

    KAUST Repository

    Assen, Ayalew Hussen Assen; Belmabkhout, Youssef; Adil, Karim; Bhatt, Prashant; Xue, Dongxu; Jiang, Hao; Eddaoudi, Mohamed

    2015-01-01

    , namely fumarate, to bridge the 12-connected RE hexanuclear clusters has afforded the contraction of the well-defined RE-fcu-MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed

  1. Quest for Highly-connected MOF Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs.

    KAUST Repository

    Alezi, Dalal; Peedikakkal, Abdul Malik P.; Weselinski, Lukasz Jan; Guillerm, Vincent; Belmabkhout, Youssef; Cairns, Amy; Chen, Zhijie; Wojtas, Lukasz; Eddaoudi, Mohamed

    2015-01-01

    that RE-MOFs with double six-membered ring (d6R) secondary building units are isolated, representing therefore a critical step forward toward the design of novel and highly coordinated materials using the supermolecular building layer approach while

  2. Simulations of hydrogen sorption in rht-MOF-1: identifying the binding sites through explicit polarization and quantum rotation calculations

    KAUST Repository

    Pham, Tony; Forrest, Katherine A.; Hogan, Adam; McLaughlin, Keith; Belof, Jonathan L.; Eckert, Juergen; Space, Brian

    2014-01-01

    . This is a charged rht-MOF that contains extra-framework nitrate counterions within the material. For the simulations performed herein, excellent agreement with experiment was achieved for the simulated hydrogen sorption isotherms and calculated isosteric

  3. Versatile Rare Earth Hexanuclear Clusters for the Design and Synthesis of Highly-connected ftw-MOFs

    KAUST Repository

    Eddaoudi, Mohamed; Luebke, Ryan; Belmabkhout, Youssef; Wojtas, Lukasz; Weseliński, Łukasz; Alkordi, Mohamed Helmi; Norton, George; Cairns, Amy; Adil, Karim

    2015-01-01

    ftw-MOF platform offers potential to assess the effect of pore functionality and size, via ligand functionalization and/or expansion, on adsorption properties of relevant gases. Examination of gas adsorption properties of these compounds showed

  4. Systematic modulation and enhancement of CO{sub 2} : N{sub 2} selectivity and water stability in an isoreticular series of bio-MOF-11 analogues

    Energy Technology Data Exchange (ETDEWEB)

    Li, Tao; Chen, De-Li; Sullivan, Jeanne E.; Kozlowski, Mark T.; Johnson, J Karl; Rosi, Nathaniel L.

    2013-02-01

    An isoreticular series of cobalt-adeninate bio-MOFs (bio-MOFs 11-14) is reported. The pores of bio-MOFs 11-14 are decorated with acetate, propionate, butyrate, and valerate, respectively. The nitrogen (N{sub 2}) and carbon dioxide (CO{sub 2}) adsorption properties of these materials are studied and compared. The isosteric heats of adsorption for CO{sub 2} are calculated, and the CO{sub 2}:N{sub 2} selectivities for each material are 10 determined. As the lengths of the aliphatic chains decorating the pores in bio-MOFs 11-14 increase, the BET surface areas decrease from 1148 m{sup 2}/g to 17 m{sup 2}/g while the CO{sub 2}:N{sub 2} selectivities predicted from ideal adsorbed solution theory at 1 bar and 273 K for a 10:90 CO{sub 2}:N{sub 2} mixture range from 73:1 for bio-MOF-11 to 123:1 for bio-MOF-12 and finally to 107:1 for bio-MOF-13. At 298 K, the selectivities are 43:1 for bio-MOF-11, 52:1 for bio-MOF-12, and 40:1 for bio-MOF-13. Additionally, it is shown that 15 bio-MOF-14 exhibits a unique molecular sieving property that allows it to adsorb CO{sub 2} but not N{sub 2} at 273 and 298 K. Finally, the water stability of bio-MOFs 11-14 increases with increasing aliphatic chain length. Bio-MOF-14 exhibits no loss of crystallinity or porosity after soaking in water for one month.

  5. Multi-Column Experimental Test Bed Using CaSDB MOF for Xe/Kr Separation

    Energy Technology Data Exchange (ETDEWEB)

    Welty, Amy Keil [Idaho National Lab. (INL), Idaho Falls, ID (United States); Greenhalgh, Mitchell Randy [Idaho National Lab. (INL), Idaho Falls, ID (United States); Garn, Troy Gerry [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2016-03-01

    Processing of spent nuclear fuel produces off-gas from which several volatile radioactive components must be separated for further treatment or storage. As part of the Off-gas Sigma Team, parallel research at INL and PNNL has produced several promising sorbents for the selective capture of xenon and krypton from these off-gas streams. In order to design full-scale treatment systems, sorbents that are promising on a laboratory scale must be proven under process conditions to be considered for pilot and then full-scale use. To that end, a bench-scale multi-column system with capability to test multiple sorbents was designed and constructed at INL. This report details bench-scale testing of CaSDB MOF, produced at PNNL, and compares the results to those reported last year using INL engineered sorbents. Two multi-column tests were performed with the CaSDB MOF installed in the first column, followed with HZ-PAN installed in the second column. The CaSDB MOF column was placed in a Stirling cryocooler while the cryostat was employed for the HZ-PAN column. Test temperatures of 253 K and 191 K were selected for the first column while the second column was held at 191 K for both tests. Calibrated volume sample bombs were utilized for gas stream analyses. At the conclusion of each test, samples were collected from each column and analyzed for gas composition. While CaSDB MOF does appear to have good capacity for Xe, the short time to initial breakthrough would make design of a continuous adsorption/desorption cycle difficult, requiring either very large columns or a large number of smaller columns. Because of the tenacity with which Xe and Kr adhere to the material once adsorbed, this CaSDB MOF may be more suitable for use as a long-term storage solution. Further testing is recommended to determine if CaSDB MOF is suitable for this purpose.

  6. Cation Exchange Strategy for the Encapsulation of a Photoactive CO-Releasing Organometallic Molecule into Anionic Porous Frameworks.

    Science.gov (United States)

    Carmona, Francisco J; Rojas, Sara; Sánchez, Purificación; Jeremias, Hélia; Marques, Ana R; Romão, Carlos C; Choquesillo-Lazarte, Duane; Navarro, Jorge A R; Maldonado, Carmen R; Barea, Elisa

    2016-07-05

    The encapsulation of the photoactive, nontoxic, water-soluble, and air-stable cationic CORM [Mn(tacn)(CO)3]Br (tacn = 1,4,7-triazacyclononane) in different inorganic porous matrixes, namely, the metalorganic framework bio-MOF-1, (NH2(CH3)2)2[Zn8(adeninate)4(BPDC)6]·8DMF·11H2O (BPDC = 4,4'-biphenyldicarboxylate), and the functionalized mesoporous silicas MCM-41-SO3H and SBA-15-SO3H, is achieved by a cation exchange strategy. The CO release from these loaded materials, under simulated physiological conditions, is triggered by visible light. The results show that the silica matrixes, which are unaltered under physiological conditions, slow the kinetics of CO release, allowing a more controlled CO supply. In contrast, bio-MOF-1 instability leads to the complete leaching of the CORM. Nevertheless, the degradation of the MOF matrix gives rise to an enhanced CO release rate, which is related to the presence of free adenine in the solution.

  7. Preparation of Zeolitic Imidazolate Framework-8 (ZIF-8) Membrane on Porous Polymeric Support via Contra-Diffusion Method

    KAUST Repository

    Tan, Xiaoyu

    2016-05-18

    In the last decade, many attempts were made to put metal organic frameworks (MOFs) in industrial applications, but most of these efforts weren’t successfully. As one of the few MOFs produced on industrial scale, ZIF-8 has interesting pore size, huge internal surface area and great thermal and chemical stability. Therefore, ZIF-8 might become the first MOF, which will be applied in industrial separation processes. In this thesis, a synthesis study is presented, which leads to a cheap and convenient way to
fabricate defect-free and thin ZIF-8 membranes on porous polymeric supports showing high selectivity and high gas permeance. The ZIF-8 layers were produced via a contra-diffusion method. Several polymeric membranes were employed as support in this study, such as PAN, PEI, PSU, PA and PTSC. We studied the influence of the polymeric support properties for the ZIF-8 membrane preparation and optimized the ZIF-8 preparation conditions. The ZIF-8 membranes were characterized via scanning electron microscopy (SEM) and X-ray diffraction (XRD). For gas permeation test, we chose a Wicke-Kallenbach apparatus to measure membrane’s gas permeance and selectivity. One of the best ZIF-8 membranes exhibited a hydrogen permeance of 3.45 × 10-8 mol m-2 s-1 Pa-1 and
an ideal selectivity of hydrogen over propane of about 500.

  8. Adsorptive removal of methyl orange from aqueous solution with metal-organic frameworks, porous chromium-benzenedicarboxylates

    International Nuclear Information System (INIS)

    Haque, Enamul; Lee, Ji Eun; Jang, In Tae; Hwang, Young Kyu; Chang, Jong-San; Jegal, Jonggeon; Jhung, Sung Hwa

    2010-01-01

    Two typical highly porous metal-organic framework (MOF) materials based on chromium-benzenedicarboxylates (Cr-BDC) obtained from Material of Institute Lavoisier with special structure of MIL-101 and MIL-53 have been used for the adsorptive removal of methyl orange (MO), a harmful anionic dye, from aqueous solutions. The adsorption capacity and adsorption kinetic constant of MIL-101 are greater than those of MIL-53, showing the importance of porosity and pore size for the adsorption. The performance of MIL-101 improves with modification: the adsorption capacity and kinetic constant are in the order of MIL-101 < ethylenediamine-grafted MIL-101 < protonated ethylenediamine-grafted MIL-101 (even though the porosity and pore size are slightly decreased with grafting and further protonation). The adsorption capacity of protonated ethylenediamine-grafted MIL-101 decreases with increasing the pH of an aqueous MO solution. These results suggest that the adsorption of MO on the MOF is at least partly due to the electrostatic interaction between anionic MO and a cationic adsorbent. Adsorption of MO at various temperatures shows that the adsorption is a spontaneous and endothermic process and that the entropy increases (the driving force of the adsorption) with MO adsorption. The adsorbent MIL-101s are re-usable after sonification in water. Based on this study, MOFs can be suggested as potential re-usable adsorbents to remove anionic dyes because of their high porosity, facile modification and ready re-activation.

  9. Highly monodisperse M III-based soc -MOFs (M = in and Ga) with cubic and truncated cubic morphologies

    KAUST Repository

    Pang, Maolin

    2012-08-15

    In this work, we carry out an investigation on shape-controlled growth of In III- and Ga III-based square-octahedral metal-organic frameworks (soc-MOFs). In particular, controllable crystal morphological evolution from simple cubes to complex octadecahedra has been achieved, and resultant highly uniform crystal building blocks promise new research opportunities for preparation of self-assembled MOF materials and related applications. © 2012 American Chemical Society.

  10. Highly monodisperse M III-based soc -MOFs (M = in and Ga) with cubic and truncated cubic morphologies

    KAUST Repository

    Pang, Maolin; Cairns, Amy; Liu, Yunling; Belmabkhout, Youssef; Zeng, Huachun; Eddaoudi, Mohamed

    2012-01-01

    In this work, we carry out an investigation on shape-controlled growth of In III- and Ga III-based square-octahedral metal-organic frameworks (soc-MOFs). In particular, controllable crystal morphological evolution from simple cubes to complex octadecahedra has been achieved, and resultant highly uniform crystal building blocks promise new research opportunities for preparation of self-assembled MOF materials and related applications. © 2012 American Chemical Society.

  11. Large negative thermal expansion provided by metal-organic framework MOF-5: A first-principles study

    International Nuclear Information System (INIS)

    Wang, Lei; Wang, Cong; Sun, Ying; Shi, Kewen; Deng, Sihao; Lu, Huiqing

    2016-01-01

    The thermodynamic properties and negative thermal expansion (NTE) behavior of metal-organic framework MOF-5 are investigated within the quasi-harmonic approximation, by using density functional theory. For nanoporous MOF-5, the temperature dependence of bulk modulus increases with increasing temperature, indicating that the resistance to compression is enhanced gradually. The large NTE behavior is obtained, which agrees reasonably with the experimental data. From the Grüneisen parameter as a function of temperature, it can be found that low-frequency phonons are closely associated with the NTE of MOF-5. The corresponding vibrational modes can be viewed as the results of local deformations (translation, rotation, twisting) of BDC (1,4-benzenedicarboxylate) linker and zinc clusters. The lowest-frequency phonon mode (the transverse motion of carboxylate groups and benzene ring, zinc clusters being as rigid units) is confirmed to be most responsible for thermal contraction. - Highlights: • The related thermodynamic properties and NTE behavior of MOF-5 are investigated by first principles. • Contrary to other inorganic NTE materials, bulk modulus of MOF-5 increases on heating. • The low-frequency phonons are closely associated with the NTE of MOF-5. • The NTE-contributing vibrational modes are elucidated clearly.

  12. Large negative thermal expansion provided by metal-organic framework MOF-5: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lei, E-mail: leiw@buaa.edu.cn; Wang, Cong, E-mail: congwang@buaa.edu.cn; Sun, Ying; Shi, Kewen; Deng, Sihao; Lu, Huiqing

    2016-06-01

    The thermodynamic properties and negative thermal expansion (NTE) behavior of metal-organic framework MOF-5 are investigated within the quasi-harmonic approximation, by using density functional theory. For nanoporous MOF-5, the temperature dependence of bulk modulus increases with increasing temperature, indicating that the resistance to compression is enhanced gradually. The large NTE behavior is obtained, which agrees reasonably with the experimental data. From the Grüneisen parameter as a function of temperature, it can be found that low-frequency phonons are closely associated with the NTE of MOF-5. The corresponding vibrational modes can be viewed as the results of local deformations (translation, rotation, twisting) of BDC (1,4-benzenedicarboxylate) linker and zinc clusters. The lowest-frequency phonon mode (the transverse motion of carboxylate groups and benzene ring, zinc clusters being as rigid units) is confirmed to be most responsible for thermal contraction. - Highlights: • The related thermodynamic properties and NTE behavior of MOF-5 are investigated by first principles. • Contrary to other inorganic NTE materials, bulk modulus of MOF-5 increases on heating. • The low-frequency phonons are closely associated with the NTE of MOF-5. • The NTE-contributing vibrational modes are elucidated clearly.

  13. Novel catalytic micromotor of porous zeolitic imidazolate framework-67 for precise drug delivery.

    Science.gov (United States)

    Wang, Linlin; Zhu, Hongli; Shi, Ying; Ge, You; Feng, Xiaomiao; Liu, Ruiqing; Li, Yi; Ma, Yanwen; Wang, Lianhui

    2018-06-07

    Micromotors hold promise as drug carriers for targeted drug delivery owing to the characteristics of self-propulsion and directional navigation. However, several defects still exist, including high cost, short movement life, low drug loading and slow release rate. Herein, a novel catalytic micromotor based on porous zeolitic imidazolate framework-67 (ZIF-67) synthesized by a greatly simplified wet chemical method assisted with ultrasonication is described as an efficient anticancer drug carrier. These porous micromotors display effective autonomous motion in hydrogen peroxide and long durable movement life of up to 90 min. Moreover, the multifunctional micromotor ZIF-67/Fe3O4/DOX exhibits excellent performance in precise drug delivery under external magnetic field with high drug loading capacity of fluorescent anticancer drug DOX up to 682 μg mg-1 owing to its porous nature, high surface area and rapid drug release based on dual stimulus of catalytic reaction and solvent effects. Therefore, these porous ZIF-67-based catalytic micromotors combine the domains of metal-organic frameworks (MOFs) and micomotors, thus developing potential resources for micromotors and holding great potential as label-free and precisely controlled high-quality candidates of drug delivery systems for biomedical applications.

  14. Theoretical model estimation of guest diffusion in Metal-Organic Frameworks (MOFs)

    KAUST Repository

    Zheng, Bin

    2015-08-11

    Characterizing molecule diffusion in nanoporous matrices is critical to understanding the novel chemical and physical properties of metal-organic frameworks (MOFs). In this paper, we developed a theoretical model to fastly and accurately compute the diffusion rate of guest molecules in a zeolitic imidazolate framework-8 (ZIF-8). The ideal gas or equilibrium solution diffusion model was modified to contain the effect of periodical media via introducing the possibility of guests passing through the framework gate. The only input in our model is the energy barrier of guests passing through the MOF’s gate. Molecular dynamics (MD) methods were employed to gather the guest density profile, which then was used to deduce the energy barrier values. This produced reliable results that require a simulation time of 5 picoseconds, which is much shorter when using pure MD methods (in the billisecond scale) . Also, we used density functional theory (DFT) methods to obtain the energy profile of guests passing through gates, as this does not require specification of a force field for the MOF degrees of freedom. In the DFT calculation, we only considered one gate of MOFs each time; as this greatly reduced the computational cost. Based on the obtained energy barrier values we computed the diffusion rate of alkane and alcohol in ZIF-8 using our model, which was in good agreement with experimental test results and the calculation values from standard MD model. Our model shows the advantage of obtaining accurate diffusion rates for guests in MOFs for a lower computational cost and shorter calculation time. Thus, our analytic model calculation is especially attractive for high-throughput computational screening of the dynamic performance of guests in a framework.

  15. MIL-53(Fe) MOF-mediated catalytic chemiluminescence for sensitive detection of glucose.

    Science.gov (United States)

    Yi, Xueling; Dong, Wenfei; Zhang, Xiaodan; Xie, Jianxin; Huang, Yuming

    2016-12-01

    Various analytical applications of metal-organic frameworks (MOFs) have been rapidly developed in the past few years. However, the employment of MOFs as catalysts in chemiluminescence (CL) analysis is rare. Here, for the first time, we found that MIL-53(Fe) MOFs could significantly enhance the CL of luminol in the presence of H 2 O 2 in an alkaline medium. The CL intensity in the luminol-H 2 O 2 -MIL-53(Fe) system was about 20 times higher than that in the luminol-H 2 O 2 system. Moreover, the XRD pattern of MIL-53(Fe) after CL reaction was almost the same as that of the original MIL-53(Fe), confirming the catalytic role of MIL-53(Fe) in the luminol-H 2 O 2 -MIL-53(Fe) system. The possible mechanism behind the enhancing phenomenon was discussed based on the results from the CL spectra, FL probe experiments, and active oxygen species measurements. By coupling with the glucose oxidase-based catalytic oxidation reaction, a sensitive and selective CL method was developed for the detection of glucose. There is a linear relationship between the logarithm of CL intensity and the logarithm of glucose concentration in the range from 0.1 to 10 μM, and a detection limit of 0.05 μM (S/N = 3) is obtained. The proposed method has been applied to the determination of glucose in human serum samples with satisfactory results. Graphical abstract MIL-53(Fe) MOFs are found to greatly enhance the chemiluminescence emission of the luminol-H 2 O 2 system, and this finding resulted in a new chemiluminescence method for biosensing of glucose when coupled with the glucose oxidase.

  16. Foams in porous media

    Energy Technology Data Exchange (ETDEWEB)

    Marsden, S.S.

    1986-07-01

    In 1978 a literature search on selective blocking of fluid flow in porous media was done by Professor S.S. Marsden and two of his graduate students, Tom Elson and Kern Huppy. This was presented as SUPRI Report No. TR-3 entitled ''Literature Preview of the Selected Blockage of Fluids in Thermal Recovery Projects.'' Since then a lot of research on foam in porous media has been done on the SUPRI project and a great deal of new information has appeared in the literature. Therefore we believed that a new, up-to-date search should be done on foam alone, one which would be helpful to our students and perhaps of interest to others. This is a chronological survey showing the development of foam flow, blockage and use in porous media, starting with laboratory studies and eventually getting into field tests and demonstrations. It is arbitrarily divided into five-year time periods. 81 refs.

  17. Porous material neutron detector

    Science.gov (United States)

    Diawara, Yacouba [Oak Ridge, TN; Kocsis, Menyhert [Venon, FR

    2012-04-10

    A neutron detector employs a porous material layer including pores between nanoparticles. The composition of the nanoparticles is selected to cause emission of electrons upon detection of a neutron. The nanoparticles have a maximum dimension that is in the range from 0.1 micron to 1 millimeter, and can be sintered with pores thereamongst. A passing radiation generates electrons at one or more nanoparticles, some of which are scattered into a pore and directed toward a direction opposite to the applied electrical field. These electrons travel through the pore and collide with additional nanoparticles, which generate more electrons. The electrons are amplified in a cascade reaction that occurs along the pores behind the initial detection point. An electron amplification device may be placed behind the porous material layer to further amplify the electrons exiting the porous material layer.

  18. Porous Silicon Nanowires

    Science.gov (United States)

    Qu, Yongquan; Zhou, Hailong; Duan, Xiangfeng

    2011-01-01

    In this minreview, we summarize recent progress in the synthesis, properties and applications of a new type of one-dimensional nanostructures — single crystalline porous silicon nanowires. The growth of porous silicon nanowires starting from both p- and n-type Si wafers with a variety of dopant concentrations can be achieved through either one-step or two-step reactions. The mechanistic studies indicate the dopant concentration of Si wafers, oxidizer concentration, etching time and temperature can affect the morphology of the as-etched silicon nanowires. The porous silicon nanowires are both optically and electronically active and have been explored for potential applications in diverse areas including photocatalysis, lithium ion battery, gas sensor and drug delivery. PMID:21869999

  19. Thermodynamics of hydrogen adsorption in MOF-177 at low temperatures: measurements and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Poirier, Eric [College of Engineering, Purdue University, West Lafayette, IN 47907 (United States); Dailly, Anne [Chemical and Environmental Sciences Laboratory, General Motors Corporation, Warren, MI 48090 (United States)], E-mail: poirierem@gmail.com, E-mail: anne.dailly@gm.com

    2009-05-20

    Hydrogen adsorption measurements and modelling for the Zn-based microporous metal-organic framework (MOF) Zn{sub 4}O(1,3,5-benzenetribenzoate){sub 2}, MOF-177, were performed over the 50-77 K and 0-40 bar ranges. The maximum excess adsorption measured under these conditions varies over about 105-70 mg g{sup -1}. An analysis of the isotherms near saturation shows that hydrogen is ultimately adsorbed in an incompressible phase whose density is comparable to that of the bulk liquid. These liquid state properties observed under supercritical conditions reveal a remarkable effect of nanoscale confinement. The entire set of adsorption isotherms can be well described using a micropore filling model. The latter is used, in particular, to determine the absolute amounts adsorbed and the adsorption enthalpy. When expressed in terms of absolute adsorption, the isotherms show considerable hydrogen storage capacities, reaching up to 125 mg g{sup -1} at 50 K and 25 bar. The adsorption enthalpies are calculated as a function of fractional filling and range from 3 to 5 kJ mol{sup -1} in magnitude, in accordance with physisorption. These results are discussed with respect to a similar analysis performed on another Zn-based MOF, Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3}, IRMOF-1, presented recently. It is found that both materials adsorb hydrogen by similar mechanisms.

  20. A study on metal organic framework (MOF-177) synthesis, characterization and hydrogen adsorption -desorption cycles

    Energy Technology Data Exchange (ETDEWEB)

    Viditha, V.; Venkateswer Rao, M.; Srilatha, K.; Himabindu, V. [Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University Hyderabad, Kukatpally, Hyderabad-500 085, A.P. (India); Yerramilli, Anjaneyulu [Director, TLGVRC, JSU Box 18739, JSU, Jackson, MS 32917-0939 (United States)

    2013-07-01

    Hydrogen has long been considered to be an ideal alternative to fossil-fuel systems and much work has now been done on its storage. There are four main methods of hydrogen storage: as a liquid; as compressed hydrogen; in the form of metal hydrides; and by physisorption. Among all the materials metal organic frameworks (MOFs) are considered to have desirable properties like high porosity, pore volume and high thermal stability. MOF-177 is considered to be an ideal storage material. In this paper we study about its synthesis and hydrogen storage capacities of MOF-177 at different pressures ranging from 25, 50, 75 and 100 bar respectively. The obtained samples are characterized by XRD, BET and SEM. The recorded results show that the obtained hydrogen capacity is 1.1, 2.20, 2.4 and 2.80 wt%. The desorption capacity is 0.9, 2.1, 2.37 and 2.7 wt% at certain temperatures like 373 K.

  1. Ionic Liquids as the MOFs/Polymer Interfacial Binder for Efficient Membrane Separation.

    Science.gov (United States)

    Lin, Rijia; Ge, Lei; Diao, Hui; Rudolph, Victor; Zhu, Zhonghua

    2016-11-23

    Obtaining strong interfacial affinity between filler and polymer is critical to the preparation of mixed matrix membranes (MMMs) with high separation efficiency. However, it is still a challenge for micron-sized metal organic frameworks (MOFs) to achieve excellent compatibility and defect-free interface with polymer matrix. Thin layer of ionic liquid (IL) was immobilized on micron-sized HKUST-1 to eliminate the interfacial nonselective voids in MMMs with minimized free ionic liquid (IL) in polymer matrix, and then the obtained IL decorated HKUST-1 was incorporated into 4,4'-(hexafluoroisopropylidene)diphthalic anhydride-2,3,5,6-tetramethyl-1,3-phenyldiamine (6FDA-Durene) to fabricate MMMs. Acting as a filler/polymer interfacial binder, the favorable MOF/IL and IL/polymer interaction can facilitate the enhancement of MOF/polymer affinity. Compared to MMM with only HKUST-1 incorporation, MMM with IL decorated HKUST-1 succeeded in restricting the formation of nonselective interfacial voids, leading to an increment in CO 2 selectivity. The IL decoration method can be an effective approach to eliminate interfacial voids in MMMs, extending the filler selection to a wide range of large-sized fillers.

  2. Thermodynamics of hydrogen adsorption in MOF-177 at low temperatures: measurements and modelling

    International Nuclear Information System (INIS)

    Poirier, Eric; Dailly, Anne

    2009-01-01

    Hydrogen adsorption measurements and modelling for the Zn-based microporous metal-organic framework (MOF) Zn 4 O(1,3,5-benzenetribenzoate) 2 , MOF-177, were performed over the 50-77 K and 0-40 bar ranges. The maximum excess adsorption measured under these conditions varies over about 105-70 mg g -1 . An analysis of the isotherms near saturation shows that hydrogen is ultimately adsorbed in an incompressible phase whose density is comparable to that of the bulk liquid. These liquid state properties observed under supercritical conditions reveal a remarkable effect of nanoscale confinement. The entire set of adsorption isotherms can be well described using a micropore filling model. The latter is used, in particular, to determine the absolute amounts adsorbed and the adsorption enthalpy. When expressed in terms of absolute adsorption, the isotherms show considerable hydrogen storage capacities, reaching up to 125 mg g -1 at 50 K and 25 bar. The adsorption enthalpies are calculated as a function of fractional filling and range from 3 to 5 kJ mol -1 in magnitude, in accordance with physisorption. These results are discussed with respect to a similar analysis performed on another Zn-based MOF, Zn 4 O(1,4-benzenedicarboxylate) 3 , IRMOF-1, presented recently. It is found that both materials adsorb hydrogen by similar mechanisms.

  3. Highly Water-Stable Lanthanide-Oxalate MOFs with Remarkable Proton Conductivity and Tunable Luminescence.

    Science.gov (United States)

    Zhang, Kun; Xie, Xiaoji; Li, Hongyu; Gao, Jiaxin; Nie, Li; Pan, Yue; Xie, Juan; Tian, Dan; Liu, Wenlong; Fan, Quli; Su, Haiquan; Huang, Ling; Huang, Wei

    2017-09-01

    Although proton conductors derived from metal-organic frameworks (MOFs) are highly anticipated for various applications including solid-state electrolytes, H 2 sensors, and ammonia synthesis, they are facing serious challenges such as poor water stability, fastidious working conditions, and low proton conductivity. Herein, we report two lanthanide-oxalate MOFs that are highly water stable, with so far the highest room-temperature proton conductivity (3.42 × 10 -3 S cm -1 ) under 100% relative humidity (RH) among lanthanide-based MOFs and, most importantly, luminescent. Moreover, the simultaneous response of both the proton conductivity and luminescence intensity to RH allows the linkage of proton conductivity with luminescence intensity. This way, the electric signal of proton conductivity variation versus RH will be readily translated to optical signal of luminescence intensity, which can be directly visualized by the naked eye. If proper lanthanide ions or even transition-metal ions are used, the working wavelengths of luminescence emissions can be further extended from visible to near infrared light for even wider-range applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Correlation between the Microstructure of Porous Materials and the Adsorption Properties of H2 and D2

    International Nuclear Information System (INIS)

    Krkljus, Ivana Biljana

    2011-01-01

    One of the most challenging tasks toward the full implementation of the hydrogen based economy is the reversible storage of hydrogen for portable applications. Three main approaches have been investigated to store the hydrogen, storage as a compressed gas or a liquid, or through a direct chemical bond between the hydrogen atom and the material. The alternative approach, the most recently investigated, is the storage of hydrogen at cryogenic conditions. Storage by physisorption within porous adsorbents has particular advantages of complete reversibility, the fast refueling time, the low heat evolution, and above all increased safety. The nature of interaction of hydrogen, deuterium, and gas mixtures with porous adsorbents was exploited by performing thermal desorption spectroscopy (TDS) measurements. This sensitive experimental technique gives qualitative information about the different adsorption sites, which show different desorption temperatures depending on the interaction energy. After an appropriate calibration the amount of gas desorbed may be quantified. To gain a more fundamental insight into the available adsorption sites multiple TDS spectra were recorded, corresponding to different surface coverages (in the pressure range of 1 to 700 mbar), and different heating regimes. Different kind of porous adsorbents, conventional carbon-based materials and novel Metal Organic Framework Materials (MOFs), were used to investigate the hydrogen/deuterium physisorption mechanism. For carbon materials an increase in the hydrogen interaction potential was observed for adsorbents with narrow pore size. The confined geometry, where hydrogen simultaneously interacts with all the surrounding adsorbent walls, strengthens the interaction potential with the adsorbate molecule, thus, maximizing the total van der Waals force on the adsorbate. Crystalline MOFs are a new class of porous materials assembled from discrete metal centers, which act as framework nodes, and organic

  5. Porous silicon gettering

    Energy Technology Data Exchange (ETDEWEB)

    Tsuo, Y.S.; Menna, P.; Pitts, J.R. [National Renewable Energy Lab., Golden, CO (United States)] [and others

    1996-05-01

    The authors have studied a novel extrinsic gettering method that uses the large surface areas produced by a porous-silicon etch as gettering sites. The annealing step of the gettering used a high-flux solar furnace. They found that a high density of photons during annealing enhanced the impurity diffusion to the gettering sites. The authors used metallurgical-grade Si (MG-Si) prepared by directional solidification casing as the starting material. They propose to use porous-silicon-gettered MG-Si as a low-cost epitaxial substrate for polycrystalline silicon thin-film growth.

  6. Porous metal for orthopedics implants

    OpenAIRE

    Matassi, Fabrizio; Botti, Alessandra; Sirleo, Luigi; Carulli, Christian; Innocenti, Massimo

    2013-01-01

    Porous metal has been introduced to obtain biological fixation and improve longevity of orthopedic implants. The new generation of porous metal has intriguing characteristics that allows bone healing and high osteointegration of the metallic implants. This article gives an overview about biomaterials properties of the contemporary class of highly porous metals and about the clinical use in orthopaedic surgery.

  7. Probing the structure, stability and hydrogen adsorption of lithium functionalized isoreticular MOF-5 (Fe, Cu, Co, Ni and Zn) by density functional theory.

    Science.gov (United States)

    Venkataramanan, Natarajan Sathiyamoorthy; Sahara, Ryoji; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

    2009-04-14

    Li adsorption on isoreticular MOFs with metal Fe, Cu, Co, Ni and Zn was studied using density function theory. Li functionalization shows a considerable structural change associated with a volume change in isoreticular MOF-5 except for the Zn metal center. Hydrogen binding energies on Li functionalized MOFs are seen to be in the range of 0.2 eV, which is the desired value for an ideal reversible storage system. This study has clearly shown that Li doping is possible only in Zn-based MOF-5, which would be better candidate to reversibly store hydrogen.

  8. Probing the Structure, Stability and Hydrogen Adsorption of Lithium Functionalized Isoreticular MOF-5 (Fe, Cu, Co, Ni and Zn by Density Functional Theory

    Directory of Open Access Journals (Sweden)

    Yoshiyuki Kawazoe

    2009-04-01

    Full Text Available Li adsorption on isoreticular MOFs with metal Fe, Cu, Co, Ni and Zn was studied using density function theory. Li functionalization shows a considerable structural change associated with a volume change in isoreticular MOF-5 except for the Zn metal center. Hydrogen binding energies on Li functionalized MOFs are seen to be in the range of 0.2 eV, which is the desired value for an ideal reversible storage system. This study has clearly shown that Li doping is possible only in Zn-based MOF-5, which would be better candidate to reversibly store hydrogen.

  9. Gas adsorption properties of highly porous metal-organic frameworks containing functionalized naphthalene dicarboxylate linkers.

    Science.gov (United States)

    Sim, Jaeung; Yim, Haneul; Ko, Nakeun; Choi, Sang Beom; Oh, Youjin; Park, Hye Jeong; Park, SangYoun; Kim, Jaheon

    2014-12-28

    Three functionalized metal-organic frameworks (MOFs), MOF-205-NH2, MOF-205-NO2, and MOF-205-OBn, formulated as Zn4O(BTB)4/3(L), where BTB is benzene-1,3,5-tribenzoate and L is 1-aminonaphthalene-3,7-dicarboxylate (NDC-NH2), 1-nitronaphthalene-3,7-dicarboxylate (NDC-NO2) or 1,5-dibenzyloxy-2,6-naphthalenedicarboxylate (NDC-(OBn)2), were synthesized and their gas (H2, CO2, or CH4) adsorption properties were compared to those of the un-functionalized, parent MOF-205. Ordered structural models for MOF-205 and its derivatives were built based on the crystal structures and were subsequently used for predicting porosity properties. Although the Brunauer-Emmett-Teller (BET) surface areas of the three MOF-205 derivatives were reduced (MOF-205, 4460; MOF-205-NH2, 4330; MOF-205-NO2, 3980; MOF-205-OBn, 3470 m(2) g(-1)), all three derivatives were shown to have enhanced H2 adsorption capacities at 77 K and CO2 uptakes at 253, 273, and 298 K respectively at 1 bar in comparison with MOF-205. The results indicate the following trend in H2 adsorption: MOF-205 < MOF-205-NO2 < MOF-205-NH2 < MOF-205-OBn. MOF-205-OBn showed good ideal adsorbed solution theory (IAST) selectivity values of 6.5 for CO2/N2 (15/85 in v/v) and 2.7 for CO2/CH4 (50/50 in v/v) at 298 K. Despite the large reduction (-22%) in the surface area, MOF-205-OBn displayed comparable total volumetric CO2 (at 48 bar) and CH4 (at 35 bar) storage capacities with those of MOF-205 at 298 K: MOF-205-OBn, 305 (CO2) and 112 (CH4) cm(3) cm(-3), and for MOF-205, 307 (CO2) and 120 (CH4) cm(3) cm(-3), respectively.

  10. Electrokinetics in porous media

    NARCIS (Netherlands)

    Luong, D.T.

    2014-01-01

    This thesis presents the PhD research on electrokinetics in porous media. Electrokinetic phenomena are induced by the relative motion between a fluid and a solid surface and are directly related to the existence of an electric double layer between the fluid and the solid grain surface.

  11. Fluorocarbon Adsorption in Hierarchical Porous Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Motkuri, Radha K.; Annapureddy, Harsha V.; Vijayakumar, M.; Schaef, Herbert T.; Martin, P F.; McGrail, B. Peter; Dang, Liem X.; Krishna, Rajamani; Thallapally, Praveen K.

    2014-07-09

    The adsorption behavior of a series of fluorocarbon derivatives was examined on a set of microporous metal organic framework (MOF) sorbents and another set of hierarchical mesoporous MOFs. The microporous M-DOBDC (M = Ni, Co) showed a saturation uptake capacity for R12 of over 4 mmol/g at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous MOF MIL-101 showed an exceptionally high uptake capacity reaching over 14 mmol/g at P/Po of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption were found to generally correlate with the polarizability of the refrigerant with R12 > R22 > R13 > R14 > methane. These results suggest the possibility of exploiting MOFs for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling and refrigeration applications.

  12. UiO-66-NH2 Metal-Organic Framework (MOF) Nucleation on TiO2, ZnO, and Al2O3 Atomic Layer Deposition-Treated Polymer Fibers: Role of Metal Oxide on MOF Growth and Catalytic Hydrolysis of Chemical Warfare Agent Simulants.

    Science.gov (United States)

    Lee, Dennis T; Zhao, Junjie; Oldham, Christopher J; Peterson, Gregory W; Parsons, Gregory N

    2017-12-27

    Metal-organic frameworks (MOFs) chemically bound to polymeric microfibrous textiles show promising performance for many future applications. In particular, Zr-based UiO-66-family MOF-textiles have been shown to catalytically degrade highly toxic chemical warfare agents (CWAs), where favorable MOF/polymer bonding and adhesion are attained by placing a nanoscale metal-oxide layer on the polymer fiber preceding MOF growth. To date, however, the nucleation mechanism of Zr-based MOFs on different metal oxides and how product performance is affected are not well understood. Herein, we provide new insight into how different inorganic nucleation films (i.e., Al 2 O 3 , ZnO, or TiO 2 ) conformally coated on polypropylene (PP) nonwoven textiles via atomic layer deposition (ALD) influence the quality, overall surface area, and the fractional yield of UiO-66-NH 2 MOF crystals solvothermally grown on fiber substrates. Of the materials explored, we find that TiO 2 ALD layers lead to the most effective overall MOF/fiber adhesion, uniformity, and a rapid catalytic degradation rate for a CWA simulant, dimethyl p-nitrophenyl phosphate (DMNP) with t 1/2 = 15 min, 580-fold faster than the catalytic performance of untreated PP textiles. Interestingly, compared to ALD TiO 2 and Al 2 O 3 , ALD ZnO induces a larger MOF yield in solution and mass loading on PP fibrous mats. However, this larger MOF yield is ascribed to chemical instability of the ZnO layer under MOF formation condition, leading to Zn 2+ ions that promote further homogeneous MOF growth. Insights presented here improve understanding of compatibility between active MOF materials and substrate surfaces, which we believe will help advanced MOF composite materials for a variety of useful functions.

  13. Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction

    KAUST Repository

    Xue, Dongxu; Belmabkhout, Youssef; Shekhah, Osama; Jiang, Hao; Adil, Karim; Cairns, Amy J; Eddaoudi, Mohamed

    2015-01-01

    Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e. Eu3+, Tb3+ and Y3+) fcu metal‒organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cut-off ideal for selective adsorption kinetics separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in-situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the RE-fcu-MOF plat-form, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded nota-ble gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol and butanol/water pair systems.

  14. Synthesis of Zn-MOF incorporating titanium-hydrides as active sites binding H{sub 2} molecules

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jongsik, E-mail: jkim40@nd.edu [Department of Chemical and Biomolecular Engineering, University of Notre Dame, 182, Fitzpatrick Hall, Notre Dame, IN 46556 (United States); Ok Kim, Dong; Wook Kim, Dong; Sagong, Kil [Hanwha Chemical Research & Development Center, 6, Shinseong-dong, Yuseong-gu, Daejeon 305-804 (Korea, Republic of)

    2015-10-15

    This paper describes the synthetic effort for a Zn-MOF imparting Ti-H as a preferential binding site potentially capturing H{sub 2} molecules via Kubas-type interaction. The formation mechanism of Ti-H innate to the final material was potentially demonstrated to follow a radical dissociation rather than a β-hydrogen elimination and a C-H reductive elimination. - Graphical abstract: This study details the synthesis and the formation mechanism of Zn-MOF adsorbent site-isolating TiH{sub 3} that can potentially capture H{sub 2} molecules via Kubas-binding mechanism. - Highlights: • OH-functionalized Zn-MOF was employed as a reactive template to site-isolate TiH{sub 3}. • This MOF was post-synthetically modified using a tetracyclohexyl titanium (IV). • This intermediate was hydrogenolyzed to change ligand from cyclohexyl to hydride. • Formation mechanism of TiH{sub 3} was investigated via two control GC–MS experiments. • Final Zn-MOF potentially site-isolating TiH{sub 3} species was used as a H{sub 2} adsorbent.

  15. Size- and shape-controlled synthesis of hexagonal bipyramidal crystals and hollow self-assembled Al-MOF spheres

    KAUST Repository

    Sarawade, Pradip; Tan, Hua; Anjum, Dalaver H.; Cha, Dong Kyu; Polshettiwar, Vivek

    2013-01-01

    We report an efficient protocol for the synthesis of monodisperse crystals of an aluminum (Al)-based metal organic framework (MOF) while obtaining excellent control over the size and shape solely by tuning of the reaction parameters without the use of a template or structure-directing agent. The size of the hexagonal crystals of the Al-MOF can be selectively varied from 100 nm to 2000 nm by simply changing the reaction time and temperature via its nucleation-growth mechanism. We also report a self-assembly phenomenon, observed for the first time in case of Al-MOF, whereby hollow spheres of Al-MOF were formed by the spontaneous organization of triangular sheet building blocks. These MOFs showed broad hysteresis loops during the CO2 capture, indicating that the adsorbed CO2 is not immediately desorbed upon decreasing the external pressure and is instead confined within the framework, which allows for the capture and subsequent selective trapping of CO2 from gaseous mixtures. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction

    KAUST Repository

    Xue, Dongxu

    2015-03-31

    Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e. Eu3+, Tb3+ and Y3+) fcu metal‒organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cut-off ideal for selective adsorption kinetics separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in-situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the RE-fcu-MOF plat-form, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded nota-ble gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol and butanol/water pair systems.

  17. Size- and shape-controlled synthesis of hexagonal bipyramidal crystals and hollow self-assembled Al-MOF spheres

    KAUST Repository

    Sarawade, Pradip

    2013-11-25

    We report an efficient protocol for the synthesis of monodisperse crystals of an aluminum (Al)-based metal organic framework (MOF) while obtaining excellent control over the size and shape solely by tuning of the reaction parameters without the use of a template or structure-directing agent. The size of the hexagonal crystals of the Al-MOF can be selectively varied from 100 nm to 2000 nm by simply changing the reaction time and temperature via its nucleation-growth mechanism. We also report a self-assembly phenomenon, observed for the first time in case of Al-MOF, whereby hollow spheres of Al-MOF were formed by the spontaneous organization of triangular sheet building blocks. These MOFs showed broad hysteresis loops during the CO2 capture, indicating that the adsorbed CO2 is not immediately desorbed upon decreasing the external pressure and is instead confined within the framework, which allows for the capture and subsequent selective trapping of CO2 from gaseous mixtures. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction.

    Science.gov (United States)

    Xue, Dong-Xu; Belmabkhout, Youssef; Shekhah, Osama; Jiang, Hao; Adil, Karim; Cairns, Amy J; Eddaoudi, Mohamed

    2015-04-22

    Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e., Eu(3+), Tb(3+), and Y(3+)) fcu metal-organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cutoff, ideal for selective adsorption kinetics based separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the first RE-fcu-MOF platform, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded notable gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol, and butanol/water pair systems.

  19. Porous anionic indium-organic framework with enhanced gas and vapor adsorption and separation ability.

    Science.gov (United States)

    Huang, Yuanbiao; Lin, Zujin; Fu, Hongru; Wang, Fei; Shen, Min; Wang, Xusheng; Cao, Rong

    2014-09-01

    A three-dimensional microporous anionic metal-organic framework (MOF) (Et4N)3[In3(TATB)4] (FJI-C1, H3TATB=4,4',4''-s-triazine-2,4,6-triyltribenzoic acid) with large unit cell volume has been synthesized. Assisted by the organic cation group Et4N in the pores of the compound, FJI-C1 not only shows high adsorption uptakes of C2 and C3 hydrocarbons, but also exhibits highly selective separation of propane, acetylene, ethane, and ethylene from methane at room temperature. Furthermore, it also exhibits high separation selectivity for propane over C2 hydrocarbons and acetylene can be readily separated from their C2 hydrocarbons mixtures at low pressure due to the high selectivity for C2H2 in comparison to C2H4 and C2H6. In addition, FJI-C1 with hydrophilic internal pores surfaces shows highly efficient adsorption separation of polar molecules from nonpolar molecules. Notably, it exhibits high separation selectivity for benzene over cyclohexane due to the π-π interactions between benzene molecules and s-triazine rings of the porous MOF. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Graded/Gradient Porous Biomaterials

    Directory of Open Access Journals (Sweden)

    Xigeng Miao

    2009-12-01

    Full Text Available Biomaterials include bioceramics, biometals, biopolymers and biocomposites and they play important roles in the replacement and regeneration of human tissues. However, dense bioceramics and dense biometals pose the problem of stress shielding due to their high Young’s moduli compared to those of bones. On the other hand, porous biomaterials exhibit the potential of bone ingrowth, which will depend on porous parameters such as pore size, pore interconnectivity, and porosity. Unfortunately, a highly porous biomaterial results in poor mechanical properties. To optimise the mechanical and the biological properties, porous biomaterials with graded/gradient porosity, pores size, and/or composition have been developed. Graded/gradient porous biomaterials have many advantages over graded/gradient dense biomaterials and uniform or homogenous porous biomaterials. The internal pore surfaces of graded/gradient porous biomaterials can be modified with organic, inorganic, or biological coatings and the internal pores themselves can also be filled with biocompatible and biodegradable materials or living cells. However, graded/gradient porous biomaterials are generally more difficult to fabricate than uniform or homogenous porous biomaterials. With the development of cost-effective processing techniques, graded/gradient porous biomaterials can find wide applications in bone defect filling, implant fixation, bone replacement, drug delivery, and tissue engineering.

  1. Convection in Porous Media

    CERN Document Server

    Nield, Donald A

    2013-01-01

    Convection in Porous Media, 4th Edition, provides a user-friendly introduction to the subject, covering a wide range of topics, such as fibrous insulation, geological strata, and catalytic reactors. The presentation is self-contained, requiring only routine mathematics and the basic elements of fluid mechanics and heat transfer. The book will be of use not only to researchers and practicing engineers as a review and reference, but also to graduate students and others entering the field. The new edition features approximately 1,750 new references and covers current research in nanofluids, cellular porous materials, strong heterogeneity, pulsating flow, and more. Recognized as the standard reference in the field Includes a comprehensive, 250-page reference list Cited over 2300 times to date in its various editions Serves as an introduction for those entering the field and as a comprehensive reference for experienced researchers Features new sections on nanofluids, carbon dioxide sequestration, and applications...

  2. Porous electrode preparation method

    Science.gov (United States)

    Arons, R.M.; Dusek, J.T.

    1983-10-18

    A porous sintered plaque is provided with a bimodal porosity that is especially well suited for use as an electrode within a molten carbonate fuel cell. The coarse porosity is sufficient for admitting gases into contact with the reaction surfaces while the fine porosity is wetted with and retains molten electrolyte on the reaction sites. The electrode structure is prepared by providing a very fine powder of such as nickel oxide and blending the powder with a suitable decomposable binder to form a solid mass. The mass is comminuted into agglomerate size particles substantially larger than the fine oxide particles and formed into a cohesive compact for subsequent sintering. Sintering is carried out at sufficient conditions to bind the agglomerates together into a porous structure having both coarse and fine porosity. Where lithiated nickel oxide cathodes are prepared, the sintering conditions can be moderate enough to retain substantial quantities of lithium within the electrode for adequate conductivity. 2 figs.

  3. Green synthesis of chromium-based metal-organic framework (Cr-MOF) from waste polyethylene terephthalate (PET) bottles for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2016-10-01

    Full Text Available It is of great economic value to produce high-value PET-based MOF materials by the veritable elimination of waste PET, and provide sufficient MOF materials for hydrogen storage applications. Consequently, this work demonstrates the use of waste PET...

  4. Effect of pendant isophthalic acid moieties on the adsorption properties of light hydrocarbons in HKUST-1-like tbo -MOFs: Application to methane purification and storage

    KAUST Repository

    Belmabkhout, Youssef; Mouttaki, Hasnaa; Eubank, Jarrod F.; Guillerm, Vincent; Eddaoudi, Mohamed

    2014-01-01

    Equilibrium adsorption of methane (CH4), C2+ gases (ethane (C2H6), ethylene (C2H4), propane (C3H8), and propylene (C3H6)), and carbon dioxide (CO2) was measured on a series of tbo-MOFs (topological analogues of the prototypical MOF, HKUST-1

  5. Understanding Hydrogen Sorption in In- soc -MOF: A Charged Metal-Organic Framework with Open-Metal Sites, Narrow Channels, and Counterions

    KAUST Repository

    Pham, Tony; Forrest, Katherine A.; Hogan, Adam; Tudor, Brant; McLaughlin, Keith; Belof, Jonathan L.; Eckert, Juergen; Space, Brian

    2015-01-01

    ,3-benzenedicarboxylate) linkers. The MOF contains nitrate counterions that are located in carcerand-like capsules of the framework. This MOF was shown to have a high hydrogen uptake at 77 K and 1.0 atm. The simulations were performed with a potential that includes

  6. Mg-MOF-74/MgF₂ Composite Coating for Improving the Properties of Magnesium Alloy Implants: Hydrophilicity and Corrosion Resistance.

    Science.gov (United States)

    Liu, Wei; Yan, Zhijie; Ma, Xiaolu; Geng, Tie; Wu, Haihong; Li, Zhongyue

    2018-03-07

    Surface modification on Mg alloys is highly promising for their application in the field of bone repair. In this study, a new metal-organic framework/MgF₂ (Mg-MOF-74/MgF₂) composite coating was prepared on the surface of AZ31B Mg alloy via pre-treatment of hydrofluoric acid and in situ hydrothermal synthesis methods. The surface topography of the composite coating is compact and homogeneous, and Mg-MOF-74 has good crystallinity. The corrosion resistance of this composite coating was investigated through Tafel polarization test and immersion test in simulated body fluid at 37 °C. It was found that Mg-MOF-74/MgF₂ composite coating significantly slowed down the corrosion rate of Mg alloy. Additionally, Mg-MOF-74/MgF₂ composite coating expresses super-hydrophilicity with the water contact angle of nearly 0°. In conclusion, on the basis of MgF₂ anticorrosive coating, the introduction of Mg-MOF-74 further improves the biological property of Mg alloys. At last, we propose that the hydrophilicity of the composite coating is mainly owing to the large number of hydroxyl groups, the high specific surface area of Mg-MOF-74, and the rough coating produced by Mg-MOF-74 particles. Hence, Mg-MOF-74 has a great advantage in enhancing the hydrophilicity of Mg alloy surface.

  7. Porous germanium multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Garralaga Rojas, Enrique; Hensen, Jan; Brendel, Rolf [Institut fuer Solarenergieforschung Hameln (ISFH), Emmerthal (Germany); Carstensen, Juergen; Foell, Helmut [Chair for General Materials Science, Faculty of Engineering, Christian-Albrechts-University of Kiel (Germany)

    2011-06-15

    We present the reproducible fabrication of porous germanium (PGe) single- and multilayers. Mesoporous layers form on heavily doped 4'' p-type Ge wafers by electrochemical etching in highly concentrated HF-based electrolytes with concentrations in a range of 30-50 wt.%. Direct PGe formation is accompanied by a constant dissolution of the already-formed porous layer at the electrolyte/PGe interface, hence yielding a thinner substrate after etching. This effect inhibits multilayer formation as the starting layer is etched while forming the second layer. We avoid dissolution of the porous layer by alternating the etching bias from anodic to cathodic. PGe formation occurs during anodic etching whereas the cathodic step passivates pore walls with H-atoms and avoids electropolishing. The passivation lasts a limited time depending on the etching current density and electrolyte concentration, necessitating a repetition of the cathodic step at suitable intervals. With optimized alternating bias mesoporous multilayer production is possible. We control the porosity of each single layer by varying the etching current density and the electrolyte (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  8. Tunable rare-earth fcu-MOFs: A platform for systematic enhancement of CO2 adsorption energetics and uptake

    KAUST Repository

    Xue, Dongxu

    2013-05-22

    A series of fcu-MOFs based on rare-earth (RE) metals and linear fluorinated/nonfluorinated, homo/heterofunctional ligands were targeted and synthesized. This particular fcu-MOF platform was selected because of its unique structural characteristics combined with the ability/potential to dictate and regulate its chemical properties (e.g., tuning of the electron-rich RE metal ions and high localized charge density, a property arising from the proximal positioning of polarizing tetrazolate moieties and fluoro-groups that decorate the exposed inner surfaces of the confined conical cavities). These features permitted a systematic gas sorption study to evaluate/elucidate the effects of distinctive parameters on CO2-MOF sorption energetics. Our study supports the importance of the synergistic effect of exposed open metal sites and proximal highly localized charge density toward materials with enhanced CO2 sorption energetics. © 2013 American Chemical Society.

  9. Ultra-Tuning of the Rare-Earth fcu-MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins

    KAUST Repository

    Assen, Ayalew Hussen Assen

    2015-10-02

    Using isoreticular chemistry allows the design and construction of a new rare-earth metal (RE) fcu-MOF with a suitable aperture size for practical steric adsorptive separations. The judicious choice of a relatively short organic building block, namely fumarate, to bridge the 12-connected RE hexanuclear clusters has afforded the contraction of the well-defined RE-fcu-MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed RE (Y and Tb) fcu-MOF analogues display unprecedented total exclusion of branched paraffins from normal paraffins. The resultant window aperture size of about 4.7 Å, regarded as a sorbate-size cut-off, enabled a complete sieving of branched paraffins from normal paraffins. The results are supported by collective single gas and mixed gas/vapor adsorption and calorimetric studies.

  10. Ultra-Tuning of the Rare-Earth fcu-MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins.

    Science.gov (United States)

    Assen, Ayalew H; Belmabkhout, Youssef; Adil, Karim; Bhatt, Prashant M; Xue, Dong-Xu; Jiang, Hao; Eddaoudi, Mohamed

    2015-11-23

    Using isoreticular chemistry allows the design and construction of a new rare-earth metal (RE) fcu-MOF with a suitable aperture size for practical steric adsorptive separations. The judicious choice of a relatively short organic building block, namely fumarate, to bridge the 12-connected RE hexanuclear clusters has afforded the contraction of the well-defined RE-fcu-MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed RE (Y(3+) and Tb(3+)) fcu-MOF analogues display unprecedented total exclusion of branched paraffins from normal paraffins. The resultant window aperture size of about 4.7 Å, regarded as a sorbate-size cut-off, enabled a complete sieving of branched paraffins from normal paraffins. The results are supported by collective single gas and mixed gas/vapor adsorption and calorimetric studies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Accurate van der Waals force field for gas adsorption in porous materials.

    Science.gov (United States)

    Sun, Lei; Yang, Li; Zhang, Ya-Dong; Shi, Qi; Lu, Rui-Feng; Deng, Wei-Qiao

    2017-09-05

    An accurate van der Waals force field (VDW FF) was derived from highly precise quantum mechanical (QM) calculations. Small molecular clusters were used to explore van der Waals interactions between gas molecules and porous materials. The parameters of the accurate van der Waals force field were determined by QM calculations. To validate the force field, the prediction results from the VDW FF were compared with standard FFs, such as UFF, Dreiding, Pcff, and Compass. The results from the VDW FF were in excellent agreement with the experimental measurements. This force field can be applied to the prediction of the gas density (H 2 , CO 2 , C 2 H 4 , CH 4 , N 2 , O 2 ) and adsorption performance inside porous materials, such as covalent organic frameworks (COFs), zeolites and metal organic frameworks (MOFs), consisting of H, B, N, C, O, S, Si, Al, Zn, Mg, Ni, and Co. This work provides a solid basis for studying gas adsorption in porous materials. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  12. The Hydrolytic Stability and Degradation Mechanism of a Hierarchically Porous Metal Alkylphosphonate Framework

    Directory of Open Access Journals (Sweden)

    Kai Lv

    2018-03-01

    Full Text Available To aid the design of a hierarchically porous unconventional metal-phosphonate framework (HP-UMPF for practical radioanalytical separation, a systematic investigation of the hydrolytic stability of bulk phase against acidic corrosion has been carried out for an archetypical HP-UMPF. Bulk dissolution results suggest that aqueous acidity has a more paramount effect on incongruent leaching than the temperature, and the kinetic stability reaches equilibrium by way of an accumulation of a partial leached species on the corrosion conduits. A variation of particle morphology, hierarchical porosity and backbone composition upon corrosion reveals that they are hydrolytically resilient without suffering any great degradation of porous texture, although large aggregates crack into sporadic fractures while the nucleophilic attack of inorganic layers cause the leaching of tin and phosphorus. The remaining selectivity of these HP-UMPFs is dictated by a balance between the elimination of free phosphonate and the exposure of confined phosphonates, thus allowing a real-time tailor of radionuclide sequestration. Moreover, a plausible degradation mechanism has been proposed for the triple progressive dissolution of three-level hierarchical porous structures to elucidate resultant reactivity. These HP-UMPFs are compared with benchmark metal-organic frameworks (MOFs to obtain a rough grading of hydrolytic stability and two feasible approaches are suggested for enhancing their hydrolytic stability that are intended for real-life separation protocols.

  13. In-situ IR monitoring of the formation of Zr-fumarate MOF

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2017-05-01

    Full Text Available monitoring of the formation of Zr-fumarate MOF Authors: Jianwei Ren, Nicholas M. Musyoka, Henrietta W. Langmi, Brian C. North, Mkhulu Mathe, Wan Pang, Mingjie Wang, Joseph Walker PII: S0169-4332(17)30296-9 DOI: http://dx.doi.org/doi:10.1016/j.apsusc.2017....01.271 Reference: APSUSC 35066 To appear in: APSUSC Received date: 21-9-2016 Revised date: 20-1-2017 Accepted date: 25-1-2017 Please cite this article as: Jianwei Ren, Nicholas M.Musyoka, Henrietta W.Langmi, Brian C.North, Mkhulu Mathe, Wan Pang, Mingjie Wang...

  14. Adsorptive desulfurization with CPO-27/MOF-74: an experimental and computational investigation.

    Science.gov (United States)

    Van de Voorde, Ben; Hezinová, Markéta; Lannoeye, Jeroen; Vandekerkhove, Annelies; Marszalek, Bartosz; Gil, Barbara; Beurroies, Isabelle; Nachtigall, Petr; De Vos, Dirk

    2015-04-28

    By combining experimental adsorption isotherms, microcalorimetric data, infrared spectroscopy and quantum chemical calculations the adsorption behaviour of the CPO-27/MOF-74 series (Ni, Co, Mg, Cu, and Zn) in the desulfurization of fuels is evaluated. The results show a clear influence of the metal ion on the adsorption capacity and affinity for S-heterocyclic compounds, with CPO-27(Ni) being the best performing material both in terms of capacity and affinity. The microcalorimetric data and infrared spectroscopy confirm the high affinity of CPO-27(Ni) for thiophene and similar compounds, while the computational data reveal that the origin of this outstanding adsorption performance is the strong sulfur-metal interaction.

  15. High-pressure, ambient temperature hydrogen storage in metal-organic frameworks and porous carbon

    Science.gov (United States)

    Beckner, Matthew; Dailly, Anne

    2014-03-01

    We investigated hydrogen storage in micro-porous adsorbents at ambient temperature and pressures up to 320 bar. We measured three benchmark adsorbents: two metal-organic frameworks, Cu3(1,3,5-benzenetricarboxylate)2 [Cu3(btc)2; HKUST-1] and Zn4O(1,3,5-benzenetribenzoate)2 [Zn4O(btb)2; MOF-177], and the activated carbon MSC-30. In this talk, we focus on adsorption enthalpy calculations using a single adsorption isotherm. We use the differential form of the Claussius-Clapeyron equation applied to the Dubinin-Astakhov adsorption model to calculate adsorption enthalpies. Calculation of the adsorption enthalpy in this way gives a temperature independent enthalpy of 5-7 kJ/mol at the lowest coverage for the three materials investigated. Additionally, we discuss the assumptions and corrections that must be made when calculating adsorption isotherms at high-pressure and adsorption enthalpies.

  16. Effect of pendant isophthalic acid moieties on the adsorption properties of light hydrocarbons in HKUST-1-like tbo -MOFs: Application to methane purification and storage

    KAUST Repository

    Belmabkhout, Youssef

    2014-01-01

    Equilibrium adsorption of methane (CH4), C2+ gases (ethane (C2H6), ethylene (C2H4), propane (C3H8), and propylene (C3H6)), and carbon dioxide (CO2) was measured on a series of tbo-MOFs (topological analogues of the prototypical MOF, HKUST-1, correspondingly dubbed tbo-MOF-1), which were developed via the supermolecular building layer (SBL) pillaring strategy. Specifically, tbo-MOF-2 and its isoreticular, functionalized analogue, tbo-MOF-2-{CH2O[Ph(CO2H)2]}2 (or tbo-MOF-3), which is characterized by pendant isophthalic acid moieties freely pointing into the cavities, were evaluated on the basis of potential use in methane storage and C2+/CH4 separation. The parent, tbo-MOF-2, showed high gravimetric and volumetric CH4 uptake, close to the U.S. Department of Energy (DOE) target for methane storage at 35 bar and room temperature. Though the presence of the pendant isophthalic acid moiety in the analogous compound, tbo-MOF-3, led to a decrease in total CH4 uptake, due mainly to the reduced size of the cavities, interestingly, it increased the affinity of the SBL-based tbo-MOF platform for propane, propene, ethane, and ethylene at low pressures compared with CH4, due additionally to the enhanced interactions of the highly polarizable light hydrocarbons with the isophthalic acid moiety. Using Ideal Adsorption Solution Theory (IAST), the predicted mixture adsorption equilibria for the C3H8/CH4, C3H6/CH4, C2H6/CH4, C2H4/CH4, and C3H8/CO2 systems showed high adsorption selectivity for C2+ over methane for tbo-MOF-3 compared with tbo-MOF-2. The high working storage capacity of tbo-MOF-2 and the high affinity of tbo-MOF-3 for C2+ over CH4 and CO2 make tbo-MOF an ideal platform for studies in gas storage and separation.

  17. UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation

    KAUST Repository

    Luo, Feng

    2016-04-26

    A new metal-organic framework Zn2(H2O)-(dobdc)·0.5(H2O) (UTSA-74, H4dobdc = 2,5-dioxido-1,4-benzenedicarboxylic acid), Zn-MOF-74/CPO-27-Zn isomer, has been synthesized and structurally characterized. It has a novel four coordinated fgl topology with one-dimensional channels of about 8.0 Å. Unlike metal sites in the wellestablished MOF-74 with a rod-packing structure in which each of them is in a five coordinate square pyramidal coordination geometry, there are two different Zn2+ sites within the binuclear secondary building units in UTSA-74 in which one of them (Zn1) is in a tetrahedral while another (Zn2) in an octahedral coordination geometry. After activation, the two axial water molecules on Zn2 sites can be removed, generating UTSA-74a with two accessible gas binding sites per Zn2 ion. Accordingly, UTSA-74a takes up a moderately high and comparable amount of acetylene (145 cm3/cm3) to Zn-MOF-74. Interestingly, the accessible Zn2+ sites in UTSA-74a are bridged by carbon dioxide molecules instead of being terminally bound in Zn-MOF-74, so UTSA-74a adsorbs a much smaller amount of carbon dioxide (90 cm3/cm3) than Zn-MOF-74 (146 cm3/cm3) at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation. X-ray crystal structures, gas sorption isotherms, molecular modeling, and simulated and experimental breakthroughs comprehensively support this result. © 2016 American Chemical Society.

  18. Isoreticular rare earth fcu-MOFs for the selective removal of H 2 S from CO 2 containing gases

    KAUST Repository

    Bhatt, Prashant

    2017-05-04

    In this work, we present the implementation of reticular chemistry and the molecular building block approach to unveil the appropriateness of Rare Earth (RE) based Metal-Organic Frameworks (MOFs) with fcu topology for H2S removal applications. Markedly, RE-fcu-MOFs, having different pore apertures sizes in the range of 4.7-6.0 Å and different functionalities, showed excellent properties for the removal of H2S from CO2 and CH4 containing gases such as natural gas, biogas and landfill gas. A series of cyclic mixed gas breakthrough experiments were carried out on three isoreticular fcu-MOFs, containing linkers of different lengths (between 8.4 and 5 Å), by using simulated natural gas mixture containing CO2/H2S/CH4 (5%/5%/90%) under different adsorption and regeneration conditions. The fcu-MOF platform has good H2S removal capacity with a high H2S/CO2 selectivity, outperforming benchmark materials like activated carbon and Zeolites in many aspects. The comparison of H2S removal performance with the related structures of the RE-fcu-MOFs provides insightful information to shed light on the relationship between the structural features of the MOF and its associated H2S separation properties. The excellent H2S/CO2 and H2S/CH4 selectivity of these materials offer great prospective for the production of pure H2S, with acceptable levels of CO2for Claus process to produce elemental sulfur.

  19. Preparation of value-added metal-organic frameworks (MOFs) using waste PET bottles as source of acid linker

    CSIR Research Space (South Africa)

    Dyosiba, Xoliswa

    2016-12-01

    Full Text Available of Value-added Metal-organic Frameworks (MOFs) Using Waste PET Bottles as Source of Acid Linker Xoliswa Dyosiba, Jianwei Ren, Nicholas M. Musyoka, Henrietta W. Langmi, Mkhulu Mathe, Maurice S. Onyango PII: S2214-9937(16)30053-7 DOI: doi:10.1016/j..., Hen- rietta W. Langmi, Mkhulu Mathe, Maurice S. Onyango, Preparation of Value-added Metal-organic Frameworks (MOFs) Using Waste PET Bottles as Source of Acid Linker, Sustainable Materials and Technologies (2016), doi:10.1016/j.susmat.2016...

  20. Simulations of hydrogen sorption in rht-MOF-1: identifying the binding sites through explicit polarization and quantum rotation calculations

    KAUST Repository

    Pham, Tony

    2014-01-01

    Grand canonical Monte Carlo (GCMC) simulations of hydrogen sorption were performed in rht-MOF-1, a metal-organic framework (MOF) that consists of isophthalate groups joined by copper paddlewheel clusters and Cu3O trimers through tetrazolate moeities. This is a charged rht-MOF that contains extra-framework nitrate counterions within the material. For the simulations performed herein, excellent agreement with experiment was achieved for the simulated hydrogen sorption isotherms and calculated isosteric heat of adsorption, Qst, values only when using a polarizable potential. Thermodynamic agreement is demonstrated via comparing to experimental isotherms and binding sites are revealed by combining simulation and inelastic neutron scattering (INS) data. Simulations involving explicit many-body polarization interactions assisted in the determination of the binding sites in rht-MOF-1 through the distribution of the induced dipoles that led to strong adsorbate interactions. Four distinct hydrogen sorption sites were determined from the polarization distribution: the nitrate ions located in the corners of the truncated tetrahedral cages, the Cu2+ ions of the paddlewheels that project into the truncated tetrahedral and truncated octahedral cages (Cu1 ions), the Cu2+ ions of the Cu3O trimers (Cu3 ions), and the sides of the paddlewheels in the cuboctahedral cage. The simulations revealed that the initial sorption sites for hydrogen in rht-MOF-1 are the nitrate ions; this site corresponds to the high initial Qst value for hydrogen (9.5 kJ mol-1) in the MOF. The radial distribution functions, g(r), about the Cu2+ ions at various loadings revealed that the Cu1 ions are the preferred open-metal sorption sites for hydrogen at low loading, while the Cu3 ions become occupied at higher loadings. The validation of the aforementioned sorption sites in rht-MOF-1 was confirmed by calculating the two-dimensional quantum rotational levels about each site and comparing the levels to the

  1. Porous ceramics out of oxides

    International Nuclear Information System (INIS)

    Bakunov, V.S.; Balkevich, V.L.; Vlasov, A.S.; Guzman, I.Ya.; Lukin, E.S.; Poluboyarinov, D.N.; Poliskij, R.Ya.

    1977-01-01

    A review is made of manufacturing procedures and properties of oxide ceramics intended for high-temperature thermal insulation and thermal protection applications. Presented are structural characteristics of porous oxide refractories and their properties. Strength and thermal conductivity was shown to depend upon porosity. Described is a procedure for manufacturing porous ceramic materials from aluminium oxide, zirconium dioxide, magnesium oxide, beryllium oxide. The thermal resistance of porous ceramics from BeO is considerably greater than that of other high-refractoriness oxides. Listed are areas of application for porous materials based on oxides

  2. Selective formation of porous silicon

    Science.gov (United States)

    Fathauer, Robert W. (Inventor); Jones, Eric W. (Inventor)

    1993-01-01

    A pattern of porous silicon is produced in the surface of a silicon substrate by forming a pattern of crystal defects in said surface, preferably by applying an ion milling beam through openings in a photoresist layer to the surface, and then exposing said surface to a stain etchant, such as HF:HNO3:H2O. The defected crystal will preferentially etch to form a pattern of porous silicon. When the amorphous content of the porous silicon exceeds 70 percent, the porous silicon pattern emits visible light at room temperature.

  3. Rational design and synthesis of Ni x Co 3−x O 4 nanoparticles derived from multivariate MOF-74 for supercapacitors

    KAUST Repository

    Chen, Siru

    2015-01-01

    © The Royal Society of Chemistry 2015. Mixed transition metal oxides have attracted much attention recently due to their potential application in energy and environmental sciences. The emergence of multivariate MOFs recently has attracted great research attention and provides an opportunity for multivariate mixed-metal oxides. In this work, five isostructural, single-phase MOF-74 structures with different divalent metals (MOF-74-Co, MOF-74-Ni, MOF-74-NiCo1, MOF-74-NiCo2 and MOF-74-NiCo4) were synthesised by varying the mole ratios of Ni/Co mixed-metal ions. After annealing at the appropriate temperature, Co3O4, NiO and three kinds of NixCo3-xO4 mixed-metal oxide nanoparticles with high surface area were easily obtained and the metal ratio was readily controlled, enabling us to systematically investigate the effect of different metal species amounts on the electrochemical properties of the mixed-metal oxide materials. When these metal oxides were used as electrode materials for supercapacitors, we found that the mixed-metal oxides NixCo3-xO4 obtained from bimetallic MOF-74-NiCo structures had obvious advantages compared with the monometallic oxides of MOF-74-Ni and MOF-74-Co. In particular, the NixCo3-xO4-1 with the Ni/Co metal ratio 1:1 exhibited the highest capacitance of 797 F g-1 and excellent cycling stability.

  4. In situ one-step synthesis of hierarchical nitrogen-doped porous carbon for high-performance supercapacitors.

    Science.gov (United States)

    Jeon, Ju-Won; Sharma, Ronish; Meduri, Praveen; Arey, Bruce W; Schaef, Herbert T; Lutkenhaus, Jodie L; Lemmon, John P; Thallapally, Praveen K; Nandasiri, Manjula I; McGrail, Benard Peter; Nune, Satish K

    2014-05-28

    A hierarchically structured nitrogen-doped porous carbon is prepared from a nitrogen-containing isoreticular metal-organic framework (IRMOF-3) using a self-sacrificial templating method. IRMOF-3 itself provides the carbon and nitrogen content as well as the porous structure. For high carbonization temperatures (950 °C), the carbonized MOF required no further purification steps, thus eliminating the need for solvents or acid. Nitrogen content and surface area are easily controlled by the carbonization temperature. The nitrogen content decreases from 7 to 3.3 at % as carbonization temperature increases from 600 to 950 °C. There is a distinct trade-off between nitrogen content, porosity, and defects in the carbon structure. Carbonized IRMOFs are evaluated as supercapacitor electrodes. For a carbonization temperature of 950 °C, the nitrogen-doped porous carbon has an exceptionally high capacitance of 239 F g(-1). In comparison, an analogous nitrogen-free carbon bears a low capacitance of 24 F g(-1), demonstrating the importance of nitrogen dopants in the charge storage process. The route is scalable in that multi-gram quantities of nitrogen-doped porous carbons are easily produced.

  5. A single-ligand ultra-microporous MOF for precombustion CO2 capture and hydrogen purification.

    Science.gov (United States)

    Nandi, Shyamapada; De Luna, Phil; Daff, Thomas D; Rother, Jens; Liu, Ming; Buchanan, William; Hawari, Ayman I; Woo, Tom K; Vaidhyanathan, Ramanathan

    2015-12-01

    Metal organic frameworks (MOFs) built from a single small ligand typically have high stability, are rigid, and have syntheses that are often simple and easily scalable. However, they are normally ultra-microporous and do not have large surface areas amenable to gas separation applications. We report an ultra-microporous (3.5 and 4.8 Å pores) Ni-(4-pyridylcarboxylate)2 with a cubic framework that exhibits exceptionally high CO2/H2 selectivities (285 for 20:80 and 230 for 40:60 mixtures at 10 bar, 40°C) and working capacities (3.95 mmol/g), making it suitable for hydrogen purification under typical precombustion CO2 capture conditions (1- to 10-bar pressure swing). It exhibits facile CO2 adsorption-desorption cycling and has CO2 self-diffusivities of ~3 × 10(-9) m(2)/s, which is two orders higher than that of zeolite 13X and comparable to other top-performing MOFs for this application. Simulations reveal a high density of binding sites that allow for favorable CO2-CO2 interactions and large cooperative binding energies. Ultra-micropores generated by a small ligand ensures hydrolytic, hydrostatic stabilities, shelf life, and stability toward humid gas streams.

  6. A series of new Eu/Tb mixed MOFs with tunable color luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Ximing; He, Xingxiang; Shi, Jie; Cui, Chenhui; Xu, Yan [College of Chemistry and Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing (China)

    2018-01-17

    Two isostructural lanthanide metal-organic frameworks [Ln-MOFs, Ln = Tb (1), Eu (8)] containing oxalic acid ligand with green, red luminescence were solvothermally synthesized. A series of Eu/Tb mixed MOFs (2-7), (C{sub 5}H{sub 6}N){sub 2}[Eu{sub x}Tb{sub 2-x}(H{sub 2}O){sub 2}(C{sub 2}O{sub 4}){sub 4}].2H{sub 2}O, were designed and obtained, which displayed highly tunable luminescence color by adjusting the excitation wavelength. Complexes 1-8 were characterized by IR, elemental analysis, ICP, powder XRD, and TG measurements. The quantum yields of the complexes 1-8 range from 6.89 to 4.15 %, whereas the fluorescence lifetime of 1-8 varies between 1.12 and 0.87 ms. Therefore, with the increase of the molar ratio of Eu, the quantum yields and fluorescence lifetime of the complexes 1-8 gradually decrease. (copyright 2018 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Fabrication of Functionalized MOFs Incorporated Mixed Matrix Hollow Fiber Membrane for Gas Separation

    Directory of Open Access Journals (Sweden)

    Haitao Zhu

    2017-01-01

    Full Text Available The metal-organic framework (MOFs of MIL-53 was functionalized by aminosilane grafting and then incorporated into Ultem®1000 polymer matrix to fabricate mixed matrix hollow fiber membrane (MMHFM with high separation performance. SEM, XRD, and TGA were performed to characterize the functionalized MIL-53 and prepared MMHFM. The filler particles were embedded in membrane successfully and dispersed well in the polymer matrix. The incorporation of MOFs endowed MMHFM better thermal stability. Moreover, effects of solvent ratio in spinning dope, spinning condition, and testing temperature on gas separation performance of MMHFM were investigated. By optimizing dope composition, air gap distance, and bore fluid composition, MMHFM containing functionalized MIL-53 achieved excellent gas permeance and CO2/N2 selectivity. The CO2 permeance increased from 12.2 GPU for pure Ultem HFM to 30.9 GPU and the ideal CO2/N2 selectivity was enhanced from 25.4 to 34.7 simultaneously. Additionally, gas permeance increased but the selectivity decreased with the temperature increase, which followed the solution-diffusion based transport mechanism.

  8. Optical performance of hybrid porous silicon-porous alumina multilayers

    Science.gov (United States)

    Cencha, L. G.; Antonio Hernández, C.; Forzani, L.; Urteaga, R.; Koropecki, R. R.

    2018-05-01

    In this work, we study the optical response of structures involving porous silicon and porous alumina in a multi-layered hybrid structure. We performed a rational design of the optimal sequence necessary to produce a high transmission and selective filter, with potential applications in chemical and biosensors. The combination of these porous materials can be used to exploit its distinguishing features, i.e., high transparency of alumina and high refractive index of porous silicon. We assembled hybrid microcavities with a central porous alumina layer between two porous silicon Bragg reflectors. In this way, we constructed a Fabry-Perot resonator with high reflectivity and low absorption that improves the quality of the filter compared to a microcavity built only with porous silicon or porous alumina. We explored a simpler design in which one of the Bragg reflectors is replaced by the aluminium that remains bound to the alumina after its fabrication. We theoretically explored the potential of the proposal and its limitations when considering the roughness of the layers. We found that the quality of a microcavity made entirely with porous silicon shows a limit in the visible range due to light absorption. This limitation is overcome in the hybrid scheme, with the roughness of the layers determining the ultimate quality. Q-factors of 220 are experimentally obtained for microcavities supported on aluminium, while Q-factors around 600 are reached for microcavities with double Bragg reflectors, centred at 560 nm. This represents a four-fold increase with respect to the optimal porous silicon microcavity at this wavelength.

  9. Fabrication of Fe{sub 3}O{sub 4}@CuO core-shell from MOF based materials and its antibacterial activity

    Energy Technology Data Exchange (ETDEWEB)

    Rajabi, S.K. [Department of Chemistry, University of Guilan, University Campus 2, Rasht (Iran, Islamic Republic of); Sohrabnezhad, Sh., E-mail: sohrabnezhad@guilan.ac.ir [Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 1914, Rasht (Iran, Islamic Republic of); Ghafourian, S. [Clinical Microbiology Research Center, Ilam University of Medical Sciences, Ilam (Iran, Islamic Republic of)

    2016-12-15

    Magnetic Fe{sub 3}O{sub 4}@CuO nanocomposite with a core/shell structure was successfully synthesized via direct calcinations of magnetic Fe{sub 3}O{sub 4}@HKUST-1 in air atmosphere. The morphology, structure, magnetic and porous properties of the as-synthesized nano composites were characterized by using scanning electron microscope (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), and vibration sample magnetometer (VSM). The results showed that the nanocomposite material included a Fe{sub 3}O{sub 4} core and a CuO shell. The Fe{sub 3}O{sub 4}@CuO core-shell can be separated easily from the medium by a small magnet. The antibacterial activity of Fe{sub 3}O{sub 4}-CuO core-shell was investigated against gram-positive and gram-negative bacteria. A new mechanism was proposed for inactivation of bacteria over the prepared sample. It was demonstrated that the core-shell exhibit recyclable antibacterial activity, acting as an ideal long-acting antibacterial agent. - Graphical abstract: Fe{sub 3}O{sub 4}@CuO core-shell release of copper ions. These Cu{sup 2+} ions were responsible for the exhibited antibacterial activity. - Highlights: • The Fe{sub 3}O{sub 4}@CuO core-shell was prepared by MOF method. • This is the first study of antibacterial activity of core-shell consist of CuO and Fe{sub 3}O{sub 4}. • The core-shell can be reused effectively. • Core-shell was separated from the reaction solution by external magnetic field.

  10. Enhanced selectivity in mixed matrix membranes for CO2 capture through efficient dispersion of amine-functionalized MOF nanoparticles

    Science.gov (United States)

    Ghalei, Behnam; Sakurai, Kento; Kinoshita, Yosuke; Wakimoto, Kazuki; Isfahani, Ali Pournaghshband; Song, Qilei; Doitomi, Kazuki; Furukawa, Shuhei; Hirao, Hajime; Kusuda, Hiromu; Kitagawa, Susumu; Sivaniah, Easan

    2017-07-01

    Mixed matrix membranes (MMMs) for gas separation applications have enhanced selectivity when compared with the pure polymer matrix, but are commonly reported with low intrinsic permeability, which has major cost implications for implementation of membrane technologies in large-scale carbon capture projects. High-permeability polymers rarely generate sufficient selectivity for energy-efficient CO2 capture. Here we report substantial selectivity enhancements within high-permeability polymers as a result of the efficient dispersion of amine-functionalized, nanosized metal-organic framework (MOF) additives. The enhancement effects under optimal mixing conditions occur with minimal loss in overall permeability. Nanosizing of the MOF enhances its dispersion within the polymer matrix to minimize non-selective microvoid formation around the particles. Amination of such MOFs increases their interaction with thepolymer matrix, resulting in a measured rigidification and enhanced selectivity of the overall composite. The optimal MOF MMM performance was verified in three different polymer systems, and also over pressure and temperature ranges suitable for carbon capture.

  11. Gaining Insights on the H2–Sorbent Interactions: Robust soc-MOF Platform as a Case Study

    KAUST Repository

    Cairns, Amy; Eckert, Juergen; Wojtas, Lukasz; Thommes, Matthias; Wallacher, Dirk; Georgiev, Peter A.; Forster, Paul M.; Belmabkhout, Youssef; Ollivier, Jacques; Eddaoudi, Mohamed

    2016-01-01

    platform to examine the impact of specific structural parameters on H2–MOF interactions via systematic gas adsorption studies. We infer that enhanced binding of molecular H2 is primarily governed by the presence and type of vacant metal centers (i.e., Fe

  12. Isoreticular rare earth fcu-MOFs for the selective removal of H 2 S from CO 2 containing gases

    KAUST Repository

    Bhatt, Prashant; Belmabkhout, Youssef; Assen, Ayalew Hussen Assen; Weselinski, Lukasz Jan; Jiang, Hao; Cadiau, Amandine; Xue, Dongxu; Eddaoudi, Mohamed

    2017-01-01

    . Markedly, RE-fcu-MOFs, having different pore apertures sizes in the range of 4.7-6.0 Å and different functionalities, showed excellent properties for the removal of H2S from CO2 and CH4 containing gases such as natural gas, biogas and landfill gas. A series

  13. Box-like gel capsules from heterostructures based on a core-shell MOF as a template of crystal crosslinking.

    Science.gov (United States)

    Ishiwata, Takumi; Michibata, Ayano; Kokado, Kenta; Ferlay, Sylvie; Hosseini, Mir Wais; Sada, Kazuki

    2018-02-06

    New polymer capsules (PCs) were obtained using a crystal crosslinking (CC) method on core-shell MOF crystals. The latter are based on the epitaxial growth of two isostructural coordination polymers which are then selectively crosslinked. Decomposition of the non-reticulated phase leads to new PCs, possessing a well-defined hollow cubic shape reflecting the heterostructure of the template.

  14. Towards protective MOFs: post-synthetic modification of MIL-101 with oxime groups and their interactions with toxic chemicals

    NARCIS (Netherlands)

    Grol, M. van; Gorzkowska-Sobasb, A.A.; Koning, M.C. de

    2017-01-01

    In an attempt to broaden the scope of protective MOFs towards toxic compounds, we decided to introduce a reactive (nucleophilic) functionality in MIL101 by post-synthesis modification 1,2. This functionality would complement already existing adsorptive properties with an ability to capture or

  15. Synthesis, Structural Characterization and Up-Conversion Luminescence Properties of NaYF4:Er3+,Yb3+@MOFs Nanocomposites

    Science.gov (United States)

    Giang, Lam Thi Kieu; Marciniak, Lukasz; Huy, Tran Quang; Vu, Nguyen; Le, Ngo Thi Hong; Binh, Nguyen Thanh; Lam, Tran Dai; Minh, Le Quoc

    2017-10-01

    This paper describes a facile synthesis of NaYF4:Er3+,Yb3+ nanoparticles embraced in metal-organic frameworks (MOFs), known as NaYF4:Er3+, Yb3+@MOFs core/shell nanostructures, by using iron(III) carboxylate (MIL-100) and zeolitic imidazolate frameworks (ZIF-8). Morphological, structural and optical characterization of these nanostructures were investigated by field emission-scanning electron microscopy, Fourier transform infrared spectroscopy, x-ray diffraction, and up-conversion luminescence measurements. Results showed that spherical-shaped NaYF4:Er3+,Yb3+@MIL-100 nanocomposites with diameters of 150-250 nm, and rod-shaped NaYF4:Er3+,Yb3+@ZIF-8 nanocomposites with lengths of 300-550 nm, were successfully synthesized. Under a 980-nm laser excitation at room temperature, the NaYF4:Er3+,Yb3+@MOFs nanocomposites exhibited strong up-conversion luminescence with two emission bands in the green part of spectrum at 520 nm and 540 nm corresponding to the 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2 transitions of Er3+ ions, respectively, and a red emission band at 655 nm corresponding to the 4F9/2 → 4I15/2 transition of Er3+ ions. The above properties of NaYF4:Er3+,Yb3+@MOFs make them promising candidates for applications in biotechnology.

  16. A more efficient way to shape metal-organic framework (MOF) powder materials for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2015-04-01

    Full Text Available operation time. This granulation approach is a more efficient way to shape MOF-type powder materials into application-specific configurations compared to the mechanical pressing method. The pellets could be conveniently packed in a small hydrogen storage...

  17. Advanced fabrication method for the preparation of MOF thin films: Liquid-phase epitaxy approach meets spin coating method.

    KAUST Repository

    Chernikova, Valeriya; Shekhah, Osama; Eddaoudi, Mohamed

    2016-01-01

    Here we report a new and advanced method for the fabrication of highly oriented/polycrystalline metal-organic framework (MOF) thin films. Building on the attractive features of the liquid-phase epitaxy (LPE) approach, a facile spin coating method

  18. The Design of Dual-Emissive Composite Material [Zn2(HL)3]+@MOF-5 as Self-Calibrating Luminescent Sensors of Al3+ Ions and Monoethanolamine.

    Science.gov (United States)

    Wu, Meng-Meng; Wang, Jiao-Yang; Sun, Rui; Zhao, Cui; Zhao, Jiong-Peng; Che, Guang-Bo; Liu, Fu-Chen

    2017-08-21

    Introducing another chromophore into a luminescent MOF is a potential way to assembling novel dual-emissive luminescent materials. Putting the chromophore, for which luminescence can be enhanced by Zn 2+ ion, into MOF-5 by the "bottle around ship" strategy is a simple but efficient synthesis method to realize such dual-emissive materials. According to this strategy, a novel dual-emissive luminescent composite material [Zn 2 (HL) 3 ] + @MOF-5 was constructed by loading the [La 3 (HL) 2 L 2 (NO 3 ) 3 H 2 O] (1) (H 2 L = 7,7'-(ethane-1,1'-diyl)8-hydro-quinoline) into MOF-5, in which the [Zn 2 (HL) 3 ] + anions were transformed from 1 with the existence of Zn 2+ . The dual-emissive composite materials show excellent luminescence with two emissions of MOF-5 at 410 nm and [Zn 2 (HL) 3 ] + at 524 nm. Furthermore, by combining characteristics of MOF-5 and the guest chromophore, the composite material is highly selectively sensitive toward Al 3+ and monoethanolamine, which makes [Zn 2 (HL) 3 ] + @MOF-5 a potential self-calibrated fluorescence sensor.

  19. Reversible hydrogen storage by NaAlH4 confined within a titanium-functionalized MOF-74(Mg) nanoreactor.

    Science.gov (United States)

    Stavila, Vitalie; Bhakta, Raghunandan K; Alam, Todd M; Majzoub, Eric H; Allendorf, Mark D

    2012-11-27

    We demonstrate that NaAlH(4) confined within the nanopores of a titanium-functionalized metal-organic framework (MOF) template MOF-74(Mg) can reversibly store hydrogen with minimal loss of capacity. Hydride-infiltrated samples were synthesized by melt infiltration, achieving loadings up to 21 wt %. MOF-74(Mg) possesses one-dimensional, 12 Å channels lined with Mg atoms having open coordination sites, which can serve as sites for Ti catalyst stabilization. MOF-74(Mg) is stable under repeated hydrogen desorption and hydride regeneration cycles, allowing it to serve as a "nanoreactor". Confining NaAlH(4) within these pores alters the decomposition pathway by eliminating the stable intermediate Na(3)AlH(6) phase observed during bulk decomposition and proceeding directly to NaH, Al, and H(2), in agreement with theory. The onset of hydrogen desorption for both Ti-doped and undoped nano-NaAlH(4)@MOF-74(Mg) is ∼50 °C, nearly 100 °C lower than bulk NaAlH(4). However, the presence of titanium is not necessary for this increase in desorption kinetics but enables rehydriding to be almost fully reversible. Isothermal kinetic studies indicate that the activation energy for H(2) desorption is reduced from 79.5 kJ mol(-1) in bulk Ti-doped NaAlH(4) to 57.4 kJ mol(-1) for nanoconfined NaAlH(4). The structural properties of nano-NaAlH(4)@MOF-74(Mg) were probed using (23)Na and (27)Al solid-state MAS NMR, which indicates that the hydride is not decomposed during infiltration and that Al is present as tetrahedral AlH(4)(-) anions prior to desorption and as Al metal after desorption. Because of the highly ordered MOF structure and monodisperse pore dimensions, our results allow key template features to be identified to ensure reversible, low-temperature hydrogen storage.

  20. One-step synthesis of highly efficient nanocatalysts on the supports with hierarchical pores using porous ionic liquid-water gel.

    Science.gov (United States)

    Kang, Xinchen; Zhang, Jianling; Shang, Wenting; Wu, Tianbin; Zhang, Peng; Han, Buxing; Wu, Zhonghua; Mo, Guang; Xing, Xueqing

    2014-03-12

    Stable porous ionic liquid-water gel induced by inorganic salts was created for the first time. The porous gel was used to develop a one-step method to synthesize supported metal nanocatalysts. Au/SiO2, Ru/SiO2, Pd/Cu(2-pymo)2 metal-organic framework (Cu-MOF), and Au/polyacrylamide (PAM) were synthesized, in which the supports had hierarchical meso- and macropores, the size of the metal nanocatalysts could be very small (esterification of benzyl alcohol to methyl benzoate, benzene hydrogenation to cyclohexane, and oxidation of benzyl alcohol to benzaldehyde because they combined the advantages of the nanocatalysts of small size and hierarchical porosity of the supports. In addition, this method is very simple.

  1. Dye@bio-MOF-1 Composite as a Dual-Emitting Platform for Enhanced Detection of a Wide Range of Explosive Molecules.

    Science.gov (United States)

    Wang, Chen; Tian, Li; Zhu, Wei; Wang, Shiqiang; Wang, Peng; Liang, Yun; Zhang, Wanlin; Zhao, Hongwei; Li, Guangtao

    2017-06-14

    By incorporating a cationic dye within a metal-organic framework (MOF) through an ion-exchange process, a responsive dye@bio-MOF-1 composite has been synthesized, serving as a dual-emitting platform for enhanced detection of different kinds of nitro-explosives, especially nitroalkanes, nitramines, and nitrate esters. The dye@bio-MOF-1 composite was constructed with free amines on their well-defined cavities, which is essential for the capture of explosives into their confined nanospace. It was observed that the encapsulation of explosives into the constructed dye@bio-MOF-1 composite could dramatically alter the luminescent properties of the dyes as well as the MOF skeletons owing to the size exclusivity and confinement-induced effect. For nitroaromatics, the dye@bio-MOF-1 composite exhibits turn-off responses via fluorescence quenching. Unexpectedly, the composite shows unique turn-on responses for aliphatic nitro-organics via confinement-induced enhancement, demonstrating enhanced ability to detecting different kinds of explosives selectively in aqueous solution. Furthermore, the dye@bio-MOF-1 film was facilely fabricated, making the chemical sensing more convenient and easier to realize the discrimination of the targeted explosives. The dual tunable responses indicate that dye@bio-MOF-1 composites are favorable materials for molecular sensing. On the basis of the host-guest properties of the constructed dye@bio-MOF-1 composite, our work can be further extended to sensing specific analytes with remarkable turn-on sensing properties, in particular those difficult to recognize with conventional methods.

  2. Brønsted instead of Lewis acidity in functionalized MIL-101Cr MOFs for efficient heterogeneous (nano-MOF) catalysis in the condensation reaction of aldehydes with alcohols.

    Science.gov (United States)

    Herbst, Annika; Khutia, Anupam; Janiak, Christoph

    2014-07-21

    Porous chromium(III) 2-nitro-, 2-amino-, and nonfunctionalized terephthalate (MIL-101Cr) metal organic frameworks are heterogeneous catalysts for diacetal formation from benzaldehyde and methanol (B-M reaction) as well as other aldehydes and alcohols. MIL-101Cr-NO2 obtained by direct reaction between CrO3 and 2-nitro-terephthalate showed the highest activity with 99% conversion in the B-M reaction in 90 min and turnover numbers of 114. The activity decreased in the order MIL-101Cr-NO2 > MIL-101Cr > MIL-101Cr-NH2. Within different samples of nonfunctionalized MIL-101Cr the activity increased with surface area. Methanol gas sorption of the different MIL materials correlates with the BET surface area and pore volume but not with the diacetalization activity. Benzaldehyde adsorption from heptane showed no significant difference for the different MILs. Gas sorption studies of CD3CN to probe for a higher Lewis acidity in MIL-101Cr-NO2 remained inconclusive. A high B-M catalytic activity of wet MIL-101Cr-NO2 excluded significant contributions from coordinatively unsaturated Lewis-acid sites. pH measurements of methanol dispersions of the MIL materials gave the most acidic pH (as low as 1.9) for MIL-101Cr-NO2, which significantly increased over MIL-101Cr (3.0) to MIL-101Cr-NH2 (3.3). The increase in acidity is of short range or a surface effect to the heterogeneous MIL particles as protons dissociating from the polarized aqua ligands (Cr-OH2) have to stay near the insoluble counteranionic framework. The variation in Brønsted acidity of MIL-101Cr-NO2 > MIL-101Cr ≈ MIL-101Cr-NH2 correlates with the withdrawing effect of NO2 and the diacetalization activity. The catalytic B-M activity of soluble, substitution-inert, and acidic Cr(NO3)3·9H2O supports the Brønsted-acid effect of the MIL materials. Filtration and centrifugation experiments with MIL-101Cr-NO2 revealed that about 2/3 of the catalytic activity comes from nano-MOF particles with a diameter below 200 nm. The MIL

  3. Discovering the enzyme mimetic activity of metal-organic framework (MOF) for label-free and colorimetric sensing of biomolecules.

    Science.gov (United States)

    Wang, Ying; Zhu, Yingjing; Binyam, Atsebeha; Liu, Misha; Wu, Yinan; Li, Fengting

    2016-12-15

    A label-free sensing strategy based on the enzyme-mimicking activity of MOF was demonstrated for colorimetric detection of biomolecules. Firstly obvious blue color was observed due to the high efficiency of peroxidase-like catalytic activity of Fe-MIL-88A (an ion-based MOF material) toward 3,3',5,5'-tetramethylbenzidine (TMB). Then in the presence of target biomolecule and corresponding aptamer, the mimetic activity of Fe-MIL-88A can be strongly inhibited and used directly to realize the colorimetric detection. On the basis of the interesting findings, we designed a straightforward, label-free and sensitive colorimetric method for biomolecule detection by using the enzyme mimetic property of MOF coupling with molecular recognition element. Compared with the existed publications, our work breaks the routine way by setting up an inorganic-organic MOF-aptamer hybrid platform for colorimetric determination of biomolecules, expanding the targets scope from H2O2 or glucose to biomolecules. As a proof of concept, thrombin and thrombin aptamer was used as a model analyte. The limit of detection of 10nM can be achieved with naked eyes and ultrahigh selectivity of thrombin toward numerous interfering substances with 10-fold concentration was demonstrated significantly. Of note, the method was further applied for the detection of thrombin in human serum samples, showing the results in agreement with those values obtained in an immobilization buffer by the colorimetric method. This inorganic-organic MOF-aptamer sensing strategy may in principle be universally applicable for the detection of a range of environmental or biomedical molecules of interests. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Applying the Power of Reticular Chemistry to Finding the Missing alb-MOF Platform Based on the (6,12)-Coordinated Edge-Transitive Net

    KAUST Repository

    Chen, Zhijie

    2017-02-05

    Highly connected and edge-transitive nets are of prime importance in crystal chemistry and are regarded as ideal blueprints for the rational design and construction of metal-organic frameworks (MOFs). We report the design and synthesis of highly connected MOFs based on reticulation of the sole two edge-transitive nets with a vertex figure as double six-membered-ring (d6R) building unit, namely the (4,12)-coordinated shp net (square and hexagonal-prism) and the (6,12)-coordinated alb net (aluminum diboride, hexagonal-prism and trigonal-prism). Decidedly, the combination of our recently isolated 12-connected (12-c) rare-earth (RE) nonanuclear [RE(μ-OH)(μ-O)(OC-)] carboxylate-based cluster, points of extension matching the 12 vertices of hexagonal-prism d6R, with 4-connected (4-c) square porphyrinic tetracarboxylate ligand led to the formation of the targeted RE-shp-MOF. This is the first time that RE-MOFs based on 12-c molecular building blocks (MBBs), d6R building units, have been deliberately targeted and successfully isolated, paving the way for the long-awaited (6,12)-c MOF with alb topology. Indeed, combination of a custom-designed hexacarboxylate ligand with RE salts led to the formation of the first related alb-MOF, RE-alb-MOF. Intuitively, we successfully transplanted the alb topology to another chemical system and constructed the first indium-based alb-MOF, In-alb-MOF, by employing trinuclear [In(μ-O)(OC-)] as the requisite 6-connected trigonal-prism and purposely made a dodecacarboxylate ligand as a compatible 12-c MBB. Prominently, the dodecacarboxylate ligand was employed to transplant shp topology into copper-based MOFs by employing the copper paddlewheel [Cu(OC-)] as the complementary square building unit, affording the first Cu-shp-MOF. We revealed that highly connected edge-transitive nets such shp and alb are ideal for topological transplantation and deliberate construction of related MOFs based on minimal edge-transitive nets.

  5. The Organic Secondary Building Unit: Strong Intermolecular π Interactions Define Topology in MIT-25, a Mesoporous MOF with Proton-Replete Channels.

    Science.gov (United States)

    Park, Sarah S; Hendon, Christopher H; Fielding, Alistair J; Walsh, Aron; O'Keeffe, Michael; Dincă, Mircea

    2017-03-15

    The structure-directing role of the inorganic secondary building unit (SBU) is key for determining the topology of metal-organic frameworks (MOFs). Here we show that organic building units relying on strong π interactions that are energetically competitive with the formation of common inorganic SBUs can also play a role in defining the topology. We demonstrate the importance of the organic SBU in the formation of Mg 2 H 6 (H 3 O)(TTFTB) 3 (MIT-25), a mesoporous MOF with the new ssp topology. A delocalized electronic hole is critical in the stabilization of the TTF triad organic SBUs and exemplifies a design principle for future MOF synthesis.

  6. Applying the Power of Reticular Chemistry to Finding the Missing alb-MOF Platform Based on the (6,12)-Coordinated Edge-Transitive Net

    KAUST Repository

    Chen, Zhijie; Weselinski, Lukasz Jan; Adil, Karim; Belmabkhout, Youssef; Shkurenko, Aleksander; Jiang, Hao; Bhatt, Prashant; Guillerm, Vincent; Dauzon, Emilie; Xue, Dongxu; O’ Keeffe, Michael; Eddaoudi, Mohamed

    2017-01-01

    Highly connected and edge-transitive nets are of prime importance in crystal chemistry and are regarded as ideal blueprints for the rational design and construction of metal-organic frameworks (MOFs). We report the design and synthesis of highly connected MOFs based on reticulation of the sole two edge-transitive nets with a vertex figure as double six-membered-ring (d6R) building unit, namely the (4,12)-coordinated shp net (square and hexagonal-prism) and the (6,12)-coordinated alb net (aluminum diboride, hexagonal-prism and trigonal-prism). Decidedly, the combination of our recently isolated 12-connected (12-c) rare-earth (RE) nonanuclear [RE(μ-OH)(μ-O)(OC-)] carboxylate-based cluster, points of extension matching the 12 vertices of hexagonal-prism d6R, with 4-connected (4-c) square porphyrinic tetracarboxylate ligand led to the formation of the targeted RE-shp-MOF. This is the first time that RE-MOFs based on 12-c molecular building blocks (MBBs), d6R building units, have been deliberately targeted and successfully isolated, paving the way for the long-awaited (6,12)-c MOF with alb topology. Indeed, combination of a custom-designed hexacarboxylate ligand with RE salts led to the formation of the first related alb-MOF, RE-alb-MOF. Intuitively, we successfully transplanted the alb topology to another chemical system and constructed the first indium-based alb-MOF, In-alb-MOF, by employing trinuclear [In(μ-O)(OC-)] as the requisite 6-connected trigonal-prism and purposely made a dodecacarboxylate ligand as a compatible 12-c MBB. Prominently, the dodecacarboxylate ligand was employed to transplant shp topology into copper-based MOFs by employing the copper paddlewheel [Cu(OC-)] as the complementary square building unit, affording the first Cu-shp-MOF. We revealed that highly connected edge-transitive nets such shp and alb are ideal for topological transplantation and deliberate construction of related MOFs based on minimal edge-transitive nets.

  7. Flexible and porous cellulose aerogels/zeolitic imidazolate framework (ZIF-8) hybrids for adsorption removal of Cr(IV) from water

    Science.gov (United States)

    Bo, Shaoguo; Ren, Wenjing; Lei, Chao; Xie, Yuanbo; Cai, Yurong; Wang, Shunli; Gao, Junkuo; Ni, Qingqing; Yao, Juming

    2018-06-01

    The low cost of adsorption treatment of heavy metal ions in water has been extensively studied. In this paper, we have demonstrated a facile method of combining two emerging materials cellulose aerogels (CA) and metal-organic frameworks (MOFs) into one highly functional aerogel to adsorption removal of heavy metal ions from water, by entrapping MOF particles into a flexible and porous CA. The resultant hybrid cellulose aerogels had a highly porous structure with zeolitic imidazolate framework-8 (ZIF-8) loadings can reach 30 wt%. The hybrid cellulose aerogels (named as ZIF-8@CA) show good adsorption capacity for Cr(Ⅵ). The adsorption process of ZIF-8@CA is better described by pseudo-second-order kinetic model and Langmuir isotherm, with maximum monolayer adsorption capacity of 41.8 mg g-1 for Cr(Ⅵ), whose adsorption capacity has greatly improved when compared with a single CA or ZIF-8. Thus, such a flexible and durable hybrid cellulose aerogel is a very prospective material for metal ions cleanup and industrial wastewater purification.

  8. Convection in porous media

    CERN Document Server

    Nield, Donald A

    1992-01-01

    This book provides a user-friendly introduction to the topic of convection in porous media The authors as- sume that the reader is familiar with the basic elements of fluid mechanics and heat transfer, but otherwise the book is self-contained The book will be useful both as a review (for reference) and as a tutorial work, suitable as a textbook in a graduate course or seminar The book brings into perspective the voluminous research that has been performed during the last two decades The field has recently exploded because of worldwide concern with issues such as energy self-sufficiency and pollution of the environment Areas of application include the insulation of buildings and equipment, energy storage and recovery, geothermal reservoirs, nuclear waste disposal, chemical reactor engineering, and the storage of heat-generating materials such as grain and coal Geophysical applications range from the flow of groundwater around hot intrusions to the stability of snow against avalanches

  9. Optimized manufacturable porous materials

    DEFF Research Database (Denmark)

    Andreassen, Erik; Andreasen, Casper Schousboe; Jensen, Jakob Søndergaard

    Topology optimization has been used to design two-dimensional material structures with specific elastic properties, but optimized designs of three-dimensional material structures are more scarsely seen. Partly because it requires more computational power, and partly because it is a major challenge...... to include manufacturing constraints in the optimization. This work focuses on incorporating the manufacturability into the optimization procedure, allowing the resulting material structure to be manufactured directly using rapid manufacturing techniques, such as selective laser melting/sintering (SLM....../S). The available manufacturing methods are best suited for porous materials (one constituent and void), but the optimization procedure can easily include more constituents. The elasticity tensor is found from one unit cell using the homogenization method together with a standard finite element (FE) discretization...

  10. Filtration in Porous Media

    DEFF Research Database (Denmark)

    Yuan, Hao; Shapiro, Alexander

    There is a considerable and ongoing effort aimed at understanding the transport and the deposition of suspended particles in porous media, especially non-Fickian transport and non-exponential deposition of particles. In this work, the influential parameters in filtration models are studied...... to understand their effects on the non-Fickian transport and the non-exponential deposition. The filtration models are validated by the comparisons between the modelling results and the experimental data.The elliptic equation with distributed filtration coefficients may be applied to model non-Fickian transport...... and hyperexponential deposition. The filtration model accounting for the migration of surface associated particles may be applied for non-monotonic deposition....

  11. Biogenic Cracks in Porous Rock

    Science.gov (United States)

    Hemmerle, A.; Hartung, J.; Hallatschek, O.; Goehring, L.; Herminghaus, S.

    2014-12-01

    Microorganisms growing on and inside porous rock may fracture it by various processes. Some of the mechanisms of biofouling and bioweathering are today identified and partially understood but most emphasis is on chemical weathering, while mechanical contributions have been neglected. However, as demonstrated by the perseverance of a seed germinating and cracking up a concrete block, the turgor pressure of living organisms can be very significant. Here, we present results of a systematic study of the effects of the mechanical forces of growing microbial populations on the weathering of porous media. We designed a model porous medium made of glass beads held together by polydimethylsiloxane (PDMS), a curable polymer. The rheological properties of the porous medium, whose shape and size are tunable, can be controlled by the ratio of crosslinker to base used in the PDMS (see Fig. 1). Glass and PDMS being inert to most chemicals, we are able to focus on the mechanical processes of biodeterioration, excluding any chemical weathering. Inspired by recent measurements of the high pressure (~0.5 Mpa) exerted by a growing population of yeasts trapped in a microfluidic device, we show that yeast cells can be cultured homogeneously within porous medium until saturation of the porous space. We investigate then the effects of such an inner pressure on the mechanical properties of the sample. Using the same model system, we study also the complex interplay between biofilms and porous media. We focus in particular on the effects of pore size on the penetration of the biofilm within the porous sample, and on the resulting deformations of the matrix, opening new perspectives into the understanding of life in complex geometry. Figure 1. Left : cell culture growing in a model porous medium. The white spheres represent the grains, bonds are displayed in grey, and microbes in green. Right: microscopy picture of glass beads linked by PDMS bridges, scale bar: 100 μm.

  12. Luminescence of porous silicon doped by erbium

    International Nuclear Information System (INIS)

    Bondarenko, V.P.; Vorozov, N.N.; Dolgij, L.N.; Dorofeev, A.M.; Kazyuchits, N.M.; Leshok, A.A.; Troyanova, G.N.

    1996-01-01

    The possibility of the 1.54 μm intensive luminescence in the silicon dense porous layers, doped by erbium, with various structures is shown. Low-porous materials of both porous type on the p-type silicon and porous silicon with wood-like structure on the n + type silicon may be used for formation of light-emitting structures

  13. Unique Chiral Interpenetrating d-f Heterometallic MOFs as Luminescent Sensors.

    Science.gov (United States)

    Wu, Zhi-Lei; Dong, Jie; Ni, Wei-Yan; Zhang, Bo-Wen; Cui, Jian-Zhong; Zhao, Bin

    2015-06-01

    One novel three-dimensional (3D) 3d-4f metal-organic framework (MOF), [TbZn(L)(CO3)2(H2O)]n (1) [HL = 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine], has been successfully synthesized and structurally characterized. Structural analysis shows that compound 1 features a unique chiral interpenetrating 3D framework for the first time. The resulting crystals of 1 are composed of enantiomers 1a (P41) and 1b (P43), as was clearly confirmed by the crystal structure and the corresponding circular dichroism (CD) analyses of eight randomly selected crystals. The investigations on CD spectra based on every single crystal clearly assigned the Cotton effect signals. The powder X-ray diffraction measurement of 1 after being immersed in common solvents reveals that 1 possess excellent solvent stability. Furthermore, luminescent studies imply that 1 displays highly selective luminescent sensing of aldehydes, such as formol, acetaldehyde, and propanal.

  14. Series of chiral interpenetrating 3d-4f heterometallic MOFs: Luminescent sensors and magnetic properties

    Science.gov (United States)

    Zhang, Xiaolei; Chen, Chen; Liu, Xiaoli; Gao, Peng; Hu, Ming

    2017-09-01

    Series of chiral 3d-4f heterometallic MOFs based on a multidentate terpyridyl carboxylic acid ligand have been synthesized under the solvothermal conditions, namely, [LnZnL(CO3)2(H2O)]n (Ln = Eu (1), Gd (2), Dy (3), Ho (4), Er (5), Tm (6), Yb (7), Lu (8)) (HL = 4‧-(4-carboxyphenyl)-2,2‧:6‧,2″-terpyridine). Compounds 1-8 were structurally characterized by the elemental analyses, infrared spectra, and single crystal X-ray diffractions. Compounds 1-8 exhibit the chiral interpenetrating 3D frameworks. Interestingly, 1 can serve as the luminescent sensor to detect nitrobenzene molecules with high sensitivity. The investigations on CD spectra of single crystals clearly assigned the Cotton effect, indicating that there exist two chiral enantiomers of 1-8 in the course of crystallization. The magnetic properties of 2 and 7 were exploited, respectively.

  15. Anisotropically Swelling Gels Attained through Axis-Dependent Crosslinking of MOF Crystals.

    Science.gov (United States)

    Ishiwata, Takumi; Kokado, Kenta; Sada, Kazuki

    2017-03-01

    Anisotropically deforming objects have attracted considerable interest for use in molecular machines and artificial muscles. Herein, we focus on a new approach based on the crystal crosslinking of organic ligands in a pillared-layer metal-organic framework (PLMOF). The approach involves the transformation from crosslinked PLMOF to polymer gels through hydrolysis of the coordination bonds between the organic ligands and metal ions, giving a network polymer that exhibits anisotropic swelling. The anisotropic monomer arrangement in the PLMOF underwent axis-dependent crosslinking to yield anisotropically swelling gels. Therefore, the crystal crosslinking of MOFs should be a useful method for creating actuators with designable deformation properties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Porous media geometry and transports

    CERN Document Server

    Adler, Pierre

    1992-01-01

    The goal of ""Porous Media: Geometry and Transports"" is to provide the basis of a rational and modern approach to porous media. This book emphasizes several geometrical structures (spatially periodic, fractal, and random to reconstructed) and the three major single-phase transports (diffusion, convection, and Taylor dispersion).""Porous Media"" serves various purposes. For students it introduces basic information on structure and transports. Engineers will find this book useful as a readily accessible assemblage of al the major experimental results pertaining to single-phase tr

  17. LDH nanocages synthesized with MOF templates and their high performance as supercapacitors

    Science.gov (United States)

    Jiang, Zhen; Li, Zhengping; Qin, Zhenhua; Sun, Haiyan; Jiao, Xiuling; Chen, Dairong

    2013-11-01

    Layered double hydroxides (LDHs) are currently attracting intense research interest for their various applications. Three LDH hollow nano-polyhedra are synthesized with zeolitic imidazolate framework-67 (ZIF-67) nanocrystals as the templates. The nanocages well inherit the rhombic dodecahedral shape of the ZIF-67 templates, and the shell is composed of nanosheets assembled with an edge-to-face stacking. This is the first synthesis of the LDH non-spherical structures. And the mechanism of utilizing metal-organic framework (MOF) nanocrystals as templates is explored. Control of the simultaneous reactions, the precipitation of the shells and the template etching, is extremely crucial to the preparation of the perfect nanocages. And the Ni-Co LDH nanocages exhibit superior pseudocapacitance property due to their novel hierarchical and submicroscopic structures.Layered double hydroxides (LDHs) are currently attracting intense research interest for their various applications. Three LDH hollow nano-polyhedra are synthesized with zeolitic imidazolate framework-67 (ZIF-67) nanocrystals as the templates. The nanocages well inherit the rhombic dodecahedral shape of the ZIF-67 templates, and the shell is composed of nanosheets assembled with an edge-to-face stacking. This is the first synthesis of the LDH non-spherical structures. And the mechanism of utilizing metal-organic framework (MOF) nanocrystals as templates is explored. Control of the simultaneous reactions, the precipitation of the shells and the template etching, is extremely crucial to the preparation of the perfect nanocages. And the Ni-Co LDH nanocages exhibit superior pseudocapacitance property due to their novel hierarchical and submicroscopic structures. Electronic supplementary information (ESI) available: Experimental details, XRD, TEM, SEM, and XPS images. See DOI: 10.1039/c3nr03829g

  18. Hydrodynamic dispersion within porous biofilms

    KAUST Repository

    Davit, Y.; Byrne, H.; Osborne, J.; Pitt-Francis, J.; Gavaghan, D.; Quintard, M.

    2013-01-01

    Many microorganisms live within surface-associated consortia, termed biofilms, that can form intricate porous structures interspersed with a network of fluid channels. In such systems, transport phenomena, including flow and advection, regulate

  19. Vibrational modes of porous silicon

    International Nuclear Information System (INIS)

    Sabra, M.; Naddaf, M.

    2012-01-01

    On the basis of theoretical and experimental investigations, the origin of room temperature photoluminescence (PL) from porous silicon is found to related to chemical complexes constituted the surface, in particular, SiHx, SiOx and SiOH groups. Ab initio atomic and molecular electronic structure calculations on select siloxane compounds were used for imitation of infrared (IR) spectra of porous silicon. These are compared to the IR spectra of porous silicon recorded by using Fourier Transform Infrared Spectroscopy (FTIR). In contrast to linear siloxane, the suggested circular siloxane terminated with linear siloxane structure is found to well-imitate the experimental spectra. These results are augmented with EDX (energy dispersive x-ray spectroscopy) measurements, which showed that the increase of SiOx content in porous silicon due to rapid oxidation process results in considerable decrease in PL peak intensity and a blue shift in the peak position. (author)

  20. Transport phenomena in porous media

    CERN Document Server

    Ingham, Derek B

    1998-01-01

    Research into thermal convection in porous media has substantially increased during recent years due to its numerous practical applications. These problems have attracted the attention of industrialists, engineers and scientists from many very diversified disciplines, such as applied mathematics, chemical, civil, environmental, mechanical and nuclear engineering, geothermal physics and food science. Thus, there is a wealth of information now available on convective processes in porous media and it is therefore appropriate and timely to undertake a new critical evaluation of this contemporary information. Transport Phenomena in Porous Media contains 17 chapters and represents the collective work of 27 of the world's leading experts, from 12 countries, in heat transfer in porous media. The recent intensive research in this area has substantially raised the expectations for numerous new practical applications and this makes the book a most timely addition to the existing literature. It includes recent major deve...

  1. Positronium chemistry in porous materials

    International Nuclear Information System (INIS)

    Kobayashi, Y.; Ito, K.; Oka, T.; Hirata, K.

    2007-01-01

    Porous materials have fascinated positron and positronium chemists for over decades. In the early 1970s it was already known that ortho-positronium (o-Ps) exhibits characteristic long lifetimes in silica gels, porous glass and zeolites. Since then, our understanding of Ps formation, diffusion and annihilation has been drastically deepened. Ps is now well recognized as a powerful porosimetric and chemical probe to study the average pore size, pore size distribution, pore connectivity and surface properties of various porous materials including thin films. In this paper, developments of Ps chemistry in porous materials undertaken in the past some 40 yr are surveyed and problems to be addressed in future are briefly discussed

  2. Porous substrates filled with nanomaterials

    Science.gov (United States)

    Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.; Stadermann, Michael

    2018-04-03

    A composition comprising: at least one porous carbon monolith, such as a carbon aerogel, comprising internal pores, and at least one nanomaterial, such as carbon nanotubes, disposed uniformly throughout the internal pores. The nanomaterial can be disposed in the middle of the monolith. In addition, a method for making a monolithic solid with both high surface area and good bulk electrical conductivity is provided. A porous substrate having a thickness of 100 microns or more and comprising macropores throughout its thickness is prepared. At least one catalyst is deposited inside the porous substrate. Subsequently, chemical vapor deposition is used to uniformly deposit a nanomaterial in the macropores throughout the thickness of the porous substrate. Applications include electrical energy storage, such as batteries and capacitors, and hydrogen storage.

  3. Influence of Filler Pore Structure and Polymer on the Performance of MOF-Based Mixed-Matrix Membranes for CO2 Capture

    KAUST Repository

    Sabetghadam, Anahid

    2018-03-24

    To gain insight into the influence of metal-organic framework (MOF) fillers and polymers on membrane performance, eight different composites were studied by combining four MOFs and two polymers. MOF materials (NH-MIL-53(Al), MIL-69(Al), MIL-96(Al) and ZIF-94) with various chemical functionalities, topologies, and dimensionalities of porosity were employed as fillers, and two typical polymers with different permeability-selectivity properties (6FDA-DAM and Pebax) were selected as matrices. The best-performing MOF-polymer composites were prepared by loading 25wt% of MIL-96(Al) as filler, which improved the permeability and selectivity of 6FDA-DAM to 32 and 10%, while for Pebax they were enhanced to 25 and 18%, respectively. The observed differences in membrane performance in the separation of CO from N are explained on the basis of gas solubility, diffusivity properties, and compatibility between the filler and polymer phases.

  4. Influence of Filler Pore Structure and Polymer on the Performance of MOF-Based Mixed-Matrix Membranes for CO2 Capture

    KAUST Repository

    Sabetghadam, Anahid; Liu, Xinlei; Benzaqui, Marvin; Gkaniatsou, Effrosyni; Orsi, Angelica; Lozinska, Magdalena M.; Sicard, Clemence; Johnson, Timothy; Steunou, Nathalie; Wright, Paul A.; Serre, Christian; Gascon, Jorge; Kapteijn, Freek

    2018-01-01

    To gain insight into the influence of metal-organic framework (MOF) fillers and polymers on membrane performance, eight different composites were studied by combining four MOFs and two polymers. MOF materials (NH-MIL-53(Al), MIL-69(Al), MIL-96(Al) and ZIF-94) with various chemical functionalities, topologies, and dimensionalities of porosity were employed as fillers, and two typical polymers with different permeability-selectivity properties (6FDA-DAM and Pebax) were selected as matrices. The best-performing MOF-polymer composites were prepared by loading 25wt% of MIL-96(Al) as filler, which improved the permeability and selectivity of 6FDA-DAM to 32 and 10%, while for Pebax they were enhanced to 25 and 18%, respectively. The observed differences in membrane performance in the separation of CO from N are explained on the basis of gas solubility, diffusivity properties, and compatibility between the filler and polymer phases.

  5. Bimetallic NiFe2O4 synthesized via confined carburization in NiFe-MOFs for efficient oxygen evolution reaction

    Science.gov (United States)

    Fang, Zhiqiang; Hao, Zhaomin; Dong, Qingsong; Cui, Yong

    2018-04-01

    Transition metal oxides that derived from metal-organic framework (MOF) precursor have intensively received attention because of their numerous electrochemical applications. Bimetallic Ni-Fe oxides have been rarely reported on the basis of MOF-related strategy. Herein, a bimetallic NiFe2O4 was successfully synthesized via confined carburization in NiFe-MOF precursors and characterized by XRD, XPS, SEM, and TEM. After conducting an investigation of oxygen evolution reaction (OER), the as-synthesized NiFe2O4 material exhibited good catalytic efficiency and high stability and durability in alkaline media. The as-synthesized NiFe2O4 material would promote the development of MOFs in non-noble-metal OER catalyst.

  6. Successful implementation of the stepwise layer-by-layer growth of MOF thin films on confined surfaces: Mesoporous silica foam as a first case study

    KAUST Repository

    Shekhah, Osama; Fu, Lei; Sougrat, Rachid; Belmabkhout, Youssef; Cairns, Amy; Giannelis, Emmanuel P.; Eddaoudi, Mohamed

    2012-01-01

    Here we report the successful growth of highly crystalline homogeneous MOF thin films of HKUST-1 and ZIF-8 on mesoporous silica foam, by employing a layer-by-layer (LBL) method. The ability to control and direct the growth of MOF thin films on confined surfaces, using the stepwise LBL method, paves the way for new prospective applications of such hybrid systems. © 2012 The Royal Society of Chemistry.

  7. Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

    Science.gov (United States)

    2016-01-01

    Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

  8. Rational construction of an ssa-type of MOF through pre-organizing the ligand's conformation and its exceptional gas adsorption properties.

    Science.gov (United States)

    Wang, Yao; He, Minghui; Tian, Zhi; Zhong, Haoyan; Zhu, Lisha; Zhang, Yingying; Zhang, Xiaoping; Chen, De-Li; He, Yabing

    2018-02-13

    Ssa-type MOFs constructed from dicopper paddlewheels and bent diisophthalate ligands exhibit a promising potential for gas adsorption which benefits from their rich open copper sites and polyhedron-based cages with suitable sizes. However, the rational construction of such types of MOFs is exceedingly challenging because the bent diisophthalate ligands employed are inclined to exhibit various conformations and thus are prone to form MOFs with varied topologies. In this work, by pre-organizing the ligand's conformation, we successfully targeted an ssa-type MOF ZJNU-57 from a bent diisophthalate ligand. More significantly, ZJNU-57 exhibits excellent hydrolytic stability and high C 2 H 2 and CO 2 uptake capacities as well as impressive C 2 H 2 /CH 4 and CO 2 /CH 4 adsorption selectivities, indicating its promising potential for C 2 H 2 /CH 4 and CO 2 /CH 4 separation, which are relevant to acetylene production and natural gas purification. This work not only provides a rare water-stable MOF based on the Cu 2 (COO) 4 cluster for highly selective adsorption of C 2 H 2 and CO 2 from CH 4 , but also demonstrates that the ligand conformation-controlled assembly strategy may be an efficient approach toward the construction of MOF materials with definite topologies for specific applications.

  9. A supermolecular building layer approach for gas separation and storage applications: the eea and rtl MOF platforms for CO 2 capture and hydrocarbon separation

    KAUST Repository

    Chen, Zhijie

    2015-02-11

    The supermolecular building layer (SBL) approach was employed to deliberately synthesize five novel metal–organic frameworks (1–5) with an exposed array of amide or amine functionalities within their pore system. The ability to decorate the pores with nitrogen donor moieties offers potential to evaluate/elucidate the structure–adsorption property relationship. Two MOF platforms, eea-MOF and rtl-MOF, based on pillaring of kgm-a or sql-a layers with heterofunctional 3-connected organic building blocks were targeted and constructed to purposely introduce and expose the desired amide or amine functionalities. Interestingly, gas adsorption properties of eea-MOF-4 (1) and eea-MOF-5 (2) showed that by simply altering the nitrogen donor position within the ligand, it is possible to relatively reduce the pore size of the related eea-MOF material and subsequently increase the associated CO2 uptake. The slightly confined pore space in 2, relative to 1, has enabled an enhancement of the pore local charge density and thus the observed relative increase in the CO2 and H2 isosteric heat of adsorption (Qst). In addition, light hydrocarbon adsorption studies revealed that 2 is more selective toward C2H6 and C3H8 over CH4 than 1, as exemplified for C2H6 : CH4 (5 : 95) or C3H8 : CH4 (5 : 95) binary gas mixtures.

  10. A POROUS, LAYERED HELIOPAUSE

    Energy Technology Data Exchange (ETDEWEB)

    Swisdak, M.; Drake, J. F. [Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, MD 20742 (United States); Opher, M., E-mail: swisdak@umd.edu, E-mail: drake@umd.edu, E-mail: mopher@bu.edu [Department of Astronomy, Boston University, 725 Commonwealth Avenue, Boston, MA 02215 (United States)

    2013-09-01

    The picture of the heliopause (HP)-the boundary between the domains of the Sun and the local interstellar medium (LISM)-as a pristine interface with a large rotation in the magnetic field fails to describe recent Voyager 1 (V1) data. Magnetohydrodynamic (MHD) simulations of the global heliosphere reveal that the rotation angle of the magnetic field across the HP at V1 is small. Particle-in-cell simulations, based on cuts through the MHD model at V1's location, suggest that the sectored region of the heliosheath (HS) produces large-scale magnetic islands that reconnect with the interstellar magnetic field while mixing LISM and HS plasma. Cuts across the simulation reveal multiple, anti-correlated jumps in the number densities of LISM and HS particles, similar to those observed, at the magnetic separatrices. A model is presented, based on both the observations and simulations, of the HP as a porous, multi-layered structure threaded by magnetic fields. This model further suggests that contrary to the conclusions of recent papers, V1 has already crossed the HP.

  11. Synthesis and integration of Fe-soc-MOF cubes into colloidosomes via a single-step emulsion-based approach

    KAUST Repository

    Pang, Maolin

    2013-07-17

    Bottom-up fabrication of complex 3D hollow superstructures from nonspherical building blocks (BBs) poses a significant challenge for scientists in materials chemistry and physics. Spherical colloidal silica or polystyrene particles are therefore often integrated as BBs for the preparation of an emerging class of materials, namely colloidosomes (using colloidal particles for Pickering stabilization and fusing them to form a permeable shell). Herein, we describe for the first time a one-step emulsion-based technique that permits the assembly of metal-organic framework (MOF) faceted polyhedral BBs (i.e., cubes instead of spheres) into 3D hollow superstructures (or "colloidosomes" ). The shell of each resultant hollow MOF colloidosome is constructed from a monolayer of cubic BBs, whose dimensions can be precisely controlled by varying the amount of emulsifier used in the synthesis. © 2013 American Chemical Society.

  12. The PM2.5 capture of poly (lactic acid)/nano MOFs eletrospinning membrane with hydrophilic surface

    Science.gov (United States)

    Wang, Yating; Dai, Xiu; Li, Xu; Wang, Xinlong

    2018-03-01

    In this article, metal organic frameworks (MOFs) material is introduced in the poly (lactic acid) (PLA) by electrospinning to fabricate the nanocomposite membrane. The acrylic acid (AA) is grafted onto the membrane under UV light. The prepared membrane is studied by scanning electron microscopy (SEM), x-ray diffraction (XRD), thermogravimetry (TG), contact angle test and tensile strength test. The SEM image and XRD indicate that nano MOFs particles adhere to the membrane. Contact angle test shows that grafting AA on the composite fiber membrane improves its hydrophilicity effectively. TG analyses show that the particulate matter (PM) capture capacity of PLA membrane with 2 wt% ZIF-8 content is 22%, which rises to 37% after grafting.

  13. Synthesis of octahedral like Cu-BTC derivatives derived from MOF calcined under different atmosphere for application in CO oxidation

    Science.gov (United States)

    Yang, Yiqiong; Dong, Han; Wang, Yin; He, Chi; Wang, Yuxin; Zhang, Xiaodong

    2018-02-01

    A series of octahedral structure Cu-BTC derivatives were successfully achieved through direct calcination of copper based metal organic framework Cu-BTC under different atmosphere (CO reaction gas, oxidizing gas O2, reducing gas H2, inert gas Ar). The Cu-BTC derivatives were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), laser Raman spectroscopy (LRS), N2 adsorption-desorption isotherm, element analysis, H2-temperature program reduction (H2-TPR) and X-ray photoelectron spectroscopic (XPS). It is found that Cu-BTC derivative derived from MOF calcined under reaction gas/O2 (Cu-BTC-CO/Cu-BTC-O) only retain Cu2O and CuO species. In addition, a weak Cu-BTC structure and Cu particles were observed on Cu-BTC derivative derived from MOF calcined under H2 (Cu-BTC-H). Obviously differently, Cu-BTC derivative derived from MOF calcined under Ar (Cu-BTC-Ar) still retains good MOF structure. The catalytic performance for CO oxidation over Cu-BTC derivatives was studied. It was found that Cu-BTC-CO showed a smaller specific surface area (8.0 m2/g), but presented an excellent catalytic performance, long-term stability and cycling stability with a complete CO conversion temperature (T100) of 140 °C, which was ascribed to the higher Cu2O/CuO ratio, good low temperature reduction behavior and a high quantity of surface active oxygen species.

  14. On demand: The singular rht net, an ideal blueprint for the construction of a metal-organic framework (mof) platform

    KAUST Repository

    Eubank, Jarrod F.

    2012-09-07

    The exceptional nature of the rht-MOF platform, based on a singular edge-transitive net (the only net for the combination of 3- and 24-connected nodes), makes it an ideal target in crystal chemistry. The high level of control indicates an unparalleled blueprint for isoreticular functional materials (without concern for interpenetration) for targeted applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Origins and Evolution of Inorganic-Based and MOF-Based Mixed-Matrix Membranes for Gas Separations

    Directory of Open Access Journals (Sweden)

    Edson V. Perez

    2016-09-01

    Full Text Available Gas separation for industrial, energy, and environmental applications requires low energy consumption and small footprint technology to minimize operating and capital costs for the processing of large volumes of gases. Among the separation methods currently being used, like distillation, amine scrubbing, and pressure and temperature swing adsorption, membrane-based gas separation has the potential to meet these demands. The key component, the membrane, must then be engineered to allow for high gas flux, high selectivity, and chemical and mechanical stability at the operating conditions of feed composition, pressure, and temperature. Among the new type of membranes studied that show promising results are the inorganic-based and the metal-organic framework-based mixed-matrix membranes (MOF-MMMs. A MOF is a unique material that offers the possibility of tuning the porosity of a membrane by introducing diffusional channels and forming a compatible interface with the polymer. This review details the origins of these membranes and their evolution since the first inorganic/polymer and MOF/polymer MMMs were reported in the open literature. The most significant advancements made in terms of materials, properties, and testing conditions are described in a chronological fashion.

  16. The quest for highly sensitive QCM humidity sensors: the coating of CNT/MOF composite sensing films as case study

    KAUST Repository

    Chappanda, Karumbaiah. N.

    2017-11-01

    The application of metal-organic frameworks (MOFs) as a sensing layer has been attracting great interest over the last decade, due to their uniform properties in terms of high porosity and tunability, which provides a large surface area and/or centers for trapping/binding a targeted analyte. Here we report the fabrication of a highly sensitive humidity sensor that is based on composite thin films of HKUST-1 MOF and carbon nanotubes (CNT). The composite sensing films were fabricated by spin coating technique on a quartz-crystal microbalance (QCM) and a comparison of their shift in resonance frequencies to adsorbed water vapor (5 to 75% relative humidity) is presented. Through optimization of the CNT and HKUST-1 composition, we could demonstrate a 230% increase in sensitivity compared to plain HKUST-1 film. The optimized CNT-HKUST-1 composite thin films are stable, reliable, and have an average sensitivity of about 2.5×10−5 (Δf/f) per percent of relative humidity, which is up to ten times better than previously reported QCM-based humidity sensors. The approach presented here is facile and paves a promising path towards enhancing the sensitivity of MOF-based sensors.

  17. Adsorption Behavior of High Stable Zr-Based MOFs for the Removal of Acid Organic Dye from Water

    Directory of Open Access Journals (Sweden)

    Ke-Deng Zhang

    2017-02-01

    Full Text Available Zirconium based metal organic frameworks (Zr-MOFs have become popular in engineering studies due to their high mechanical stability, thermostability and chemical stability. In our work, by using a theoretical kinetic adsorption isotherm, we can exert MOFs to an acid dye adsorption process, experimentally exploring the adsorption of MOFs, their external behavior and internal mechanism. The results indicate their spontaneous and endothermic nature, and the maximum adsorption capacity of this material for acid orange 7 (AO7 could be up to 358 mg·g−1 at 318 K, estimated by the Langmuir isotherm model. This is ascribed to the presence of an open active metal site that significantly intensified the adsorption, by majorly increasing the interaction strength with the adsorbates. Additionally, the enhanced π delocalization and suitable pore size of UiO-66 gave rise to the highest host–guest interaction, which further improves both the adsorption capacity and separation selectivity at low concentrations. Furthermore, the stability of UiO-66 was actually verified for the first time, through comparing the structure of the samples before and after adsorption mainly by Powder X-ray diffraction and thermal gravimetric analysis.

  18. Copper-Based Metal-Organic Porous Materials for CO2 Electrocatalytic Reduction to Alcohols.

    Science.gov (United States)

    Albo, Jonathan; Vallejo, Daniel; Beobide, Garikoitz; Castillo, Oscar; Castaño, Pedro; Irabien, Angel

    2017-03-22

    The electrocatalytic reduction of CO 2 has been investigated using four Cu-based metal-organic porous materials supported on gas diffusion electrodes, namely, (1) HKUST-1 metal-organic framework (MOF), [Cu 3 (μ 6 -C 9 H 3 O 6 ) 2 ] n ; (2) CuAdeAce MOF, [Cu 3 (μ 3 -C 5 H 4 N 5 ) 2 ] n ; (3) CuDTA mesoporous metal-organic aerogel (MOA), [Cu(μ-C 2 H 2 N 2 S 2 )] n ; and (4) CuZnDTA MOA, [Cu 0.6 Zn 0.4 (μ-C 2 H 2 N 2 S 2 )] n . The electrodes show relatively high surface areas, accessibilities, and exposure of the Cu catalytic centers as well as favorable electrocatalytic CO 2 reduction performance, that is, they have a high efficiency for the production of methanol and ethanol in the liquid phase. The maximum cumulative Faradaic efficiencies for CO 2 conversion at HKUST-1-, CuAdeAce-, CuDTA-, and CuZnDTA-based electrodes are 15.9, 1.2, 6, and 9.9 %, respectively, at a current density of 10 mA cm -2 , an electrolyte-flow/area ratio of 3 mL min cm -2 , and a gas-flow/area ratio of 20 mL min cm -2 . We can correlate these observations with the structural features of the electrodes. Furthermore, HKUST-1- and CuZnDTA-based electrodes show stable electrocatalytic performance for 17 and 12 h, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Polyoxometalates@Metal-Organic Frameworks Derived Porous MoO3@CuO as Electrodes for Symmetric All-Solid-State Supercapacitor

    International Nuclear Information System (INIS)

    Zhang, Yidong; Lin, Baoping; Wang, Junchuan; Han, Pei; Xu, Tong; Sun, Ying; Zhang, Xueqin; Yang, Hong

    2016-01-01

    Highlights: • Porous MoO 3 @CuO was obtained from POMs@MOFs template. • A good charge capacity of 86.3 mAh g −1 was achieved in 1 M LiOH electrolyte. • The MoO 3 @CuO electrode was assembled into an all-solid-state device. • The introduction of MoO 3 improves the charge capacity. • The MoO 3 @CuO composite has good uniformity and porosity. - Abstract: The demand of uniformity and porosity for composite supercapacitor material has triggered tremendous research efforts for the development of doping method. Herein, we report an effective strategy for homogeneous and polyporous MoO 3 @CuO composite by heating a POMs@MOFs template (POMs = polyoxometalates, MOFs = Metal-organic frameworks), in which the Mo-POMs are incorporated into Cu-MOFs as secondary building units. The excellent doping of MoO 3 to CuO leads to an obvious improvement in specific discharge capacity (from 15.4 mAh g −1 for CuO to 86.3 mAh g −1 for MoO 3 @CuO). The layered structure of MoO 3 plays a key role in providing facilitated ion transport and electron diffusion pathways for the composite material. This electrode demonstrates excellent electrochemical performance with a specific discharge capacity of 86.3 mAh g −1 at 1 A g −1 in 1 M LiOH. When this porous MoO 3 @CuO electrode is assembled into a symmetric all-solid-state device with PVA-LiOH gel polymer, the as-fabricated device demonstrates good performance with an energy density of 7.9 W h kg −1 , power density of 8726 W kg −1 , and excellent cycle life. This work presents a new template to improve the uniformity and porosity of composite metal oxides, which can be used for high-performance supercapacitors.

  20. The development of new materials such MOFs for CO2 capture and alkylation of aromatic compounds

    International Nuclear Information System (INIS)

    Ravon, U.

    2010-01-01

    This thesis is a European project TOPCOMBI of 22 partners. More specifically, this work is the result of collaboration between ENI (Italy), ITQ (Spain), Repsol (Spain) and IRCELYON (France). This work consists of 2 different themes which improvements can be obtained by finding new materials tailored to the needs. The global energy demands are and will be constantly rising in the coming years. In order to meet this need, new resources must be found and further optimized. Fossil fuels are among the most used resources in the world. Among this 3, natural gas appears to be the most promising point of view of energy efficiency and ecological impact. However, many gas fields cannot be treated because there are too small or too contaminated to be economically viable. One way to make them attractive is to lower the cost of purification using novel separation techniques such as the PSA system. However, there is no currently effective adsorbent to allow a viable economic cleansing. Today, the alkylation reactions represent a very important economic interest. Industrial processes are typically carried out by homogeneous acid reactions or not. Seeing the new environmental restrictions, some homogeneous catalytic processes must be replaced by heterogeneous catalytic reactions with the same yields. To do this, new materials to acid characters were used: the zeolites. However the small size of pores of these compounds prevents selective alkylation reactions of molecules too large compounds such as poly-aromatic. For twenty years, new microporous crystalline compounds have emerged: the MOFs, Metal Organic Frameworks. These compounds have the characteristic to be obtained with different metal cations and organic ligands. These combinations give a wide variety of these compounds at the level of reactivity, pore volume and pore size. In this work, we tried to get different materials with specific characteristics in order to use them in methods for purification of methane in acid

  1. Quest for anionic MOF membranes: Continuous sod -ZMOF membrane with Co2 adsorption-driven selectivity

    KAUST Repository

    Almaythalony, Bassem; Shekhah, Osama; Swaidan, Raja; Belmabkhout, Youssef; Pinnau, Ingo; Eddaoudi, Mohamed

    2015-01-01

    We report the fabrication of the first continuous zeolite-like metal-organic framework (ZMOF) thin-film membrane. A pure phase sod-ZMOF, sodalite topology, membrane was grown and supported on a porous alumina substrate using a solvothermal

  2. Modulated synthesis of Cr-MOF (MIL 101) for hydrogen storage applications

    CSIR Research Space (South Africa)

    Segakweng, T

    2014-08-01

    Full Text Available as a fuel into fuel cell technologies is only possible when safe and effective hydrogen storage systems become available. Complete usage of hydrogen is only possible if proper and effective storage systems with fast kinetics becomes available. Porous...

  3. Preparation and catalytic effect of porous Co3O4 on the hydrogen storage properties of a Li-B-N-H system

    Directory of Open Access Journals (Sweden)

    You Li

    2017-02-01

    Full Text Available A porous Co3O4 with a particle size of 1–3 µm was successfully prepared by heating Co-based metal organic frameworks MOF-74(Co up to 500 °C in air atmospheric conditions. The as-prepared porous Co3O4 significantly reduced the dehydrogenation temperatures of the LiBH4-2LiNH2 system and improved the purity of the released hydrogen. The LiBH4-2LiNH2-0.05/3Co3O4 sample started to release hydrogen at 140 °C and released hydrogen levels of approximately 9.7 wt% at 225 °C. The end temperature for hydrogen release was lowered by 125 °C relative to that of the pristine sample. Structural analyses revealed that the as-prepared porous Co3O4 is in-situ reduced to metallic Co, which functions as an active catalyst, reducing the kinetic barriers and lowering the dehydrogenation temperatures of the LiBH4-2LiNH2 system. More importantly, the porous Co3O4-containing sample exhibited partially improved reversibility for hydrogen storage in the LiBH4-2LiNH2 system.

  4. Magnetic porous Fe3O4/carbon octahedra derived from iron-based metal-organic framework as heterogeneous Fenton-like catalyst

    Science.gov (United States)

    Li, Wenhui; Wu, Xiaofeng; Li, Shuangde; Tang, Wenxiang; Chen, Yunfa

    2018-04-01

    The synthesis of effective and recyclable Fenton-like catalyst is still a key factor for advanced oxidation processes. Herein, magnetic porous Fe3O4/carbon octahedra were constructed by a two-step controlled calcination of iron-based metal organic framework. The porous octahedra were assembled by interpenetrated Fe3O4 nanoparticles coated with graphitic carbon layer, offering abundant mesoporous channels for the solid-liquid contact. Moreover, the oxygen-containing functional groups on the surface of graphitic carbon endow the catalysts with hydrophilic nature and well-dispersion into water. The porous Fe3O4/carbon octahedra show efficiently heterogeneous Fenton-like reactions for decomposing the organic dye methylene blue (MB) with the help of H2O2, and nearly 100% removal efficiency within 60 min. Furthermore, the magnetic catalyst retains the activity after ten cycles and can be easily separated by external magnetic field, indicating the long-term catalytic durability and recyclability. The good Fenton-like catalytic performance of the as-synthesized Fe3O4/carbon octahedra is ascribed to the unique mesoporous structure derived from MOF-framework, as well as the sacrificial role and stabilizing effect of graphitic carbon layer. This work provides a facile strategy for the controllable synthesis of integrated porous octahedral structure with graphitic carbon layer, and thereby the catalyst holds significant potential for wastewater treatment.

  5. Porous (Swiss-Cheese Graphite

    Directory of Open Access Journals (Sweden)

    Joseph P. Abrahamson

    2018-05-01

    Full Text Available Porous graphite was prepared without the use of template by rapidly heating the carbonization products from mixtures of anthracene, fluorene, and pyrene with a CO2 laser. Rapid CO2 laser heating at a rate of 1.8 × 106 °C/s vaporizes out the fluorene-pyrene derived pitch while annealing the anthracene coke. The resulting structure is that of graphite with 100 nm spherical pores. The graphitizablity of the porous material is the same as pure anthracene coke. Transmission electron microscopy revealed that the interfaces between graphitic layers and the pore walls are unimpeded. Traditional furnace annealing does not result in the porous structure as the heating rates are too slow to vaporize out the pitch, thereby illustrating the advantage of fast thermal processing. The resultant porous graphite was prelithiated and used as an anode in lithium ion capacitors. The porous graphite when lithiated had a specific capacity of 200 mAh/g at 100 mA/g. The assembled lithium ion capacitor demonstrated an energy density as high as 75 Wh/kg when cycled between 2.2 V and 4.2 V.

  6. Micromechanical analysis of porous SMA

    International Nuclear Information System (INIS)

    Sepe, V; Marfia, S; Sacco, E; Auricchio, F

    2015-01-01

    The present paper deals with computational micromechanical analyses of porous shape memory alloy (SMA). Porous SMAs are considered composite materials made of a dense SMA matrix including voids. A three-dimensional constitutive law is presented for the dense SMA able to reproduce the pseudo-elastic as well as the shape memory effects and, moreover, to account for the different elastic properties of the austenite and martensite phases. Furthermore, a numerical procedure is developed and the overall behavior of the porous SMA is recovered studying a representative volume element. Comparisons between the numerical results, recovered using the proposed modeling, and experimental data available in the literature are presented. The case of closed and open porosity is investigated. Parametric studies have been conducted in order to investigate the influence of the porosity, the shape and orientation of the pores on the overall mechanical response and, mainly, on the energy absorption dissipation capability. (paper)

  7. Theoretical prediction the removal of mercury from flue gas by MOFs

    KAUST Repository

    Liu, Yang; Li, Hailong; Liu, Jing

    2016-01-01

    Removal of mercury from flue gas has been considered as one of the hot topics in both the scientific and industrial world. Adsorption of elemental mercury (Hg) and oxidized mercury species (HgCl, HgO, and HgS) on a novel metal organic framework (MOF) material, named Mg/DOBDC, with unsaturated metal centers was investigated using density functional theory (DFT) calculations. The results show that Hg stably physi-sorbed on the unsaturated metal center (magnesium ion) of Mg/DOBDC with a binding energy (BE) of −27.5 kJ/mol. A direct interaction between Hg and magnesium ion was revealed by the partial density of state (PDOS) analysis. HgCl multi-interacts with two neighboring magnesium ions simultaneously by its Cl endings and thus resulted in strong adsorption strength (−89.0 kJ/mol). The adsorption energies of HgO and HgS on the Mg/DOBDC were as high as −117.0 kJ/mol and −169.7 kJ/mol, respectively, indicating a strong chemisorption. Theoretical calculations in this study reveal that Mg/DOBDC has the potential to serve as an efficient material for removal of mercury from flue gas.

  8. Immobilization of silver nanoparticles in Zr-based MOFs: induction of apoptosis in cancer cells

    Science.gov (United States)

    Han, Congcong; Yang, Jian; Gu, Jinlou

    2018-03-01

    Silver nanoparticles (AgNPs) are a potential class of nanomaterial for antibiosis and chemotherapeutic effects against human carcinoma cells. However, the DNA-damaging ability of free AgNPs pose the critical issues in their biomedical applications. Herein, we demonstrated a facile method to capture Ag+ ions and reduce them into active AgNPs within Zr-based metal-organic frameworks (MOFs) of UiO-66 with a mild reductant of DMF (AgNPs@UiO-66(DMF)). The average diameters of UiO-66 carriers and AgNPs were facilely controlled to be 140 and 10 nm, respectively. The obtained UiO-66 nanocarriers exhibited excellent biocompatibility and could be effectively endocytosed by cancer cells. Additionally, the AgNPs@UiO-66(DMF) could rapidly release Ag+ ions and efficiently inhibit the growth of cancer cells. The half maximal inhibitory concentration (IC50) values of the encapsulated AgNPs were calculated to be 2.7 and 2.45 μg mL-1 for SMMC-7721 and HeLa cells, respectively, which were much lower than those of free AgNPs in the reported works. Therefore, the developed AgNPs@UiO-66(DMF) not only maintained the therapeutic effect against cancer cells but also reduced the dosage of free AgNPs in chemotherapy treatment. [Figure not available: see fulltext.

  9. Theoretical prediction the removal of mercury from flue gas by MOFs

    KAUST Repository

    Liu, Yang

    2016-07-19

    Removal of mercury from flue gas has been considered as one of the hot topics in both the scientific and industrial world. Adsorption of elemental mercury (Hg) and oxidized mercury species (HgCl, HgO, and HgS) on a novel metal organic framework (MOF) material, named Mg/DOBDC, with unsaturated metal centers was investigated using density functional theory (DFT) calculations. The results show that Hg stably physi-sorbed on the unsaturated metal center (magnesium ion) of Mg/DOBDC with a binding energy (BE) of −27.5 kJ/mol. A direct interaction between Hg and magnesium ion was revealed by the partial density of state (PDOS) analysis. HgCl multi-interacts with two neighboring magnesium ions simultaneously by its Cl endings and thus resulted in strong adsorption strength (−89.0 kJ/mol). The adsorption energies of HgO and HgS on the Mg/DOBDC were as high as −117.0 kJ/mol and −169.7 kJ/mol, respectively, indicating a strong chemisorption. Theoretical calculations in this study reveal that Mg/DOBDC has the potential to serve as an efficient material for removal of mercury from flue gas.

  10. Metrology of nanosize biopowders using porous silicon surface

    International Nuclear Information System (INIS)

    Zhuravel', L.V.; Latukhina, N.V.; Pisareva, E.V.; Vlasov, M.Yu.; Volkov, A.V.; Volodkin, B.O.

    2008-01-01

    Powders of hydroxyapatite deposited on porous silicon surface were investigated by TEM and STM methods. Thickness of porous lay was 1-100 micrometers; porous diameter was 0.01-10 micrometers. Images of porous silicon surface with deposited particles give possibility to estimate particles size and induce that only proportionate porous diameter particles have good adhesion to porous silicon surface.

  11. Characteristics of porous zirconia coated with hydroxyapatite

    Indian Academy of Sciences (India)

    However, porous hydroxyapatite bodies are mechanically weak and brittle, which makes shaping and implantation difficult. One way to solve this problem is to introduce a strong porous network onto which hydroxyapatite coating is applied. In this study, porous zirconia and alumina-added zirconia ceramics were prepared ...

  12. Process of preparing tritiated porous silicon

    Science.gov (United States)

    Tam, Shiu-Wing

    1997-01-01

    A process of preparing tritiated porous silicon in which porous silicon is equilibrated with a gaseous vapor containing HT/T.sub.2 gas in a diluent for a time sufficient for tritium in the gas phase to replace hydrogen present in the pore surfaces of the porous silicon.

  13. Porous silicon: X-rays sensitivity

    International Nuclear Information System (INIS)

    Gerstenmayer, J.L.; Vibert, Patrick; Mercier, Patrick; Rayer, Claude; Hyvernage, Michel; Herino, Roland; Bsiesy, Ahmad

    1994-01-01

    We demonstrate that high porosity anodically porous silicon is radioluminescent. Interests of this study are double. Firstly: is the construction of porous silicon X-rays detectors (imagers) possible? Secondly: is it necessary to protect silicon porous based optoelectronic systems from ionising radiations effects (spatial environment)? ((orig.))

  14. Understanding Hydrogen Sorption in In- soc -MOF: A Charged Metal-Organic Framework with Open-Metal Sites, Narrow Channels, and Counterions

    KAUST Repository

    Pham, Tony

    2015-03-04

    © 2015 American Chemical Society. Grand canonical Monte Carlo (GCMC) simulations of hydrogen sorption were performed in In-soc-MOF, a charged metal-organic framework (MOF) that contains In3O trimers coordinated to 5,5′-azobis(1,3-benzenedicarboxylate) linkers. The MOF contains nitrate counterions that are located in carcerand-like capsules of the framework. This MOF was shown to have a high hydrogen uptake at 77 K and 1.0 atm. The simulations were performed with a potential that includes explicit many-body polarization interactions, which were important for modeling gas sorption in a charged/polar MOF such as In-soc-MOF. The simulated hydrogen sorption isotherms were in good agreement with experiment in this challenging platform for modeling. The simulations predict a high initial isosteric heat of adsorption, Qst, value of about 8.5 kJ mol-1, which is in contrast to the experimental value of 6.5 kJ mol-1 for all loadings. The difference in the Qst behavior between experiment and simulation is attributed to the fact that, in experimental measurements, the sorbate molecules cannot access the isolated cages containing the nitrate ions, the most energetically favorable site in the MOF, at low pressures due to an observed diffusion barrier. In contrast, the simulations were able to capture the sorption of hydrogen onto the nitrate ions at low loading due to the equilibrium nature of GCMC simulations. The experimental Qst values were reproduced in simulation by blocking access to all of the nitrate ions in the MOF. Furthermore, at 77 K, the sorbed hydrogen molecules were reminiscent of a dense fluid in In-soc-MOF starting at approximately 5.0 atm, and this was verified by monitoring the isothermal compressibility, βT, values. The favorable sites for hydrogen sorption were identified from the polarization distribution as the nitrate ions, the In3O trimers, and the azobenzene nitrogen atoms. Lastly, the two-dimensional quantum rotational levels

  15. Porous squeeze-film flow

    KAUST Repository

    Knox, D. J.; Wilson, S. K.; Duffy, B. R.; McKee, S.

    2013-01-01

    surface moving under a prescribed constant load and a flat thin porous bed coating a stationary flat impermeable surface is considered. Unlike in the classical case of an impermeable bed, in which an infinite time is required for the two surfaces to touch

  16. On strength of porous material

    DEFF Research Database (Denmark)

    Nielsen, Lauge Fuglsang

    1999-01-01

    The question of non-destructive testing of porous materials has always been of interest for the engineering profession. A number of empirically based MOE-MOR relations between stiffness (Modulus Of Elasticity) and strength (Modulus OF Rupture) of materials have been established in order to control...

  17. Porous Materials - Structure and Properties

    DEFF Research Database (Denmark)

    Nielsen, Anders

    1997-01-01

    The paper presents some viewpoints on the description of the pore structure and the modelling of the properties of the porous building materials. Two examples are given , where it has been possible to connect the pore structure to the properties: Shrinkage of autoclaved aerated concrete...

  18. Porous Concrete and Its Application

    Directory of Open Access Journals (Sweden)

    V. V. Opekunov

    2005-01-01

    Full Text Available Some aspects of resource saving problem in the process of mass construction and operation of heated construction installations are considered in the paper. A special attention is paid to necessary application of porous concrete products in the process of the housing construction. The preference is given to the products made of autoclave cellular concrete and cement hydrophobisized cement perlite concrete.

  19. Constitutive model for porous materials

    International Nuclear Information System (INIS)

    Weston, A.M.; Lee, E.L.

    1982-01-01

    A simple pressure versus porosity compaction model is developed to calculate the response of granular porous bed materials to shock impact. The model provides a scheme for calculating compaction behavior when relatively limited material data are available. While the model was developed to study porous explosives and propellants, it has been applied to a much wider range of materials. The early development of porous material models, such as that of Hermann, required empirical dynamic compaction data. Erkman and Edwards successfully applied the early theory to unreacted porous high explosives using a Gruneisen equation of state without yield behavior and without trapped gas in the pores. Butcher included viscoelastic rate dependance in pore collapse. The theoretical treatment of Carroll and Holt is centered on the collapse of a circular pore and includes radial inertia terms and a complex set of stress, strain and strain rate constitutive parameters. Unfortunately data required for these parameters are generally not available. The model described here is also centered on the collapse of a circular pore, but utilizes a simpler elastic-plastic static equilibrium pore collapse mechanism without strain rate dependence, or radial inertia terms. It does include trapped gas inside the pore, a solid material flow stress that creates both a yield point and a variation in solid material pressure with radius. The solid is described by a Mie-Gruneisen type EOS. Comparisons show that this model will accurately estimate major mechanical features which have been observed in compaction experiments

  20. Additively manufactured porous tantalum implants

    NARCIS (Netherlands)

    Wauthle, Ruben; Van Der Stok, Johan; Yavari, Saber Amin; Van Humbeeck, Jan; Kruth, Jean Pierre; Zadpoor, Amir Abbas; Weinans, Harrie; Mulier, Michiel; Schrooten, Jan

    2015-01-01

    The medical device industry's interest in open porous, metallic biomaterials has increased in response to additive manufacturing techniques enabling the production of complex shapes that cannot be produced with conventional techniques. Tantalum is an important metal for medical devices because of

  1. Ultrasound-promoted coating of MOF-5 on silk fiber and study of adsorptive removal and recovery of hazardous anionic dye "congo red".

    Science.gov (United States)

    Khanjani, Somayeh; Morsali, Ali

    2014-07-01

    A metal-organic framework MOF-5 has been synthesized on silk fiber through electrostatic layer-by-layer assembly. The silk surface coating was formed via sequential dipping in an alternating bath of metal and ligand solutions at room temperature by direct mixing. SEM was used to investigate the growth of MOF-5 coating as materials for separation membrane due to their desirable properties in adsorptive removal of congo red (CR) from contaminated water. The adsorption capacity of MOF-5 is remarkable high in the liquid phase. The adsorption of CR at various concentration and contact time in spontaneous process were studied. The silk fibers containing MOF-5 open a wide field of possible applications, such as protection layers or membranes in pollution remediation wastewater and any effluent. Desorption of the dye can be carried out by using NaOH solution with more than about 50% recovery of congo red from MOF-5 coated on silk membrane filtration. In order to investigate the role of sonicating on the morphology of products, one of the reactions was performed with ultrasound irradiation and the crystal growth is completed more than other methods. The samples and adsorption of CR were characterized with SEM, powder X-ray diffraction (XRD) and UV-visible spectroscopy. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Porous silicon carbide (SIC) semiconductor device

    Science.gov (United States)

    Shor, Joseph S. (Inventor); Kurtz, Anthony D. (Inventor)

    1996-01-01

    Porous silicon carbide is fabricated according to techniques which result in a significant portion of nanocrystallites within the material in a sub 10 nanometer regime. There is described techniques for passivating porous silicon carbide which result in the fabrication of optoelectronic devices which exhibit brighter blue luminescence and exhibit improved qualities. Based on certain of the techniques described porous silicon carbide is used as a sacrificial layer for the patterning of silicon carbide. Porous silicon carbide is then removed from the bulk substrate by oxidation and other methods. The techniques described employ a two-step process which is used to pattern bulk silicon carbide where selected areas of the wafer are then made porous and then the porous layer is subsequently removed. The process to form porous silicon carbide exhibits dopant selectivity and a two-step etching procedure is implemented for silicon carbide multilayers.

  3. Enhanced Raman scattering in porous silicon grating.

    Science.gov (United States)

    Wang, Jiajia; Jia, Zhenhong; Lv, Changwu

    2018-03-19

    The enhancement of Raman signal on monocrystalline silicon gratings with varying groove depths and on porous silicon grating were studied for a highly sensitive surface enhanced Raman scattering (SERS) response. In the experiment conducted, porous silicon gratings were fabricated. Silver nanoparticles (Ag NPs) were then deposited on the porous silicon grating to enhance the Raman signal of the detective objects. Results show that the enhancement of Raman signal on silicon grating improved when groove depth increased. The enhanced performance of Raman signal on porous silicon grating was also further improved. The Rhodamine SERS response based on Ag NPs/ porous silicon grating substrates was enhanced relative to the SERS response on Ag NPs/ porous silicon substrates. Ag NPs / porous silicon grating SERS substrate system achieved a highly sensitive SERS response due to the coupling of various Raman enhancement factors.

  4. Thermochemistry of paddle wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1.

    Science.gov (United States)

    Bhunia, Manas K; Hughes, James T; Fettinger, James C; Navrotsky, Alexandra

    2013-06-25

    Metal-organic framework (MOF) porosity relies upon robust metal-organic bonds to retain structural rigidity upon solvent removal. Both the as-synthesized and activated Cu and Zn polymorphs of HKUST-1 were studied by room temperature acid solution calorimetry. Their enthalpies of formation from dense assemblages (metal oxide (ZnO or CuO), trimesic acid (TMA), and N,N-dimethylformamide (DMF)) were calculated from the calorimetric data. The enthalpy of formation (ΔHf) of the as-synthesized Cu-HKUST-H2O ([Cu3TMA2·3H2O]·5DMF) is -52.70 ± 0.34 kJ per mole of Cu. The ΔHf for Zn-HKUST-DMF ([Zn3TMA2·3DMF]·2DMF) is -54.22 ± 0.57 kJ per mole of Zn. The desolvated Cu-HKUST-dg [Cu3TMA2] has a ΔHf of 16.66 ± 0.51 kJ/mol per mole Cu. The ΔHf for Zn-HKUST-amorph [Zn3TMA2·2DMF] is -3.57 ± 0.21 kJ per mole of Zn. Solvent stabilizes the Cu-HKUST-H2O by -69.4 kJ per mole of Cu and Zn-HKUST-DMF by at least -50.7 kJ per mole of Zn. Such strong chemisorption of solvent is similar in magnitude to the strongly exothermic binding at low coverage for chemisorbed H2O on transition metal oxide nanoparticle surfaces. The strongly exothermic solvent-framework interaction suggests that solvent can play a critical role in obtaining a specific secondary building unit (SBU) topology.

  5. Rapid Formation of Metal-Organic Frameworks (MOFs) Based Nanocomposites in Microdroplets and Their Applications for CO2 Photoreduction.

    Science.gov (United States)

    He, Xiang; Gan, Zhuoran; Fisenko, Sergey; Wang, Dawei; El-Kaderi, Hani M; Wang, Wei-Ning

    2017-03-22

    A copper-based metal-organic framework (MOF), [Cu 3 (TMA) 2 (H 2 O) 3 ] n (also known as HKUST-1, where TMA stands for trimesic acid), and its TiO 2 nanocomposites were directly synthesized in micrometer-sized droplets via a rapid aerosol route for the first time. The effects of synthesis temperature and precursor component ratio on the physicochemical properties of the materials were systematically investigated. Theoretical calculations on the mass and heat transfer within the microdroplets revealed that the fast solvent evaporation and high heat transfer rates are the major driving forces. The fast droplet shrinkage because of evaporation induces the drastic increase in the supersaturation ratio of the precursor, and subsequently promotes the rapid nucleation and crystal growth of the materials. The HKUST-1-based nanomaterials synthesized via the aerosol route demonstrated good crystallinity, large surface area, and great photostability, comparable with those fabricated by wet-chemistry methods. With TiO 2 embedded in the HKUST-1 matrix, the surface area of the composite is largely maintained, which enables significant improvement in the CO 2 photoreduction efficiency, as compared with pristine TiO 2 . In situ diffuse reflectance infrared Fourier transform spectroscopy analysis suggests that the performance enhancement was due to the stable and high-capacity reactant adsorption by HKUST-1. The current work shows great promise in the aerosol route's capability to address the mass and heat transfer issues of MOFs formation at the microscale level, and ability to synthesize a series of MOFs-based nanomaterials in a rapid and scalable manner for energy and environmental applications.

  6. An alkaline one-pot reaction to synthesize luminescent Eu-BTC MOF nanorods, highly pure and water-insoluble, under room conditions

    Energy Technology Data Exchange (ETDEWEB)

    Medina-Velazquez, D. Y., E-mail: dyolotzin@correo.azc.uam.mx; Alejandre-Zuniga, B. Y.; Loera-Serna, S.; Ortiz, E. M. [Universidad Autónoma Metropolitana-Azcapotzalco, División de Ciencias Básicas e Ingeniería (Mexico); Morales-Ramirez, A. de J. [CIITEC IPN, Instituto Politécnico Nacional (Mexico); Garfias-Garcia, E. [Universidad Autónoma Metropolitana-Azcapotzalco, División de Ciencias Básicas e Ingeniería (Mexico); Garcia-Murillo, A. [CIITEC IPN, Instituto Politécnico Nacional (Mexico); Falcony, C. [Centro de Investigación y Estudios Avanzados, Departamento de Física (Mexico)

    2016-12-15

    The increasing demand for optoelectronic devices requires the development of luminescent materials with high luminescence efficiency and low energy demands, and the metalorganic frameworks (MOFs) with lanthanides ions offer great potential in this area. The metalorganic materials provide properties of flexibility, low density, low-cost methods of synthesis, and insolubility in water, which gives them an advantage over traditional phosphors. In this study, a benzenetricarboxylate ligand (BTC) with a Eu{sup 3+} MOF was synthesized, and its structural and luminescent properties were measured. The metalorganic compound was generated in a one-pot reaction from europium nitrate and trimesic acid precursors. Through characterization by X-ray diffraction powder, infrared spectroscopy, SEM structural characterization, and luminescent spectroscopy, the formation of Europium benzenetricarboxylate (Eu-BTC) MOF nanorods was tested and the calculated value was in the range of 30–60 nm. A red luminescent emission with high intensity was observed for all the procedures.

  7. From an equilibrium based MOF adsorbent to a kinetic selective carbon molecular sieve for paraffin/iso-paraffin separation

    KAUST Repository

    Li, Baiyan

    2016-11-04

    We unveil a unique kinetic driven separation material for selectively removing linear paraffins from iso-paraffins via a molecular sieving mechanism. Subsequent carbonization and thermal treatment of CD-MOF-2, the cyclodextrin metal-organic framework, afforded a carbon molecular sieve with a uniform and reduced pore size of ca. 5.0 Å, and it exhibited highly selective kinetic separation of n-butane and n-pentane from iso-butane and iso-pentane, respectively. © The Royal Society of Chemistry.

  8. Colloidal Photoluminescent Amorphous Porous Silicon, Methods Of Making Colloidal Photoluminescent Amorphous Porous Silicon, And Methods Of Using Colloidal Photoluminescent Amorphous Porous Silicon

    KAUST Repository

    Chaieb, Sahraoui

    2015-04-09

    Embodiments of the present disclosure provide for a colloidal photoluminescent amorphous porous silicon particle suspension, methods of making a colloidal photoluminescent amorphous porous silicon particle suspension, methods of using a colloidal photoluminescent amorphous porous silicon particle suspension, and the like.

  9. Colloidal Photoluminescent Amorphous Porous Silicon, Methods Of Making Colloidal Photoluminescent Amorphous Porous Silicon, And Methods Of Using Colloidal Photoluminescent Amorphous Porous Silicon

    KAUST Repository

    Chaieb, Saharoui; Mughal, Asad Jahangir

    2015-01-01

    Embodiments of the present disclosure provide for a colloidal photoluminescent amorphous porous silicon particle suspension, methods of making a colloidal photoluminescent amorphous porous silicon particle suspension, methods of using a colloidal photoluminescent amorphous porous silicon particle suspension, and the like.

  10. Selective carbon dioxide sorption by a new breathing three-dimensional Zn-MOF with Lewis basic nitrogen-rich channels.

    Science.gov (United States)

    Kim, Hyun-Chul; Huh, Seong; Lee, Do Nam; Kim, Youngmee

    2018-04-03

    Lewis basic heteroatoms orderly located inside the well-defined channels of metal-organic frameworks (MOFs) are potentially ideal active sites for selective gas sorption and catalysis. To develop functional MOFs with Lewis basic sites inside channels, a new C2h-symmetric dicarboxylate-based bridging ligand, 3,3'-(pyrazine-2,5-diyl)dibenzoic acid (3,3'-PDBA), was prepared by a Suzuki coupling reaction. Subsequently, two new Zn-MOFs containing the C2h-symmetric 3,3'-PDBA bridging ligand and two different bis(pyridyl)-based pillars, 1,2-bis(4-pyridyl)ethane (bpa) or 1,2-bis(4-pyridyl)ethylene (bpe), were prepared through a thermal reaction in N,N-dimethylformamide (DMF). The resulting two Zn-MOFs of the general formula of three-dimensional (3D) [Zn2(μ4-3,3'-PDBA)2(μ2-bpa)]3·(DMF)5(H2O)13 (1) or 3D-like 2D [Zn2(μ4-3,3'-PDBA)2(μ2-bpe)]·(H2O) (2) displayed primitive cubic pcu net and 2D sql net, respectively. Both Zn-MOFs 1 and 2 contain uncoordinated Lewis basic pyrazinyl nitrogen atoms in the frameworks. The solvent-free 1 with flexible bpa linkers only showed a potential porosity of 15.9% by PLATON analysis. Zn-MOF 1 with openly accessible Lewis basic sites exhibited selective sorption of CO2 over N2, H2, and CH4 at low temperature. The adsorption and desorption isotherms for CO2 sorption at 196 K showed phenomenal hysteretic behaviour indicative of a breathing process through an adsorbate-discriminatory gate-opening process toward CO2 at a low gas pressure.

  11. Heterometallic metal-organic framework-templated synthesis of porous Co3O4/ZnO nanocage catalysts for the carbonylation of glycerol

    Science.gov (United States)

    Lü, Yinyun; Jiang, Yating; Zhou, Qi; Li, Yunmei; Chen, Luning; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

    2017-12-01

    The efficient synthesis of glycerol carbonate (GLC) has recently received great attention due to its significance in reducing excess glycerol in biodiesel production as well as its promising applications in several industrial fields. However, the achievement of high conversion and high selectivity of GLC from glycerol in heterogeneous catalytic processes remains a challenge due to the absence of high-performance solid catalysts. Herein, highly porous nanocage catalysts composed of well-mixed Co3O4 and ZnO nanocrystals were successfully fabricated via a facile heterometallic metal-organic framework (MOF)-templated synthetic route. Benefiting from a high porosity and the synergistic effect between Co3O4 and ZnO, the as-prepared composite catalysts exhibited a significantly enhanced production efficiency of GLC in the carbonylation reaction of glycerol with urea compared to the single-component counterparts. The yield of GLC over the Co50Zn50-350 catalyst reached 85.2%, with 93.3% conversion and near 91% GLC selectivity, and this catalytic performance was superior to that over most heterogeneous catalysts. More importantly, the proposed templated synthetic strategy of heterometallic MOFs facilitates the regulation of catalyst composition and surface structure and can therefore be potentially extended in the tailoring of other metal oxide composite catalysts.

  12. Introduction of π-complexation into porous aromatic framework for highly selective adsorption of ethylene over ethane

    KAUST Repository

    Li, Baiyan

    2014-06-18

    In this work, we demonstrate for the first time the introduction of π-complexation into a porous aromatic framework (PAF), affording significant increase in ethylene uptake capacity, as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and an equimolar ethylene/ethane ratio at 296 K reveal that PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivity (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. The formation of π-complexation between ethylene molecules and Ag(I) ions in PAF-1-SO 3Ag has been evidenced by the high isosteric heats of adsorption of C2H4 and also proved by in situ IR spectroscopy studies. Transient breakthrough experiments, supported by simulations, indicate the feasibility of PAF-1-SO3Ag for producing 99.95%+ pure C 2H4 in a Pressure Swing Adsorption operation. Our work herein thus suggests a new perspective to functionalizing PAFs and other types of advanced porous materials for highly selective adsorption of ethylene over ethane. © 2014 American Chemical Society.

  13. Introduction of π-complexation into porous aromatic framework for highly selective adsorption of ethylene over ethane

    KAUST Repository

    Li, Baiyan; Zhang, Yiming; Krishna, Rajamani; Yao, Kexin; Han, Yu; Wu, Zili; Ma, Dingxuan; Shi, Zhan; Pham, Tony T.; Space, Brian; Liu, Jian; Thallapally, Praveen K.; Liu, Jun; Chrzanowski, Matthew; Ma, Shengqian

    2014-01-01

    In this work, we demonstrate for the first time the introduction of π-complexation into a porous aromatic framework (PAF), affording significant increase in ethylene uptake capacity, as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and an equimolar ethylene/ethane ratio at 296 K reveal that PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivity (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. The formation of π-complexation between ethylene molecules and Ag(I) ions in PAF-1-SO 3Ag has been evidenced by the high isosteric heats of adsorption of C2H4 and also proved by in situ IR spectroscopy studies. Transient breakthrough experiments, supported by simulations, indicate the feasibility of PAF-1-SO3Ag for producing 99.95%+ pure C 2H4 in a Pressure Swing Adsorption operation. Our work herein thus suggests a new perspective to functionalizing PAFs and other types of advanced porous materials for highly selective adsorption of ethylene over ethane. © 2014 American Chemical Society.

  14. Scattering characteristics from porous silicon

    Directory of Open Access Journals (Sweden)

    R. Sabet-Dariani

    2000-12-01

    Full Text Available   Porous silicon (PS layers come into existance as a result of electrochemical anodization on silicon. Although a great deal of research has been done on the formation and optical properties of this material, the exact mechanism involved is not well-understood yet.   In this article, first, the optical properties of silicon and porous silicon are described. Then, previous research and the proposed models about reflection from PS and the origin of its photoluminescence are reveiwed. The reflecting and scattering, absorption and transmission of light from this material, are then investigated. These experiments include,different methods of PS sample preparation their photoluminescence, reflecting and scattering of light determining different characteristics with respect to Si bulk.

  15. Gas transport in porous media

    CERN Document Server

    Ho, Clifford K

    2006-01-01

    This book presents a compilation of state-of-the art studies on gas and vapor transport processes in porous and fractured media. A broad set of models and processes are presented, including advection/diffusion, the Dusty Gas Model, enhanced vapor diffusion, phase change, coupled processes, solid/vapor sorption, and vapor-pressure lowering. Numerous applications are also presented that illustrate these processes and models in current problems facing the scientific community. This book fills a gap in the general area of transport in porous and fractured media; an area that has historically been dominated by studies of liquid-phase flow and transport. This book identifies gas and vapor transport processes that may be important or dominant in various applications, and it exploits recent advances in computational modeling and experimental methods to present studies that distinguish the relative importance of various mechanisms of transport in complex media.

  16. POROUS STRUCTURE OF ROAD CONCRETE

    Directory of Open Access Journals (Sweden)

    M. K. Pshembaev

    2016-01-01

    Full Text Available Having a great number of concrete structure classifications it is recommended to specify the following three principal types: microstructure – cement stone structure; mesostructure – structure of cement-sand mortar in concrete; macrostucture – two-component system that consists of mortar and coarse aggregate. Every mentioned-above structure has its own specific features which are related to the conditions of their formation. Thus, microstructure of cement stone can be characterized by such structural components as crystal intergrowth, tobermorite gel, incompletely hydrated cement grains and porous space. The most important technological factors that influence on formation of cement stone microstructure are chemical and mineralogical cement composition, its grinding fineness, water-cement ratio and curing condition. Specific cement stone microstructure is formed due to interrelation of these factors. Cement stone is a capillary-porous body that consists of various solid phases represented predominantly by sub-microcrystals of colloidal dispersion. The sub-microcrystals are able adsorptively, osmotically and structurally to withhold (to bind some amount of moisture. Protection of road concrete as a capillary-porous body is considered as one of the topical issues. The problem is solved with the help of primary and secondary protection methods. Methods of primary protection are used at the stage of designing, preparation and placing of concrete. Methods of secondary protection are applied at the operational stage of road concrete pavement. The paper considers structures of concrete solid phase and characteristics of its porous space. Causes of pore initiation, their shapes, dimensions and arrangement in the concrete are presented in the paper. The highest hazard for road concrete lies in penetration of aggressive liquid in it and moisture transfer in the cured concrete. Water permeability of concrete characterizes its filtration factor which

  17. Porous squeeze-film flow

    KAUST Repository

    Knox, D. J.

    2013-11-14

    © 2013 © The authors 2013. Published by Oxford University Press on behalf of the Institute of Mathematics and its Applications. All rights reserved. The squeeze-film flow of a thin layer of Newtonian fluid filling the gap between a flat impermeable surface moving under a prescribed constant load and a flat thin porous bed coating a stationary flat impermeable surface is considered. Unlike in the classical case of an impermeable bed, in which an infinite time is required for the two surfaces to touch, for a porous bed contact occurs in a finite contact time. Using a lubrication approximation, an implicit expression for the fluid layer thickness and an explicit expression for the contact time are obtained and analysed. In addition, the fluid particle paths are calculated, and the penetration depths of fluid particles into the porous bed are determined. In particular, the behaviour in the asymptotic limit of small permeability, in which the contact time is large but finite, is investigated. Finally, the results are interpreted in the context of lubrication in the human knee joint, and some conclusions are drawn about the contact time of the cartilage-coated femoral condyles and tibial plateau and the penetration of nutrients into the cartilage.

  18. Pt Electrodes Enable the Formation of μ4-O Centers in MOF-5 from Multiple Oxygen Sources.

    Science.gov (United States)

    Li, Minyuan M; Dincă, Mircea

    2017-10-04

    The μ 4 -O 2- ions in the Zn 4 O(O 2 C-) 6 secondary building units of Zn 4 O(1,4-benzenedicarboxylate) 3 (MOF-5) electrodeposited under cathodic bias can be sourced from nitrate, water, and molecular oxygen when using platinum gauze as working electrodes. The use of Zn(ClO 4 ) 2 ·6H 2 O, anhydrous Zn(NO 3 ) 2 , or anhydrous Zn(CF 3 SO 3 ) 2 as Zn 2+ sources under rigorous control of other sources of oxygen, including water and O 2 , confirm that the source of the μ 4 -O 2- ions can be promiscuous. Although this finding reveals a relatively complicated manifold of electrochemical processes responsible for the crystallization of MOF-5 under cathodic bias, it further highlights the importance of hydroxide intermediates in the formation of the Zn 4 O(O 2 C-R) secondary building units in this iconic material and is illustrative of the complicated crystallization mechanisms of metal-organic frameworks in general.

  19. On the direct synthesis of Cu(BDC) MOF nanosheets and their performance in mixed matrix membranes

    Energy Technology Data Exchange (ETDEWEB)

    Shete, Meera; Kumar, Prashant; Bachman, Jonathan E.; Ma, Xiaoli; Smith, Zachary P.; Xu, Wenqian; Mkhoyan, K. Andre; Long, Jeffrey R.; Tsapatsis, Michael

    2018-03-01

    High aspect-ratio nanosheets of metal-organic frameworks (MOFs) hold promise for use as selective flakes in gas separation membranes. However, simple and scalable methods for the synthesis of MOF nanosheets have thus far remained elusive. Here, we describe the direct synthesis of Cu(BDC) (BDC2-= 1,4-benzenedicarboxylate) nanosheets with an average lateral size of 2.5 mu m and a thickness of 25 nm from a well-mixed solution. Characterization of the nanosheets by powder and thin film X-ray diffraction, electron microscopy, and electron diffraction reveals pronounced structural disorder that may affect their pore structure. Incorporation of the Cu (BDC) nanosheets into a Matrimid polymer matrix results in mixed matrix membranes (MMMs) that exhibit a 70% increase in the CO2/CH4 selectivity compared with that of Matrimid. Analysis of new and previously reported permeation data for Cu(BDC) MMMs using a mathematical model for selective flake composites indicates that further performance improvements could be achieved with the selection of different polymers for use in the continuous phase.

  20. A luminescent ratiometric pH sensor based on a nanoscale and biocompatible Eu/Tb-mixed MOF.

    Science.gov (United States)

    Xia, Tifeng; Zhu, Fengliang; Jiang, Ke; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2017-06-13

    The precise and real-time monitoring of localized pH changes is of great importance in many engineering and environmental fields, especially for monitoring small pH changes in biological environments and living cells. Metal-organic frameworks (MOFs) with their nanoscale processability show very promising applications in bioimaging and biomonitoring, but the fabrication of nanoscale MOFs is still a challenge. In this study, we synthesized a nanoscale mixed-lanthanide metal-organic framework by a microemulsion method. The morphology and size of the NMOF can be simply adjusted by the addition of different amounts of the CTAB surfactant. This NMOF exhibits significant pH-dependent luminescence emission, which can act as a self-referenced pH sensor based on two emissions of Tb 3+ at 545 nm and Eu 3+ at 618 nm in the pH range from 3.00 to 7.00. The MTT assay and optical microscopy assay demonstrate the low cytotoxicity and good biocompatibility of the nanosensor.

  1. Atomic layer deposition of molybdenum disulfide films using MoF 6 and H 2 S

    Energy Technology Data Exchange (ETDEWEB)

    Mane, Anil U. [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Letourneau, Steven [Micron School of Materials Science and Engineering, Boise State University, 1910 University Dr., Boise, Idaho 83725; Mandia, David J. [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Liu, Jian [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208; Libera, Joseph A. [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Lei, Yu [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Peng, Qing [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Graugnard, Elton [Micron School of Materials Science and Engineering, Boise State University, 1910 University Dr., Boise Idaho 83725; Elam, Jeffrey W. [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave, Argonne, Illinois 60439

    2018-01-01

    Molybdenum sulfide films were grown by atomic layer deposition on silicon and fused silica substrates using molybdenum hexafluoride (MoF6) and hydrogen sulfide at 200 degrees C. In situ quartz crystal microbalance (QCM) measurements confirmed linear growth at 0.46 angstrom/cycle and self-limiting chemistry for both precursors. Analysis of the QCM step shapes indicated that MoS2 is the reaction product, and this finding is supported by x-ray photoelectron spectroscopy measurements showing that Mo is predominantly in the Mo(IV) state. However, Raman spectroscopy and x-ray diffraction measurements failed to identify crystalline MoS2 in the as-deposited films, and this might result from unreacted MoFx residues in the films. Annealing the films at 350 degrees C in a hydrogen rich environment yielded crystalline MoS2 and reduced the F concentration in the films. Optical transmission measurements yielded a bandgap of 1.3 eV. Finally, the authors observed that the MoS2 growth per cycle was accelerated when a fraction of the MoF6 pulses were substituted with diethyl zinc. Published by the AVS

  2. Mof-associated complexes have overlapping and unique roles in regulating pluripotency in embryonic stem cells and during differentiation

    Science.gov (United States)

    Ravens, Sarina; Fournier, Marjorie; Ye, Tao; Stierle, Matthieu; Dembele, Doulaye; Chavant, Virginie; Tora, Làszlò

    2014-01-01

    The histone acetyltransferase (HAT) Mof is essential for mouse embryonic stem cell (mESC) pluripotency and early development. Mof is the enzymatic subunit of two different HAT complexes, MSL and NSL. The individual contribution of MSL and NSL to transcription regulation in mESCs is not well understood. Our genome-wide analysis show that i) MSL and NSL bind to specific and common sets of expressed genes, ii) NSL binds exclusively at promoters, iii) while MSL binds in gene bodies. Nsl1 regulates proliferation and cellular homeostasis of mESCs. MSL is the main HAT acetylating H4K16 in mESCs, is enriched at many mESC-specific and bivalent genes. MSL is important to keep a subset of bivalent genes silent in mESCs, while developmental genes require MSL for expression during differentiation. Thus, NSL and MSL HAT complexes differentially regulate specific sets of expressed genes in mESCs and during differentiation. DOI: http://dx.doi.org/10.7554/eLife.02104.001 PMID:24898753

  3. Effective Adsorption and Removal of Phosphate from Aqueous Solutions and Eutrophic Water by Fe-based MOFs of MIL-101.

    Science.gov (United States)

    Xie, Qiying; Li, Yan; Lv, Zhaoling; Zhou, Hang; Yang, Xiangjun; Chen, Jing; Guo, Hong

    2017-06-12

    Although many efforts have been devoted to the adsorptive removal of phosphate from aqueous solutions and eutrophic water, it is still highly desirable to develop novel adsorbents with high adsorption capacities. In this study, Fe-based metal-organic frameworks (MOFs), MIL-101 and NH 2 -MIL-101, are fabricated through a general facile strategy. Their performance as an adsorbent for phosphate removal is investigated. Experiments are performed to study the effects of various factors on the phosphate adsorption, including adsorbent dosage, contact time and co-existing ions. Both MIL-101(Fe) and NH 2 -MIL-101(Fe) show highly effective removal of phosphates from aqueous solutions, and the concentration of phosphates decrease sharply from the initial 0.60 mg·L -1 to 0.045 and 0.032 mg·L -1 , respectively, within just 30 min of exposure. The adsorption kinetics and adsorption isotherms reveal that NH 2 -MIL-101(Fe) has higher adsorption capacity than MIL-101(Fe) possibly due to the amine group. Furthermore, the Fe-based MOFs also exhibit a high selectivity towards phosphate over other anions such as chloride, bromide, nitrate and sulfate. Particularly, the prepared Fe-based MIL-101 materials are also capable of adsorbing phosphate in an actual eutrophic water sample and display better removal effect.

  4. Geometry and topology of porous materials

    International Nuclear Information System (INIS)

    Cohen, M.H.

    1985-01-01

    A very general definition of porous materials is given. The method of Lin and Cohen for the simple but exact description of the topology of porous materials is reviewed. The method leads to a precise definition of chambers, channels, and throats in the pore space. The power and utility of the method is illustrated via a discussion of the remarkable morphological features of porous rocks. These are enumerated and explained

  5. Porous silicon technology for integrated microsystems

    Science.gov (United States)

    Wallner, Jin Zheng

    With the development of micro systems, there is an increasing demand for integrable porous materials. In addition to those conventional applications, such as filtration, wicking, and insulating, many new micro devices, including micro reactors, sensors, actuators, and optical components, can benefit from porous materials. Conventional porous materials, such as ceramics and polymers, however, cannot meet the challenges posed by micro systems, due to their incompatibility with standard micro-fabrication processes. In an effort to produce porous materials that can be used in micro systems, porous silicon (PS) generated by anodization of single crystalline silicon has been investigated. In this work, the PS formation process has been extensively studied and characterized as a function of substrate type, crystal orientation, doping concentration, current density and surfactant concentration and type. Anodization conditions have been optimized for producing very thick porous silicon layers with uniform pore size, and for obtaining ideal pore morphologies. Three different types of porous silicon materials: meso porous silicon, macro porous silicon with straight pores, and macro porous silicon with tortuous pores, have been successfully produced. Regular pore arrays with controllable pore size in the range of 2mum to 6mum have been demonstrated as well. Localized PS formation has been achieved by using oxide/nitride/polysilicon stack as masking materials, which can withstand anodization in hydrofluoric acid up to twenty hours. A special etching cell with electrolytic liquid backside contact along with two process flows has been developed to enable the fabrication of thick macro porous silicon membranes with though wafer pores. For device assembly, Si-Au and In-Au bonding technologies have been developed. Very low bonding temperature (˜200°C) and thick/soft bonding layers (˜6mum) have been achieved by In-Au bonding technology, which is able to compensate the potentially

  6. A study of positron irradiated porous silicon

    International Nuclear Information System (INIS)

    Huang Yuanming; Xue Qing; Zhai Baogai; Xu Aijun; Liu Shewen; Yu Weizhong

    1998-01-01

    The effect of positron irradiation on photoluminescence (PL) of porous silicon has been studied. After four hour positron irradiation, the red PL spectrum of porous silicon blue shifts into greenish spectral region, and a higher energy luminescence band is introduced into this blueshifted spectrum. The fourier transform infrared absorption experiment shows that the positron irradiation can cause further oxidization of porous silicon. A possible mechanism causing this change of PL spectra after positron irradiation is suggested

  7. Film condensation on a porous vertical surface in a porous media

    International Nuclear Information System (INIS)

    Ebinuma, C.D.; Liu, C.Y.; Ismail, K.A.R.

    1983-01-01

    The problem of dry saturated steam film condensation by natural convection on a porous surface in a porous medium is presented. Through the classical Darcy law for flow in porous medium and the approximations considered in the Boundary layer theory, it is shown that the analytical solution exists only when the normal velocity to the porous wall is inversly proportional to the square root of the distance along the plate. (E.G.) [pt

  8. Chemistry in Confinement: Copper and Palladium Catalyzed Ecofriendly Organic Transformations within Porous Frameworks.

    Science.gov (United States)

    Kumar, Basuvaraj Suresh; Pitchumani, Kasi

    2018-05-01

    A concise account on the use of transition metals copper (Cu) and palladium (Pd), as their cations as well as nanoparticles exchanged/immobilized onto porous frameworks such as zeolites, metal organic frameworks (MOFs), covalent organic polymers (COPs) and hollow nanostructures, functioning as catalysts in organic synthesis is presented. This biomimetic account, "focusing on catalytic systems in confinement" within zero-dimensional microenvironments and second sphere coordination covers primarily results from our group on N-sulfonylketenimine mediated cycloaddition, hydrogenation and C-C bond forming reactions, thus providing an interesting insight into the versatility and utility of these Cu and Pd catalysts. Other significant advantages and green credentials of confinement such as stability, selectivity, reusability, promotion of multicomponent reactions, use of green solvents, atom economy, and use of ambient conditions are highlighted at appropriate places. In the final section, our views on the current achievements and the future prospects in this area are summarized. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Porous media heat transfer for injection molding

    Science.gov (United States)

    Beer, Neil Reginald

    2016-05-31

    The cooling of injection molded plastic is targeted. Coolant flows into a porous medium disposed within an injection molding component via a porous medium inlet. The porous medium is thermally coupled to a mold cavity configured to receive injected liquid plastic. The porous medium beneficially allows for an increased rate of heat transfer from the injected liquid plastic to the coolant and provides additional structural support over a hollow cooling well. When the temperature of the injected liquid plastic falls below a solidifying temperature threshold, the molded component is ejected and collected.

  10. Modelling of Emulsion Flow in Porous Media

    Energy Technology Data Exchange (ETDEWEB)

    Abou-Kassem, J.H. [UAE University (United Arab Emirates); Farouq Ali, S.M. [UAE University (United Arab Emirates)

    1995-06-01

    Oil recovery methods predominantly involve emulsion formation. Oil recovery simulation requires the incorporation of emulsion characteristics and flow in porous media, in order to optimize oil recovery from petroleum reservoirs. This paper explored the nature and rheology of emulsions, and evaluated several models of flow of Newtonian and non-Newtonian fluids in porous media. It also summarized in situ emulsion formation in porous media. A model for both Newtonian and non-Newtonian emulsion fluid flow was proposed, with special emphasis on pore size, and tortuosity in the porous media.

  11. The kinetics of porous insertion electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Atlung, S; West, K [British Columbia Univ., Vancouver (Canada)

    1989-05-01

    The principles of porous electrodes are discussed as well as the discharge of the insertion compound, the working potential, transport in the electrolyte, the time dependence of the electrolyte concentration, and modeling of the porous electrode. The simulation of a TiS2 porous electrode and the composite insertion electrode are considered as well. The influence of electrode thickness and porosity in a typical porous TiS2 electrode is revealed. It is shown that the use of insertion compounds as battery electrodes is limited by the requirement that the inserted ion must be distributed in the interior of the insertion compound particle. 15 refs.

  12. MOF-derived Cu-Pd/nanoporous carbon composite as an efficient catalyst for hydrogen evolution reaction: A comparison between hydrothermal and electrochemical synthesis

    Science.gov (United States)

    Mandegarzad, Sakineh; Raoof, Jahan Bakhsh; Hosseini, Sayed Reza; Ojani, Reza

    2018-04-01

    In this study, a novel catalyst based on Cu-Pd bimetallic nanoparticles supported on nanoporous carbon composite (NPCC) is successfully fabricated through three-step process and used as an electrocatalyst towards hydrogen evolution reaction (HER). At the first step, MOF-199 is synthesized via two distinct strategies; (1) hydrothermal (HT) and (2) electrochemical (EC). Next, the synthesized MOF-199 is used as a template in order to prepare Cu/NPCC by direct carbonization under N2 atmosphere followed by galvanic replacement reaction of Cu metals by PdII ions. All the prepared materials are characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and nitrogen adsorption/desorption measurements. The effect of synthesis method of MOF-199 on the electrocatalytic activity of the final product towards HER is investigated. The electrochemical measurements indicate that Cu-Pd/NPCC derived from the MOF prepared by EC method (Cu-Pd/NPCC/EC) exhibits an enhanced catalytic activity towards HER in H2SO4 solution than the Cu-Pd/NPCC/HT. This improvement may be attributed to using of supporting electrolyte in the preparation of Cu-Pd/NPCC/EC.

  13. A Fine-Tuned MOF for Gas and Vapor Separation: A Multipurpose Adsorbent for Acid Gas Removal, Dehydration, and BTX Sieving

    KAUST Repository

    Haja Mohideen, Mohamed Infas; Pillai, Renjith S.; Adil, Karim; Bhatt, Prashant; Belmabkhout, Youssef; Shkurenko, Aleksander; Maurin, Guillaume; Eddaoudi, Mohamed

    2017-01-01

    Summary The development of highly stable separation agents is recognized as a decisive step toward the successful deployment of energy-efficient and cost-effective separation processes. Here, we report the synthesis and construction of a metal-organic framework (MOF), kag-MOF-1, that has adequate structural and chemical features and affords a stable adsorbent with unique and appropriate adsorption properties for gas processing akin to acid gas removal, dehydration, and benzene-toluene-xylene (BTX) sieving. A combination of X-ray diffraction experiments, adsorption studies, mixed-gas breakthrough adsorption column testing, calorimetric measurements, and molecular simulations corroborated the exceptional separation performance of kag-MOF-1 and its prospective use as a multifunctional adsorbent. The unique adsorption properties of kag-MOF-1, resulting from the contracted pore system with aligned periodic array of exposed functionalities, attest to the prominence of this new generation of ultra-microporous material as a prospective practical adsorbent toward cost-effective and more simplified gas and vapor processing flowcharts for natural gas upgrading and flue gas scrubbing.

  14. Synthesis of a novel Au nanoparticles decorated Ni-MOF/Ni/NiO nanocomposite and electrocatalytic performance for the detection of glucose in human serum.

    Science.gov (United States)

    Chen, Jingyuan; Xu, Qin; Shu, Yun; Hu, Xiaoya

    2018-07-01

    A nonenzymatic glucose electrochemical sensor was constructed based on Au nanoparticles (AuNPs) decorated Ni metal-organic-framework (MOF)/Ni/NiO nanocomposite. Ni-MOF/Ni/NiO nanocomposite was synthesized by one-step calcination of Ni-MOF. Then AuNPs were loaded onto the Ni-based nanocomposites' surface through electrostatic adsorption. Through characterization by transmission electron microscopy (TEM), high resolution TEM (HRTEM) and energy disperse spectroscopy (EDS) mapping, it is found that the AuNPs were well distributed on the surface of Ni-based nanocomposite. Cyclic voltammetric (CV) study showed the electrocatalytic activity of Au-Ni nanocomposite was highly improved after loading AuNPs onto it. Amperometric study demonstrated that the Au-Ni nanocomposites modified glassy carbon electrode (GCE) exhibited a high sensitivity of 2133.5 mA M -1 cm -2 and a wide linear range (0.4-900 μM) toward the oxidation of glucose with a detection limit as low as 0.1 μM. Moreover, the reproducibility, selectivity and stability of the sensor all exhibited outstanding performance. We applied the as-fabricated high performance sensor to measure the glucose levels in human serum and obtained satisfactory results. It is believed that AuNPs decorated Ni MOF/Ni/NiO nanocomposite provides a new platform for developing highly performance electrochemical sensors in practical applications. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. A Fine-Tuned MOF for Gas and Vapor Separation: A Multipurpose Adsorbent for Acid Gas Removal, Dehydration, and BTX Sieving

    KAUST Repository

    Haja Mohideen, Mohamed Infas

    2017-10-19

    Summary The development of highly stable separation agents is recognized as a decisive step toward the successful deployment of energy-efficient and cost-effective separation processes. Here, we report the synthesis and construction of a metal-organic framework (MOF), kag-MOF-1, that has adequate structural and chemical features and affords a stable adsorbent with unique and appropriate adsorption properties for gas processing akin to acid gas removal, dehydration, and benzene-toluene-xylene (BTX) sieving. A combination of X-ray diffraction experiments, adsorption studies, mixed-gas breakthrough adsorption column testing, calorimetric measurements, and molecular simulations corroborated the exceptional separation performance of kag-MOF-1 and its prospective use as a multifunctional adsorbent. The unique adsorption properties of kag-MOF-1, resulting from the contracted pore system with aligned periodic array of exposed functionalities, attest to the prominence of this new generation of ultra-microporous material as a prospective practical adsorbent toward cost-effective and more simplified gas and vapor processing flowcharts for natural gas upgrading and flue gas scrubbing.

  16. Carbon-embedded Ni nanocatalysts derived from MOFs by a sacrificial template method for efficient hydrogenation of furfural to tetrahydrofurfuryl alcohol.

    Science.gov (United States)

    Su, Yanping; Chen, Chun; Zhu, Xiaoguang; Zhang, Yong; Gong, Wanbing; Zhang, Haimin; Zhao, Huijun; Wang, Guozhong

    2017-05-16

    We report a fast and simple method for the synthesis of Ni-based metal-organic-frameworks (Ni-MOFs). Due to the existence of nickel ions and an organic ligand, the MOFs are employed as a sacrificial template for the facile preparation of carbon-embedded Ni (Ni/C) catalysts by a direct thermal decomposition method. The obtained Ni/C catalysts exhibit excellent catalytic activity for selectively transforming furfural (FAL) to tetrahydrofurfuryl alcohol (THFOL) due to the Ni nanoparticles (NPs) embedded uniformly in the ligand-derived carbon. The exemplified results illustrate that the catalytic performance of the Ni/C catalyst is greatly affected by the calcination conditions (temperature and time), composition of the Ni-MOF precursor and the catalysis conditions. The conversion of FAL and selectivity of THFOL both reached 100% under the conditions of 120 °C, 1 MPa H 2 pressure and 120 min of hydrogenation over the Ni/C-500 catalyst, derived from the pyrolysis of Ni-MOFs (Ni : BTC mole ratio of 1.0) at 500 °C for 120 min, which exhibits an average nanoparticle size of ∼14 nm and uniform dispersion, and the highest BET surface area (∼92 m 2 g -1 ) among all investigated Ni/C catalysts. This facilely prepared heterogeneous catalyst would be very promising for the replacement of noble metal catalysts for the efficient catalytic conversion of biomass-derived feedstocks into value-added chemicals.

  17. Metal–organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2S

    KAUST Repository

    Belmabkhout, Youssef; Pillai, Renjith S.; Alezi, Dalal; Shekhah, Osama; Bhatt, Prashant; Chen, Zhijie; Adil, Karim; Vaesen, Sebastien; De Weireld, Guy; Pang, Maolin; Suetin, Mikhail; Cairns, Amy; Solovyeva, Vera; Shkurenko, Aleksander; El Tall, Omar; Maurin, Guillaume; Eddaoudi, Mohamed

    2017-01-01

    -framework counter ions (NO3-, Cl- and Br-). In3+-, Fe3+-, Ga3+-and the newly isolated Al(III)-based isostructural soc-MOF were extensively studied and evaluated for the separation-based production of high-quality fuels (i.e., CH4, C3H8 and n-C4H10) and olefins

  18. Influence of Filler Pore Structure and Polymer on the Performance of MOF-based Mixed Matrix Membranes for CO2 Capture.

    Science.gov (United States)

    Sabetghadam, Anahid; Liu, Xinlei; Benzaqui, Marvin; Gkaniatsou, Effrosyni; Orsi, Angelica; Lozinska, Magdalena M; Sicard, Clemence; Johnson, Timothy; Steunou, Nathalie; Wright, Paul A; Serre, Christian; Gascon, Jorge; Kapteijn, Freek

    2018-03-24

    In order to gain insight into the influence of metal-organic framework (MOF) filler and polymer on membrane performance, eight different composites are studied by combining four MOFs and two polymers. MOF materials (NH2-MIL-53(Al), MIL-69(Al), MIL-96(Al) and ZIF-94) with various chemical functionalities, topologies, and dimensionalities of porosity were employed as fillers, while two typical polymers with different permeability-selectivity properties (6FDA-DAM and Pebax) were deliberately selected as matrices. The best performing MOF-polymer composites were prepared by loading 25 wt.% of MIL-96(Al) as filler which improved the permeability and selectivity of 6FDA-DAM up to 32% and 10%, while for Pebax this enhancement was 25% and 18%, respectively. The observed differences in membrane performance in the separation of CO2 from N2 are explained on the basis of gas solubility, diffusivity properties and compatibility between the filler and polymer phases. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. A Chemical Route to Activation of Open Metal Sites in the Copper-Based Metal-Organic Framework Materials HKUST-1 and Cu-MOF-2.

    Science.gov (United States)

    Kim, Hong Ki; Yun, Won Seok; Kim, Min-Bum; Kim, Jeung Yoon; Bae, Youn-Sang; Lee, JaeDong; Jeong, Nak Cheon

    2015-08-12

    Open coordination sites (OCSs) in metal-organic frameworks (MOFs) often function as key factors in the potential applications of MOFs, such as gas separation, gas sorption, and catalysis. For these applications, the activation process to remove the solvent molecules coordinated at the OCSs is an essential step that must be performed prior to use of the MOFs. To date, the thermal method performed by applying heat and vacuum has been the only method for such activation. In this report, we demonstrate that methylene chloride (MC) itself can perform the activation role: this process can serve as an alternative "chemical route" for the activation that does not require applying heat. To the best of our knowledge, no previous study has demonstrated this function of MC, although MC has been popularly used in the pretreatment step prior to the thermal activation process. On the basis of a Raman study, we propose a plausible mechanism for the chemical activation, in which the function of MC is possibly due to its coordination with the Cu(2+) center and subsequent spontaneous decoordination. Using HKUST-1 film, we further demonstrate that this chemical activation route is highly suitable for activating large-area MOF films.

  20. A sensitive, colorimetric immunosensor based on Cu-MOFs and HRP for detection of dibutyl phthalate in environmental and food samples.

    Science.gov (United States)

    Zhu, Nuanfei; Zou, Yanmin; Huang, Menglu; Dong, Shuaibing; Wu, Xiangyang; Liang, Guoxi; Han, Zhixiang; Zhang, Zhen

    2018-08-15

    A sensitive and artful colorimetric immunosensor based on horseradish peroxidase (HRP) was designed by labelling metal-organic frameworks (Cu-MOFs) on the second antibody (Cu-MOFs@Ab 2 ) as signal amplification for the detection of trace dibutyl phthalate (DBP). In this system, when Cu-MOFs@Ab 2 was captured by antigen- primary antibody (Ab 1 ) complex, tremendous Cu(II) will be released from Cu-MOFs in the presence of nitric acid (HNO 3 ), and Cu(II) will be further reduced to Cu(I) after the addition of sodium ascorbate (SA), consequently, inhibiting the HRP to catalyse the colorless 3,3',5,5'-tetramethylbenzidine (TMB) into blue oxidized TMB (ox TMB). Under the optimized conditions, the limit of detection (LOD) was 1 μg L -1 , which was almost 60 times lower than that using a conventional ELISA with the same antibody. In addition, our method showed good accuracy and reproducibility (recoveries of 87.73-103.4%; CV values of 1.46-5.95%) through a spike-recovery analysis. The proposed immunosensor indicated great potential for trace DBP determination from environmental and food samples. Copyright © 2018. Published by Elsevier B.V.

  1. The first example of commensurate adsorption of atomic gas in a MOF and effective separation of xenon from other noble gases

    KAUST Repository

    Wang, Hao; Yao, Kexin; Zhang, Zhijuan; Jagiełło, Jacek; Gong, Qihan; Han, Yu; Li, Jing

    2014-01-01

    demonstrates high adsorption capacity for xenon and its IAST selectivity for Xe-Kr is the largest among all MOFs investigated to date. To mimic real world conditions, breakthrough experiments are conducted on Xe-Kr binary mixtures at room temperature and 1

  2. Quest for anionic MOF membranes: Continuous sod -ZMOF membrane with Co2 adsorption-driven selectivity

    KAUST Repository

    Almaythalony, Bassem

    2015-02-11

    We report the fabrication of the first continuous zeolite-like metal-organic framework (ZMOF) thin-film membrane. A pure phase sod-ZMOF, sodalite topology, membrane was grown and supported on a porous alumina substrate using a solvothermal crystallization method. The absence of pinhole defects in the film was confirmed and supported by the occurrence of quantifiable time-lags, for all studied gases, during constant volume/variable pressure permeation tests. For both pure and mixed gas feeds, the sod-ZMOF-1 membrane exhibits favorable permeation selectivity toward carbon dioxide over relevant industrial gases such as H2, N2, and CH4, and it is mainly governed by favorable CO2 adsorption.

  3. Particle transport in porous media

    Science.gov (United States)

    Corapcioglu, M. Yavuz; Hunt, James R.

    The migration and capture of particles (such as colloidal materials and microorganisms) through porous media occur in fields as diversified as water and wastewater treatment, well drilling, and various liquid-solid separation processes. In liquid waste disposal projects, suspended solids can cause the injection well to become clogged, and groundwater quality can be endangered by suspended clay and silt particles because of migration to the formation adjacent to the well bore. In addition to reducing the permeability of the soil, mobile particles can carry groundwater contaminants adsorbed onto their surfaces. Furthermore, as in the case of contamination from septic tanks, the particles themselves may be pathogens, i.e., bacteria and viruses.

  4. Positronium chemistry in porous adsorbents

    International Nuclear Information System (INIS)

    Foti, G.; Nagy, L.G.; Moravcsik, G.; Schay, G.

    1981-01-01

    Kinetic studies on the annihilation of orthopositronium in porous adsorbents have been performed using lifetime spectroscopy. The positron source applied was 22 Na with 0.2 MBq activity. The adsorbents investigated were silica gels of different particle size and pore structure. The appearance of the long-lived component in the lifetime spectra can be explained by the diffusion of the orthopositronium into the pores affected by the particle size and the pore size of the adsorbent, the coverage on it and the chemical nature of the adsorbate. The long-term aim of the work is to determine and to explain these effects. (author)

  5. Reversible flexible structural changes in multidimensional MOFs by guest molecules (I{sub 2}, NH{sub 3}) and thermal stimulation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yang; Li, Libo; Yang, Jiangfeng; Wang, Shuang; Li, Jinping, E-mail: Jpli211@hotmail.com

    2015-03-15

    Three metal–organic frameworks (MOFs), [Cu(INA){sub 2}], [Cu(INA){sub 2}I{sub 2}] and [Cu(INA){sub 2}(H{sub 2}O){sub 2}(NH{sub 3}){sub 2}], were synthesized with 3D, 2D, and 0D structures, respectively. Reversible flexible structural changes of these MOFs were reported. Through high temperature (60–100 °C) stimulation of I{sub 2} or ambient temperature stimulation of NH{sub 3}, [Cu(INA){sub 2}] (3D) converted to [Cu(INA){sub 2}I{sub 2}] (2D) and [Cu(INA){sub 2}(H{sub 2}O){sub 2}(NH{sub 3}){sub 2}] (0D); as the temperature increased to 150 °C, the MOFs changed back to their original form. In this way, this 3D MOF has potential application in the capture of I{sub 2} and NH{sub 3} from polluted water and air. XRD, TGA, SEM, NH{sub 3}-TPD, and the measurement of gas adsorption were used to describe the changes in processes regarding the structure, morphology, and properties. - Graphical abstract: Through I{sub 2}, NH{sub 3} molecules and thermal stimulation, the three MOFs can achieve reversible flexible structural changes. Different methods were used to prove the flexible reversible changes. - Highlights: • [Cu(INA){sub 2}] can flexible transform to [Cu(INA){sub 2}I{sub 2}] and [Cu(INA){sub 2}(H{sub 2}O){sub 2}(NH{sub 3}){sub 2}] by adsorbing I{sub 2} or NH{sub 3}. • The reversible flexible transformation related to material source, temperature and concentration. • Potential applications for the capture of I{sub 2} and NH{sub 3} from polluted water or air.

  6. The Cu-MOF-199/single-walled carbon nanotubes modified electrode for simultaneous determination of hydroquinone and catechol with extended linear ranges and lower detection limits

    International Nuclear Information System (INIS)

    Zhou, Jian; Li, Xi; Yang, Linlin; Yan, Songlin; Wang, Mengmeng; Cheng, Dan; Chen, Qi; Dong, Yulin; Liu, Peng; Cai, Weiquan; Zhang, Chaocan

    2015-01-01

    A novel electrochemical sensor based on Cu-MOF-199 [Cu-MOF-199 = Cu 3 (BTC) 2 (BTC = 1,3,5-benzenetricarboxylicacid)] and SWCNTs (single-walled carbon nanotubes) was fabricated for the simultaneous determination of hydroquinone (HQ) and catechol (CT). The modification procedure was carried out through casting SWCNTs on the bare glassy carbon electrode (GCE) and followed by the electrodeposition of Cu-MOF-199 on the SWCNTs modified electrode. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were performed to characterize the electrochemical performance and surface characteristics of the as-prepared sensor. The composite electrode exhibited an excellent electrocatalytic activity with increased electrochemical signals towards the oxidation of HQ and CT, owing to the synergistic effect of SWCNTs and Cu-MOF-199. Under the optimized condition, the linear response range were from 0.1 to 1453 μmol L −1 (R HQ  = 0.9999) for HQ and 0.1–1150 μmol L −1 (R CT  = 0.9990) for CT. The detection limits for HQ and CT were as low as 0.08 and 0.1 μmol L −1 , respectively. Moreover, the modified electrode presented the good reproducibility and the excellent anti-interference performance. The analytical performance of the developed sensor for the simultaneous detection of HQ and CT had been evaluated in practical samples with satisfying results. - Highlights: • Cu-MOF-199/SWCNTs/GCE was facilely fabricated by the electrodeposition on SWCNTs/GCE. • An electrochemical sensor for detecting HQ and CT was constructed based on this modified electrode. • The proposed electrochemical sensor showed an extended linear range and lower detection limits. • The proposed electrochemical sensor had an excellent stability and reproducibility.

  7. Electron beam selectively seals porous metal filters

    Science.gov (United States)

    Snyder, J. A.; Tulisiak, G.

    1968-01-01

    Electron beam welding selectively seals the outer surfaces of porous metal filters and impedances used in fluid flow systems. The outer surface can be sealed by melting a thin outer layer of the porous material with an electron beam so that the melted material fills all surface pores.

  8. Induction Healing of Porous Asphalt Concrete

    NARCIS (Netherlands)

    Liu, Q.

    2012-01-01

    Porous asphalt shows excellent performance in both noise reduction and water drainage. Although porous asphalt has these great qualities, its service life is much shorter (sometimes only half) compared to dense graded asphalt roads. Ravelling, which is the loss of aggregate particles from the

  9. Coumarin-modified microporous-mesoporous Zn-MOF-74 showing ultra-high uptake capacity and photo-switched storage/release of U{sup VI} ions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Le; Wang, Lin Lin; Gong, Le Le; Feng, Xue Feng; Luo, Ming Biao; Luo, Feng, E-mail: ecitluofeng@163.com

    2016-07-05

    Graphical abstract: Table of content Herein, through coordination-based post-synthetic strategy, microporous-mesoporous Zn-MOF-74 was easily functionalized by grafting coumarin on coordinatively unsaturated Zn(II) centers, yielding a series of coumarin-modified Zn-MOF-74 materials. The obtained samples afforded ultra-high adsorption capacity for UVI ions from water with maximum adsorption capacities as high as 360 mg/g (the record value in MOFs) and remarkable photo-switched capability of 50 mg/g. - Highlights: • This work shows the record uptake capability of U{sup VI} (360 mg/g) in MOFs. • This work shows, for the first time, photo-switching behaviour towards U{sup VI} in aqueous solution. • This work demonstrates a simple and effective method to largely enhance uptake capability of U{sup VI}. • This work demonstrates a distinct method to prepare photo-sensitive MOFs for photo-switching behaviour towards guest molecules. - Abstract: Driven by an energy crisis but consequently puzzled by various environmental problems, uranium, as the basic material of nuclear energy, is now receiving extensive attentions. In contrast to numerous sorbents applied in this field, metal-organic framework (MOFs), as a renovated material platform, has only recently been developed. How to improve the adsorption capacity of MOF materials towards U{sup VI} ions, as well as taking advantage of the nature of these MOFs to design photo-switched behaviour for photo-triggered storage/release of U{sup VI} ions are at present urgent problems and great challenges to be solved. Herein, we show a simple and facile method to target the goal. Through coordination-based post-synthetic strategy, microporous- mesoporous Zn-MOF-74 was easily functionalized by grafting coumarin on coordinatively unsaturated Zn(II) centers, yielding a series of coumarin-modified Zn-MOF-74 materials. The obtained samples displayed ultra-high adsorption capacity for U{sup VI} ions from water at pH value of 4 with

  10. Mixed convection in fluid superposed porous layers

    CERN Document Server

    Dixon, John M

    2017-01-01

    This Brief describes and analyzes flow and heat transport over a liquid-saturated porous bed. The porous bed is saturated by a liquid layer and heating takes place from a section of the bottom. The effect on flow patterns of heating from the bottom is shown by calculation, and when the heating is sufficiently strong, the flow is affected through the porous and upper liquid layers. Measurements of the heat transfer rate from the heated section confirm calculations. General heat transfer laws are developed for varying porous bed depths for applications to process industry needs, environmental sciences, and materials processing. Addressing a topic of considerable interest to the research community, the brief features an up-to-date literature review of mixed convection energy transport in fluid superposed porous layers.

  11. Manufactured Porous Ambient Surface Simulants

    Science.gov (United States)

    Carey, Elizabeth M.; Peters, Gregory H.; Chu, Lauren; Zhou, Yu Meng; Cohen, Brooklin; Panossian, Lara; Green, Jacklyn R.; Moreland, Scott; Backes, Paul

    2016-01-01

    The planetary science decadal survey for 2013-2022 (Vision and Voyages, NRC 2011) has promoted mission concepts for sample acquisition from small solar system bodies. Numerous comet-sampling tools are in development to meet this standard. Manufactured Porous Ambient Surface Simulants (MPASS) materials provide an opportunity to simulate variable features at ambient temperatures and pressures to appropriately test potential sample acquisition systems for comets, asteroids, and planetary surfaces. The original "flavor" of MPASS materials is known as Manufactured Porous Ambient Comet Simulants (MPACS), which was developed in parallel with the development of the Biblade Comet Sampling System (Backes et al., in review). The current suite of MPACS materials was developed through research of the physical and mechanical properties of comets from past comet missions results and modeling efforts, coordination with the science community at the Jet Propulsion Laboratory and testing of a wide range of materials and formulations. These simulants were required to represent the physical and mechanical properties of cometary nuclei, based on the current understanding of the science community. Working with cryogenic simulants can be tedious and costly; thus MPACS is a suite of ambient simulants that yields a brittle failure mode similar to that of cryogenic icy materials. Here we describe our suite of comet simulants known as MPACS that will be used to test and validate the Biblade Comet Sampling System (Backes et al., in review).

  12. Microelectromechanical pump utilizing porous silicon

    Science.gov (United States)

    Lantz, Jeffrey W [Albuquerque, NM; Stalford, Harold L [Norman, OK

    2011-07-19

    A microelectromechanical (MEM) pump is disclosed which includes a porous silicon region sandwiched between an inlet chamber and an outlet chamber. The porous silicon region is formed in a silicon substrate and contains a number of pores extending between the inlet and outlet chambers, with each pore having a cross-section dimension about equal to or smaller than a mean free path of a gas being pumped. A thermal gradient is provided along the length of each pore by a heat source which can be an electrical resistance heater or an integrated circuit (IC). A channel can be formed through the silicon substrate so that inlet and outlet ports can be formed on the same side of the substrate, or so that multiple MEM pumps can be connected in series to form a multi-stage MEM pump. The MEM pump has applications for use in gas-phase MEM chemical analysis systems, and can also be used for passive cooling of ICs.

  13. Capacitance effects in porous media

    International Nuclear Information System (INIS)

    Jasti, J.K.; Vaidya, R.N.; Fogler, H.S.

    1987-01-01

    The velocity dependence of the parameters in the Coats-Smith model for tracer dispersion and tailing in porous media was investigated in this study. Numerical simulations show that eddies with recirculation flow are formed in the pockets due to flow separation. The tracer transport between the eddies in the dead zones and the main channel was found to be diffusion limited. The simulations reveal that in the Stokes' flow regime the mass transfer coefficient between the two regions is independent of interstitial velocity. Core flood experiments were performed using radioactive tracers to verify the hypothesis that the capcitance effects are not due to a change in flowing fraction. The experimental results confirm that racer tailing is a function of the ratio of the molecular diffusivity to the flow rate. In light of these findings, the authors investigated the validity of the Coats-Smith model to predict dispersion and tailing in porous medium. Their studies indicate that the Coats-Smith model may be used, however, certain restrictions apply to the procedure for estimation of parameters and are described in this paper

  14. Size-selective QD@MOF core-shell nanocomposites for the highly sensitive monitoring of oxidase activities.

    Science.gov (United States)

    Wang, Ke; Li, Nan; Zhang, Jing; Zhang, Zhiqi; Dang, Fuquan

    2017-01-15

    In this work, we proposed a novel and facile method to monitor oxidase activities based on size-selective fluorescent quantum dot (QD)@metal-organic framework (MOF) core-shell nanocomposites (CSNCPs). The CSNCPs were synthesized from ZIF-8 and CdTe QDs in aqueous solution in 40min at room temperature with stirring. The prepared CdTe@ZIF-8 CSNCPs , which have excellent water dispersibility and stability, displays distinct fluorescence responses to hole scavengers of different molecular sizes (e.g., H 2 O 2 , substrate, and oxidase) due to the aperture limitation of the ZIF-8 shell. H 2 O 2 can efficiently quench the fluorescence of CdTe@ZIF-8 CSNCPs over a linearity range of 1-100nM with a detection limit of 0.29nM, whereas large molecules such as substrate and oxidase have very little effect on its fluorescence. Therefore, the highly sensitive detection of oxidase activities was achieved by monitoring the fluorescence quenching of CdTe@ZIF-8 CSNCPs by H 2 O 2 produced in the presence of substrate and oxidase, which is proportional to the oxidase activities. The linearity ranges of the uricase and glucose oxidase activity are 0.1-50U/L and 1-100U/L, respectively, and their detection limits are 0.024U/L and 0.26U/L, respectively. Therefore, the current QD@MOF CSNCPs based sensing system is a promising, widely applicable means of monitoring oxidase activities in biochemical research. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Post-Synthesis Functionalization of Porous Organic Polymers for CO2 Capture

    KAUST Repository

    Al Otaibi, Mona S.

    2014-07-01

    Solid porous materials are network materials that contain space void. Porous Organic Polymers (POPs) are porous materials, which are constructed from organic building blocks and exhibit large surface area with low densities. Due to these characteristics, POPs have attracted attentions because of their potential use in application such as gas storage and chemical separation. This thesis presents a study of the synthesis of novel POP being a network based on 2,5- dibromobenzaldehyde and 1,3,5-triethynylbenzene linked together via Sonogashira- Hagihara (SH) coupling. This network showed a relatively good surface area of 770 m2/g and total pore volume of 0.59 cc/g. In addition, it proved to be chemically and thermally stable, maintaining the thermal stability up to 350oC. In addition to synthesize novel aldehyde-POP network, it was also possible to post synthetically modify a network via one-step post synthetic functionalization by amine. Ethelynediamine (EDA), Diethylenetriamine (DETA), and Tris(2-aminoethyl)amine (Tris-amine) are three different amines used for aldehyde-POP functionalization. The produced networks were aminated via different amine species substitution the aldehyde group present within the network. Modification to these networks resulted in a decrease in surface area from 770 m2.g-1 to 333 m2.g-1, 162 m2.g-1, and 211 m2.g-1 in respective to EDA, DETA, and Tris-amine. Although the surface areas were decreased, the CO2 adsorption was enhanced as evidenced by the increase of Qst (i.e., from 25 to 45 kJ.mol-1 for DETA at low coverage). Our findings are expected to strengthen existing research areas of the influence of different type of amines (e.g aromatic amine) on CO2 adsorption. Although amine grafting has been studied in other systems (e.g., PAFs and MOFs), we are the first to reported amine functionalized POPs using a novel one-step amine grafting PSM procedure. Future research might extend to study the interaction between CO2 and amine species under

  16. Photonic Crystal Sensors Based on Porous Silicon

    Directory of Open Access Journals (Sweden)

    Claudia Pacholski

    2013-04-01

    Full Text Available Porous silicon has been established as an excellent sensing platform for the optical detection of hazardous chemicals and biomolecular interactions such as DNA hybridization, antigen/antibody binding, and enzymatic reactions. Its porous nature provides a high surface area within a small volume, which can be easily controlled by changing the pore sizes. As the porosity and consequently the refractive index of an etched porous silicon layer depends on the electrochemial etching conditions photonic crystals composed of multilayered porous silicon films with well-resolved and narrow optical reflectivity features can easily be obtained. The prominent optical response of the photonic crystal decreases the detection limit and therefore increases the sensitivity of porous silicon sensors in comparison to sensors utilizing Fabry-Pérot based optical transduction. Development of porous silicon photonic crystal sensors which allow for the detection of analytes by the naked eye using a simple color change or the fabrication of stacked porous silicon photonic crystals showing two distinct optical features which can be utilized for the discrimination of analytes emphasize its high application potential.

  17. Photonic Crystal Sensors Based on Porous Silicon

    Science.gov (United States)

    Pacholski, Claudia

    2013-01-01

    Porous silicon has been established as an excellent sensing platform for the optical detection of hazardous chemicals and biomolecular interactions such as DNA hybridization, antigen/antibody binding, and enzymatic reactions. Its porous nature provides a high surface area within a small volume, which can be easily controlled by changing the pore sizes. As the porosity and consequently the refractive index of an etched porous silicon layer depends on the electrochemial etching conditions photonic crystals composed of multilayered porous silicon films with well-resolved and narrow optical reflectivity features can easily be obtained. The prominent optical response of the photonic crystal decreases the detection limit and therefore increases the sensitivity of porous silicon sensors in comparison to sensors utilizing Fabry-Pérot based optical transduction. Development of porous silicon photonic crystal sensors which allow for the detection of analytes by the naked eye using a simple color change or the fabrication of stacked porous silicon photonic crystals showing two distinct optical features which can be utilized for the discrimination of analytes emphasize its high application potential. PMID:23571671

  18. Moisture Sorption in Porous Materials

    DEFF Research Database (Denmark)

    Nielsen, Lauge Fuglsang

    2007-01-01

    pressure and weight data can be "translated" to pore geometry by known physical relationships. In this context, analytical descriptions are important which can relate moisture condensation in pore structures to ambient vapor pressure. Such a description, the extended BET-relation, is presented...... physical parameters, the so-called BET-parameters: The heat property factor, C, and the pore surface, SBET (derived from the so-called uni-molecular moisture content uBET). A software ‘SORP07’ has been developed to handle any calculations made in the paper. For readers who have a special interest...... in the subject considered this software is available on request to the author. Keywords: Porous materials, moisture, adsorption, desorption, BET-parameters....

  19. Flow in fissured porous media

    International Nuclear Information System (INIS)

    Stichel, Sabine

    2014-01-01

    The flow simulation in fissured porous media is of importance for hydro-geological applications like ground water contamination in the neighborhood of waste disposal sites, radioactive waste repositories, fossil fuel mining or underground CO2 storage facilities. The permeability within the fissures - that are preferred transport paths - could influence the flow profile. The anisotropic geometry and the excursive parameter changes produce enormous challenges to numerical methods. A low-dimensional approach is used to model then processes within the fissures, acceptable results were reached. Based on the properties of the fissure and flow parameters a criterion was defined that allows to judge whether the application of the low-dimensional approach is sufficient. A dimension-adapting approach is presented that allow the change tp a full-dimensional model according to the criterion.

  20. Properties of porous netted materials

    International Nuclear Information System (INIS)

    Daragan, V.D.; Drozdov, B.G.; Kotov, A.Yu.; Mel'nikov, G.N.; Pustogarov, A.V.

    1987-01-01

    Hydraulic and strength characteristics, efficient heat conduction and inner heat exchange coefficient are experimentally studied for porous netted materials on the base of the brass nets as dependent on porosity, cell size and method of net laying. Results of the studies are presented. It is shown that due to anisotropy of the material properties the hydraulic resistance in the direction parallel to the nets plane is 1.3-1.6 times higher than in the perpendicular one. Values of the effective heat conduction in the direction perpendicular to the nets plane at Π>0.45 agree with the data from literature, at Π<0.45 a deviation from the calculated values is marked in the direction of the heat conduction decrease

  1. Thermal flow in porous media

    International Nuclear Information System (INIS)

    Ene, H.I.; Poliwevski, D.

    1987-01-01

    Thermal flows in porous media are important in a wide range of areas: oil recovery, geothermal development, chemical and nuclear industry, civil engineering, energy storage and energy conversion. This book uses a systematic, rigorous and unified treatment to provide a general understanding of the phenomena involved. General equations for single- or multiphase flows (including an arbitrary number of components inside each phase), diffusion and chemical reactions are presented. The boundary conditions which may be imposed, the non-dimensional para meters, the structures of the solutions, the stability of the finite amplitude solutions and many other related topics ae also studied. Although the treatment is basically mathematical, specific physical problems are also dealt with. There are two major fields of applications: natural convection and underground combustion. Both are discussed in detail. Various examples with exact or numerical solutions, for the case of bounded or unbounded domains, are presented, accompanied by extensive comment

  2. Additive manufacturing technologies of porous metal implants

    Directory of Open Access Journals (Sweden)

    Yang Quanzhan

    2014-06-01

    Full Text Available Biomedical metal materials with good corrosion resistance and mechanical properties are widely used in orthopedic surgery and dental implant materials, but they can easily cause stress shielding due to the significant difference in elastic modulus between the implant and human bones. The elastic modulus of porous metals is lower than that of dense metals. Therefore, it is possible to adjust the pore parameters to make the elastic modulus of porous metals match or be comparable with that of the bone tissue. At the same time, the open porous metals with pores connected to each other could provide the structural condition for bone ingrowth, which is helpful in strengthening the biological combination of bone tissue with the implants. Therefore, the preparation technologies of porous metal implants and related research have been drawing more and more attention due to the excellent features of porous metals. Selective laser melting (SLM and electron beam melting technology (EBM are important research fields of additive manufacturing. They have the advantages of directly forming arbitrarily complex shaped metal parts which are suitable for the preparation of porous metal implants with complex shape and fine structure. As new manufacturing technologies, the applications of SLM and EBM for porous metal implants have just begun. This paper aims to understand the technology status of SLM and EBM, the research progress of porous metal implants preparation by using SLM and EBM, and the biological compatibility of the materials, individual design and manufacturing requirements. The existing problems and future research directions for porous metal implants prepared by SLM and EBM methods are discussed in the last paragraph.

  3. Formation and properties of porous silicon layers

    International Nuclear Information System (INIS)

    Vitanov, P.; Kamenova, M.; Dimova-Malinovska, D.

    1993-01-01

    Preparation, properties and application of porous silicon films are investigated. Porous silicon structures were formed by an electrochemical etching process resulting in selective dissolution of the silicon substrate. The silicon wafers used with a resistivity of 5-10Ω.cm were doped with B to concentrations 6x10 18 -1x10 19 Ω.cm -3 in the temperature region 950 o C-1050 o C. The density of each porous films was determined from the weight loss during the anodization and it depends on the surface resistivity of the Si wafer. The density decreases with decreasing of the surface resistivity. The surface of the porous silicon layers was studied by X-ray photoelectron spectroscopy which indicates the presence of SiF 4 . The kinetic dependence of the anode potential and the porous layer thickness on the time of anodization in a galvanostatic regime for the electrolytes with various HF concentration were studied. In order to compare the properties of the resulting porous layers and to establish the dependence of the porosity on the electrolyte, three types of electrolytes were used: concentrated HF, diluted HF:H 2 O=1:1 and ethanol-hydrofluoric solutions HF:C 2 H 5 OH:H 2 O=2:1:1. High quality uniform and reproducible layers were formed using aqueous-ethanol-hydrofluoric electrolyte. Both Kikuchi's line and ring patterns were observed by TEM. The porous silicon layer was single crystal with the same orientation as the substrate. The surface shows a polycrystalline structure only. The porous silicon layers exhibit visible photoluminescence (PL) at room temperature under 480 nm Ar + laser line excitation. The peak of PL was observed at about 730 nm with FWHM about 90 nm. Photodiodes was made with a W-porous silicon junction. The current voltage and capacity voltage characteristics were similar to those of an isotype heterojunction diode. (orig.)

  4. Hydrodynamic dispersion within porous biofilms

    KAUST Repository

    Davit, Y.

    2013-01-23

    Many microorganisms live within surface-associated consortia, termed biofilms, that can form intricate porous structures interspersed with a network of fluid channels. In such systems, transport phenomena, including flow and advection, regulate various aspects of cell behavior by controlling nutrient supply, evacuation of waste products, and permeation of antimicrobial agents. This study presents multiscale analysis of solute transport in these porous biofilms. We start our analysis with a channel-scale description of mass transport and use the method of volume averaging to derive a set of homogenized equations at the biofilm-scale in the case where the width of the channels is significantly smaller than the thickness of the biofilm. We show that solute transport may be described via two coupled partial differential equations or telegrapher\\'s equations for the averaged concentrations. These models are particularly relevant for chemicals, such as some antimicrobial agents, that penetrate cell clusters very slowly. In most cases, especially for nutrients, solute penetration is faster, and transport can be described via an advection-dispersion equation. In this simpler case, the effective diffusion is characterized by a second-order tensor whose components depend on (1) the topology of the channels\\' network; (2) the solute\\'s diffusion coefficients in the fluid and the cell clusters; (3) hydrodynamic dispersion effects; and (4) an additional dispersion term intrinsic to the two-phase configuration. Although solute transport in biofilms is commonly thought to be diffusion dominated, this analysis shows that hydrodynamic dispersion effects may significantly contribute to transport. © 2013 American Physical Society.

  5. Immobilization of cellulase using porous polymer matrix

    International Nuclear Information System (INIS)

    Kumakura, M.; Kaetsu, I.

    1984-01-01

    A new method is discussed for the immobilization of cellulase using porous polymer matrices, which were obtained by radiation polymerization of hydrophilic monomers. In this method, the immobilized enzyme matrix was prepared by enzyme absorbtion in the porous polymer matrix and drying treatment. The enzyme activity of the immobilized enzyme matrix varied with monomer concentration, cooling rate of the monomer solution, and hydrophilicity of the polymer matrix, takinn the change of the nature of the porous structure in the polymer matrix. The leakage of the enzymes from the polymer matrix was not observed in the repeated batch enzyme reactions

  6. Tritium transport in lithium ceramics porous media

    International Nuclear Information System (INIS)

    Tam, S.W.; Ambrose, V.

    1991-01-01

    A random network model has been utilized to analyze the problem of tritium percolation through porous Li ceramic breeders. Local transport in each pore channel is described by a set of convection-diffusion-reaction equations. Long range transport is described by a matrix technique. The heterogeneous structure of the porous medium is accounted for via Monte Carlo methods. The model was then applied to an analysis of the relative contribution of diffusion and convective flow to tritium transport in porous lithium ceramics. 15 refs., 4 figs

  7. METHOD OF IMPREGNATING A POROUS MATERIAL

    Science.gov (United States)

    Steele, G.N.

    1960-06-01

    A method of impregnating a porous body with an inorganic uranium- containing salt is outlined and comprises dissolving a water-soluble uranium- containing salt in water; saturating the intercommunicating pores of the porous body with the salt solution; infusing ammonia gas into the intercommunicating pores of the body, the ammonia gas in water chemically reacting with the water- soluble uranium-containing salt in the water solvent to form a nonwater-soluble uranium-containing precipitant; and evaporating the volatile unprecipitated products from the intercommunicating pores whereby the uranium-containing precipitate is uniformly distributed in the intercommunicating peres of the porous body.

  8. Porous and Nanoporous Semiconductors and Emerging Applications

    Directory of Open Access Journals (Sweden)

    Helmut Föll

    2006-01-01

    Full Text Available Pores in single-crystalline semiconductors can be produced in a wide range of geometries and morphologies, including the “nanometer” regime. Porous semiconductors may have properties completely different from the bulk, and metamaterials with, for example, optical properties not encountered in natural materials are emerging. Possible applications of porous semiconductors include various novel sensors, but also more “exotic” uses as, for example, high explosives or electrodes for micro-fuel cells. The paper briefly reviews pore formation (including more applied aspects of large area etching, properties of porous semiconductors, and emerging applications.

  9. Simulating microtransport in realistic porous media

    NARCIS (Netherlands)

    Lopez Penha, D.J.

    2012-01-01

    Simulations in porous media widely adopt macroscopic models of transport phenomena. These models are computationally efficient as not all geometrical details at the pore scale are accounted for. Generally, these models require closure relations for effective transport parameters, where the

  10. Ab initio model of porous periclase

    International Nuclear Information System (INIS)

    Drummond, Neil D.; Swift, Damian C.; Ackland, Graeme J.

    2004-01-01

    A two-phase equilibrium equation of state (EOS) for periclase (MgO) was constructed using ab initio quantum mechanics, including a rigorous calculation of quasiharmonic phonon modes. Much of the shock wave data reported for periclase is on porous material. We compared the theoretical EOS with porous data using a simple 'snowplough' treatment and also a model using finite equilibration rates suitable for continuum mechanics simulations. (This model has been applied previously to various heterogeneous explosives as well as other porous materials.) The results were consistent and matched the data well at pressures above the regime affected by strength - and ramp-wave formation - during compaction. Ab initio predictions of the response of porous material have been cited recently as a novel and advanced capability; we feel that this is a fairly routine extension to established ab initio techniques

  11. Porous Organic Polymers for CO2 Capture

    KAUST Repository

    Teng, Baiyang

    2013-01-01

    to reduce the emission of CO2 to atmosphere. Porous organic polymers (POPs) are promising candidates for this application due to their readily tunable textual properties and surface functionalities. The objective of this thesis work is to develop new POPs

  12. ynthèse et caractérisation de MOFs dérivés d’Al (III) et Fe (III) benzendicarboxylate

    OpenAIRE

    MOULAY MELIANI, AMINA

    2015-01-01

    Ce travail interdisciplinaire nous a permis de maitriser les techniques de synthèse des MOFs en général, et l’exploitation des spectres des différentes technique d’analyse spectrale comme : l’infrarouge (IR) et diffraction des Rayon X (DRX) en particulier. Il est important de souligner l’apport original de ce travail qui consiste en la possibilité de l’élaboration de composés purs à partir de réactifs non purifiés, alors qu’il est connu que pour la synthèse de MOFs, il est indispensable d’...

  13. The next chapter in MOF pillaring strategies: Trigonal heterofunctional ligands to access targeted high-connected three dimensional nets, isoreticular platforms

    KAUST Repository

    Eubank, Jarrod F.

    2011-11-09

    A new pillaring strategy, based on a ligand-to-axial approach that combines the two previous common techniques, axial-to-axial and ligand-to-ligand, and permits design, access, and construction of higher dimensional MOFs, is introduced and validated. Trigonal heterofunctional ligands, in this case isophthalic acid cores functionalized at the 5-position with N-donor (e.g., pyridyl- or triazolyl-type) moieties, are designed and utilized to pillar pretargeted two-dimensional layers (supermolecular building layers, SBLs). These SBLs, based on edge transitive Kagomé and square lattices, are cross-linked into predicted three-dimensional MOFs with tunable large cavities, resulting in isoreticular platforms. © 2011 American Chemical Society.

  14. The next chapter in MOF pillaring strategies: Trigonal heterofunctional ligands to access targeted high-connected three dimensional nets, isoreticular platforms

    KAUST Repository

    Eubank, Jarrod F.; Wojtas, Łukasz; Hight, Matthew R.; Bousquet, Till; Kravtsov, Victor Ch H; Eddaoudi, Mohamed

    2011-01-01

    A new pillaring strategy, based on a ligand-to-axial approach that combines the two previous common techniques, axial-to-axial and ligand-to-ligand, and permits design, access, and construction of higher dimensional MOFs, is introduced and validated. Trigonal heterofunctional ligands, in this case isophthalic acid cores functionalized at the 5-position with N-donor (e.g., pyridyl- or triazolyl-type) moieties, are designed and utilized to pillar pretargeted two-dimensional layers (supermolecular building layers, SBLs). These SBLs, based on edge transitive Kagomé and square lattices, are cross-linked into predicted three-dimensional MOFs with tunable large cavities, resulting in isoreticular platforms. © 2011 American Chemical Society.

  15. Porous Silicon Sensors- Elusive and Erudite

    OpenAIRE

    H. Saha, Prof.

    2017-01-01

    Porous Silicon Sensors have been fabricated and tested successfully over the last few years as humidity sensors, vapour sensors, gas sensors, piezoresistive pressure sensors and bio- sensors. In each case it has displayed remarkably sensitivity, relatively low temperature operation and ease of fabrication. Brief description of fabrication and properties of all these types of different sensors is reported in this paper. The barriers of porous silicon like contact, non- uniformity, instability ...

  16. Porous polymeric materials for hydrogen storage

    Science.gov (United States)

    Yu, Luping; Liu, Di-Jia; Yuan, Shengwen; Yang, Junbing

    2013-04-02

    A porous polymer, poly-9,9'-spirobifluorene and its derivatives for storage of H.sub.2 are prepared through a chemical synthesis method. The porous polymers have high specific surface area and narrow pore size distribution. Hydrogen uptake measurements conducted for these polymers determined a higher hydrogen storage capacity at the ambient temperature over that of the benchmark materials. The method of preparing such polymers, includes oxidatively activating solids by CO.sub.2/steam oxidation and supercritical water treatment.

  17. Porous titanium bases for osteochondral tissue engineering

    Science.gov (United States)

    Nover, Adam B.; Lee, Stephanie L.; Georgescu, Maria S.; Howard, Daniel R.; Saunders, Reuben A.; Yu, William T.; Klein, Robert W.; Napolitano, Anthony P.; Ateshian, Gerard A.

    2015-01-01

    Tissue engineering of osteochondral grafts may offer a cell-based alternative to native allografts, which are in short supply. Previous studies promote the fabrication of grafts consisting of a viable cell-seeded hydrogel integrated atop a porous, bone-like metal. Advantages of the manufacturing process have led to the evaluation of porous titanium as the bone-like base material. Here, porous titanium was shown to support the growth of cartilage to produce native levels of Young’s modulus, using a clinically relevant cell source. Mechanical and biochemical properties were similar or higher for the osteochondral constructs compared to chondral-only controls. Further investigation into the mechanical influence of the base on the composite material suggests that underlying pores may decrease interstitial fluid pressurization and applied strains, which may be overcome by alterations to the base structure. Future studies aim to optimize titanium-based tissue engineered osteochondral constructs to best match the structural architecture and strength of native grafts. Statement of Significance The studies described in this manuscript follow up on previous studies from our lab pertaining to the fabrication of osteochondral grafts that consist of a bone-like porous metal and a chondrocyte-seeded hydrogel. Here, tissue engineered osteochondral grafts were cultured to native stiffness using adult chondrocytes, a clinically relevant cell source, and a porous titanium base, a material currently used in clinical implants. This porous titanium is manufactured via selective laser melting, offering the advantages of precise control over shape, pore size, and orientation. Additionally, this manuscript describes the mechanical influence of the porous base, which may have applicability to porous bases derived from other materials. PMID:26320541

  18. CoM(M=Fe,Cu,Ni)-embedded nitrogen-enriched porous carbon framework for efficient oxygen and hydrogen evolution reactions

    Science.gov (United States)

    Feng, Xiaogeng; Bo, Xiangjie; Guo, Liping

    2018-06-01

    Rational synthesis and development of earth-abundant materials with efficient electrocatalytic activity and stability for water splitting is a critical but challenging step for sustainable energy application. Herein, a family of bimetal (CoFe, CoCu, CoNi) embedded nitrogen-doped carbon frameworks is developed through a facile and simple thermal conversion strategy of metal-doped zeolitic imidazolate frameworks. Thanks to collaborative superiorities of abundant M-N-C species, modulation action of secondary metal, cobalt-based electroactive phases, template effect of MOFs and unique porous structure, bimetal embedded nitrogen-doped carbon frameworks materials manifest good oxygen and hydrogen evolution catalytic activity. Especially, after modulating the species and molar ratio of metal sources, optimal Co0.75Fe0.25 nitrogen-doped carbon framework catalyst just requires a low overpotential of 303 mV to achieve 10 mA cm-2 with a low Tafel slope (39.49 mV dec-1) for oxygen evolution reaction, which even surpasses that of commercial RuO2. In addition, the optimal catalyst can function as an efficient bifunctional electrocatalyst for overall water splitting with satisfying activity and stability. This development offers an attractive direction for the rational design and fabrication of porous carbon materials for electrochemical energy applications.

  19. CdS nanoparticles immobilized on porous carbon polyhedrons derived from a metal-organic framework with enhanced visible light photocatalytic activity for antibiotic degradation

    Science.gov (United States)

    Yang, Cao; Cheng, Jianhua; Chen, Yuancai; Hu, Yongyou

    2017-10-01

    The CdS/MOF-derived porous carbon (MPC) composite as an efficient visible-light-driven photocatalyst was prepared through the pyrolysis of ZIF-8 and subsequent growth of CdS. The porous and functionalized MPC enables intimate and discrete growth of CdS nanoparticles. This unique structure not only reduces the bulk recombination owing to nano-size effect of CdS, but also suppresses the surface recombination due to the discrete growth of CdS nanoparticles on MPC polyhedrons, which facilitates electron transfer and charge separation. Moreover, such a composite material possessed good adsorption ability toward the antibiotic pollutants because of the amino-functionalized surface. As a result, the as-prepared CdS/MPC composites showed excellent photocatalytic performance for the antibiotic degradation, significantly improving the photoactivity of CdS. Importantly, the CdS/MPC composite with the CdS loading of 20 wt% exhibited the highest photocatalytic efficiency of approximately 91% and apparent rate constant of 0.024 min-1.

  20. High-energy lithium-ion hybrid supercapacitors composed of hierarchical urchin-like WO3/C anodes and MOF-derived polyhedral hollow carbon cathodes.

    Science.gov (United States)

    Xu, Juan; Li, Yuanyuan; Wang, Lei; Cai, Qifa; Li, Qingwei; Gao, Biao; Zhang, Xuming; Huo, Kaifu; Chu, Paul K

    2016-09-22

    A lithium-ion hybrid supercapacitor (Li-HSC) comprising a Li-ion battery type anode and an electrochemical double layer capacitance (EDLC) type cathode has attracted much interest because it accomplishes a large energy density without compromising the power density. In this work, hierarchical carbon coated WO 3 (WO 3 /C) with a unique mesoporous structure and metal-organic framework derived nitrogen-doped carbon hollow polyhedra (MOF-NC) are prepared and adopted as the anode and the cathode for Li-HSCs. The hierarchical mesoporous WO 3 /C microspheres assembled by radially oriented WO 3 /C nanorods along the (001) plane enable effective Li + insertion, thus exhibit high capacity, excellent rate performance and a long cycling life due to their high Li + conductivity, electronic conductivity and structural robustness. The WO 3 /C structure shows a reversible specific capacity of 508 mA h g -1 at a 0.1 C rate (1 C = 696 mA h g -1 ) after 160 discharging-charging cycles with excellent rate capability. The MOF-NC achieved the specific capacity of 269.9 F g -1 at a current density of 0.2 A g -1 . At a high current density of 6 A g -1 , 92.4% of the initial capacity could be retained after 2000 discharging-charging cycles, suggesting excellent cycle stability. The Li-HSC comprising a WO 3 /C anode and a MOF-NC cathode boasts a large energy density of 159.97 W h kg -1 at a power density of 173.6 W kg -1 and 88.3% of the capacity is retained at a current density of 5 A g -1 after 3000 charging-discharging cycles, which are better than those previously reported for Li-HSCs. The high energy and power densities of the Li-HSCs of WO 3 /C//MOF-NC render large potential in energy storage.

  1. A combined stretching-tilting mechanism produces negative, zero and positive linear thermal expansion in a semi-flexible Cd(II)-MOF.

    Science.gov (United States)

    Lama, Prem; Das, Raj Kumar; Smith, Vincent J; Barbour, Leonard J

    2014-06-21

    A novel semi-flexible Cd(II)-MOF has been synthesized and characterized by variable temperature powder and single-crystal X-ray diffraction. The material displays an unusual combination of thermal expansion (TE) i.e. negative, zero and positive, which is an extremely rare finding, especially for metal-organic frameworks as a result of a combined stretching-tilting mechanism.

  2. Desarrollo de materiales Metal-Orgánicos (MOFs) como catalizadores heterogéneos para reacciones en una o varias etapas

    OpenAIRE

    García Cirujano, Francisco Cristobal

    2016-01-01

    [EN] This thesis summarizes our efforts to contribute to the development of novel heterogeneous catalysts based on Metal-Organic Framework compounds (MOFs) with a remarkable high thermal and chemical resistance; namely MIL-101 and UiO-66 type compounds. Special emphasis has been placed in the simultaneous introduction of two different active sites, either accidentally or intentionally through linker functionalization or post-synthesis encapsulation. This strategy could lead to multifunctional...

  3. A novel 3D Ag(I)-MOF: Surfactant-directed syntheses and catalytic degradation of o/m/p-Nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Xue-Qian [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Wen, Guo-Xuan [College of Science, China Three Gorges University, Yichang 443002 (China); Wu, Ya-Pan; Dong, Wen-Wen; Zhao, Jun [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China)

    2016-10-15

    For the first time, sodium caprylate has been investigated to direct the crystal growth of 3D Ag-MOF, [Ag{sub 2}(ddcba)(4,4′-bipy){sub 2}] (1), constructing from 3,5-(di(2′,5′-dicarboxylphenyl)benozoic acid and 4,4′-bipy. The single crystal diffraction analyses shows that complex 1 possess 3D neutral framework with a three-connected ThSi{sub 2} (10{sup 3}-b) topology. Compound 1 exhibits predominant catalytic activity towards the degradation of o-Nitrophenol (ONP), m-Nitrophenol (MNP) and p-Nitrophenol (PNP) in aqueous solution. The kinetics of such catalytic degradation reactions was also studied. - Graphical abstract: A novel 3D Ag(I)-MOF with ThSi{sub 2} (10{sup 3}-b) topology exhibits predominant catalytic activity towards the degradation of o-Nitrophenol (ONP), m-Nitrophenol (MNP) and p-Nitrophenol (PNP) in aqueous solution. - Highlights: • A novel 3D Ag(I)-MOF with ThSi{sub 2} (10{sup 3}-b) topology. • Surfactant as additive for directing the crystal growth. • Predominant catalytic activities for the degradation of o/m/p-nitrophenol.

  4. Direct in Situ Conversion of Metals into Metal-Organic Frameworks: A Strategy for the Rapid Growth of MOF Films on Metal Substrates.

    Science.gov (United States)

    Ji, Hoon; Hwang, Sunhyun; Kim, Keonmok; Kim, CheolGi; Jeong, Nak Cheon

    2016-11-30

    The fabrication of metal-organic framework (MOF) films on conducting substrates has demonstrated great potential in applications such as electronic conduction and sensing. For these applications, direct contact of the film to the conducting substrate without a self-assembled monolayer (SAM) is a desired step that must be achieved prior to the use of MOF films. In this report, we propose an in situ strategy for the rapid one-step conversion of Cu metal into HKUST-1 films on conducting Cu substrates. The Cu substrate acts both as a conducting substrate and a source of Cu 2+ ions during the synthesis of HKUST-1. This synthesis is possible because of the simultaneous reaction of an oxidizing agent and a deprotonating agent, in which the former agent dissolves the metal substrate to form Cu 2+ ions while the latter agent deprotonates the ligand. Using this strategy, the HKUST-1 film could not only be rapidly synthesized within 5 min but also be directly attached to the Cu substrate. Based on microscopic studies, we propose a plausible mechanism for the growth reaction. Furthermore, we show the versatility of this in situ conversion methodology, applying it to ZIF-8, which comprises Zn 2+ ions and imidazole-based ligands. Using an I 2 -filled HKUST-1 film, we further demonstrate that the direct contact of the MOF film to the conducting substrate makes the material more suitable for use as a sensor or electronic conductor.

  5. Colloid migration in porous media

    International Nuclear Information System (INIS)

    Hunt, J.R.; McDowell-Boyer; Sitar, N.

    1985-01-01

    Retention of radionuclides for long periods near waste repositories depends upon multiple barriers, one of which is adsorption to immobile solid surfaces. Since small particles and colloidal matter have high adsorption capacities per unit mass and can be mobile in subsurface flows, colloidal transport of waste components requires analysis. Theories for predicting colloid migration through porous media have been developed in the filtration literature. The applicability of filtration theories for predicting particle and colloid transport. Emphasis is on suspended matter much smaller than pore sizes, where physical and chemical forces control migration rather than size dependent physical straining. In general, experimentally verifiable theories exist for particle filtration by clean media, and a sensitivity analysis is possible on particle and media properties and fluid flow rate. When particle aggregates accumulate within pores, media permeability decreases, resulting in flow field alteration and possible radionuclide isolation. An analysis of the limited experimental data available indicates that present theories cannot predict long-term colloid transport when permeability reduction occurs. The coupling of colloid attachment processes and the hydrologic flow processes requires more extensive laboratory field research than has currently been carried out. An emphasis on the fundamental mechanisms is necessary to enhance long-term predictability

  6. Xenon fractionation in porous planetesimals

    Science.gov (United States)

    Zahnle, Kevin; Pollack, James B.; Kasting, James F.

    1990-01-01

    The distinctively fractionated Xe on Mars and earth may have its root in a common source from which both planets accreted. Beginning with Ozima and Nakazawa's (1980) hypothesis that terrestrial Xe fractionation was caused by gravitational separation of adsorbed solar nebular gases inside large porous planetesimals, it is pointed out that Xe would have been trapped as the planetesimal grew and pores were squeezed shut by lithostatic pressure. It is shown that enough fractionated Xe to supply the earth could have been trapped this way. The degree of fractionation is controlled by the lithostatic pressure at the pore-closing front and so would have been roughly the same for all large planetesimals. The predicted degree of fractionation agrees well with that preserved in terrestrial and Martian Xe. Relative to Xe, this source is strongly depleted in other noble gases. In contrast to the original Ozima and Nakazawa hypothesis, the present hypothesis predicts the observed fractionation, and it allows planetary accretion to occur after the dissipation of the solar nebula.

  7. Xenon fractionation in porous planetesimals

    International Nuclear Information System (INIS)

    Zahnle, K.; Pollack, J.B.; Kasting, J.F.

    1990-01-01

    The distinctively fractionated Xe on Mars and Earth may have its root in a common source from which both planets accreted. We begin with Ozima and Nakazawa's hypothesis that terrestrial Xe fractionation was caused by gravitational separation of adsorbed solar nebular gases inside large porous planetesimals. We point out that Xe would have been trapped as the planetesimal grew and pores were squeezed shut by lithostatic pressure. We show that enough fractionated Xe to supply the Earth could have been trapped this way. The degree of fractionation is controlled by the lithostatic pressure at the pore-closing front and so would have been roughly the same for all large planetesimals. The predicted degree of fractionation agrees well with that preserved in terrestrial and martian Xe. Relative to Xe, this source is strongly depleted in other noble gases. In contrast to the original Ozima and Nakazawa hypothesis, our hypothesis predicts the observed fractionation, and it allows planetary accretion to occur after the dissipation of the solar nebula. The required planetesimals are large, representing a class of object now extinct in the solar system

  8. Synthesis and electrochemical capacitive properties of nitrogen-doped porous carbon micropolyhedra by direct carbonization of zeolitic imidazolate framework-11

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Fei; Li, Li; Zhang, Xiaohua, E-mail: mickyxie@hnu.edu.cn; Chen, Jinhua, E-mail: chenjinhua@hnu.edu.cn

    2015-06-15

    Highlights: • Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were prepared from ZIF-11. • The activated N-PCMPs with fused KOH (N-PCMPs-A) have high specific surface area. • N-PCMPs-A exhibits high specific capacitance. • N-PCMPs-A reveals good cycling performance even at a high current density. - Abstract: Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were successfully prepared by direct carbonization of ZIF-11 polyhedra and further activated with fused KOH to obtain N-PCMPs-A. The morphology and microstructure of samples were examined by scanning electron microscopy, X-ray diffraction, and micropore and chemisorption analyzer. Electrochemical properties were characterized by cyclic voltammetry and galvanostatic charge/discharge method in 1.0 M H{sub 2}SO{sub 4} aqueous solution on a standard three-electrode system. Results show that, compared with N-PCMPs, N-PCMPs-A has higher specific surface area (2188 m{sup 2} g{sup −1}) and exhibits improved electrochemical capacitive properties (307 F g{sup −1} at 1.0 A g{sup −1}). The mass specific capacitance of N-PCMPs-A is also higher than that of most MOF-derived carbons, some carbide-derived carbons and carbon aerogel-derived carbons. In addition, the capacitance of the N-PCMPs-A retains 90% after 4000 cycles even at a high current density of 10 A g{sup −1}. These imply that N-PCMPs-A is the promising materials for the construction of a high-performance supercapacitor.

  9. From porous gold nanocups to porous nanospheres and solid particles - A new synthetic approach

    KAUST Repository

    Ihsan, Ayesha

    2015-05-01

    We report a versatile approach for the synthesis of porous gold nanocups, porous gold nanospheres and solid gold nanoparticles. Gold nanocups are formed by the slow reduction of gold salt (HAuCl4{dot operator}3H2O) using aminoantipyrene (AAP) as a reducing agent. Adding polyvinylpyrrolidone (PVP) to the gold salt followed by reduction with AAP resulted in the formation of porous gold nanospheres. Microwave irradiation of both of these porous gold particles resulted in the formation of slightly smaller but solid gold particles. All these nanoparticles are thoroughly characterized by UV-visible spectroscopy, scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM) and bright-field tomography. Due to the larger size, porous nature, low density and higher surface area, these nanomaterials may have interesting applications in catalysis, drug delivery, phototherapy and sensing.

  10. From porous gold nanocups to porous nanospheres and solid particles - A new synthetic approach

    KAUST Repository

    Ihsan, Ayesha; Katsiev, Habib; AlYami, Noktan; Anjum, Dalaver H.; Khan, Waheed S.; Hussain, Irshad

    2015-01-01

    We report a versatile approach for the synthesis of porous gold nanocups, porous gold nanospheres and solid gold nanoparticles. Gold nanocups are formed by the slow reduction of gold salt (HAuCl4{dot operator}3H2O) using aminoantipyrene (AAP) as a reducing agent. Adding polyvinylpyrrolidone (PVP) to the gold salt followed by reduction with AAP resulted in the formation of porous gold nanospheres. Microwave irradiation of both of these porous gold particles resulted in the formation of slightly smaller but solid gold particles. All these nanoparticles are thoroughly characterized by UV-visible spectroscopy, scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM) and bright-field tomography. Due to the larger size, porous nature, low density and higher surface area, these nanomaterials may have interesting applications in catalysis, drug delivery, phototherapy and sensing.

  11. Topological identification of the first uninodal 8-connected lsz MOF built from 2,2'-difluorobiphenyl-4,4'-dicarboxylate pillars and cadmium(II)-triazolate layers.

    Science.gov (United States)

    Zhang, Yuchi; Wu, Yuanhua; He, Xin; Ma, Junhan; Shen, Xuan; Zhu, Dunru

    2018-03-01

    Using polynuclear metal clusters as nodes, many high-symmetry high-connectivity nets, like 8-connnected bcu and 12-connected fcu, have been attained in metal-organic frameworks (MOFs). However, construction of low-symmetry high-connected MOFs with a novel topology still remains a big challenge. For example, a uninodal 8-connected lsz network, observed in inorganic ZrSiO 4 , has not been topologically identified in MOFs. Using 2,2'-difluorobiphenyl-4,4'-dicarboxylic acid (H 2 L) as a new linker and 1,2,4-triazole (Htrz) as a coligand, a novel three-dimensional Cd II -MOF, namely poly[tetrakis(μ 4 -2,2'-difluorobiphenyl-4,4'-dicarboxylato-κ 5 O 1 ,O 1' :O 1' :O 4 :O 4' )tetrakis(N,N-dimethylformamide-κO)tetrakis(μ 3 -1,2,4-triazolato-κ 3 N 1 :N 2 :N 4 )hexacadmium(II)], [Cd 6 (C 14 H 6 F 2 O 4 ) 4 (C 2 H 2 N 3 ) 4 (C 3 H 7 NO) 4 ] n , (I), has been prepared. Single-crystal structure analysis indicates that six different Cd II ions co-exist in (I) and each Cd II ion displays a distorted [CdO 4 N 2 ] octahedral geometry with four equatorial O atoms and two axial N atoms. Three Cd II ions are connected by four carboxylate groups and four trz - ligands to form a linear trinuclear [Cd 3 (COO) 4 (trz) 4 ] cluster, as do the other three Cd II ions. Two Cd 3 clusters are linked by trz - ligands in a μ 1,2,4 -bridging mode to produce a two-dimensional Cd II -triazolate layer with (6,3) topology in the ab plane. These two-dimensional layers are further pillared by the L 2- ligands along the c axis to generate a complicated three-dimensional framework. Topologically, regarding the Cd 3 cluster as an 8-connected node, the whole architecture of (I) is a uninodal 8-connected lsz framework with the Schläfli symbol (4 22 ·6 6 ). Complex (I) was further characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, thermogravimetric analysis and a photoluminescence study. MOF (I) has a high thermal and water stability.

  12. Porous silicon: Synthesis and optical properties

    International Nuclear Information System (INIS)

    Naddaf, M.; Awad, F.

    2006-01-01

    Formation of porous silicon by electrochemical etching method of both p and n-type single crystal silicon wafers in HF based solutions has been performed by using three different modes. In addition to DC and pulsed voltage, a novel etching mode is developed to prepare light-emitting porous silicon by applying and holding-up a voltage in gradient steps form periodically, between the silicon wafer and a graphite electrode. Under same equivalent etching conditions, periodic gradient steps voltage etching can yield a porous silicon layer with stronger photoluminescence intensity and blue shift than the porous silicon layer prepared by DC or pulsed voltage etching. It has been found that the holding-up of the applied voltage during the etching process for defined interval of time is another significant future of this method, which highly affects the blue shift. This can be used for tailoring a porous layer with novel properties. The actual mechanism behind the blue shift is not clear exactly, even the experimental observation of atomic force microscope and purist measurements in support with quantum confinement model. It has been seen also from Fourier Transform Infrared study that interplays between O-Si-H and Si-H bond intensities play key role in deciding the efficiency of photoluminescence emission. Study of relative humidity sensing and photonic crystal properties of pours silicon samples has confirmed the advantages of the new adopted etching mode. The sensitivity at room temperature of porous silicon prepared by periodic gradient steps voltage etching was found to be about 70% as compared to 51% and 45% for the porous silicon prepared by DC and pulsed voltage etching, respectively. (author)

  13. Porous silicon: Synthesis and optical properties

    International Nuclear Information System (INIS)

    Naddaf, M.; Awad, F.

    2006-06-01

    Formation of porous silicon by electrochemical etching method of both p and n-type single crystal silicon wafers in HF based solutions has been performed by using three different modes. In addition to DC and pulsed voltage, a novel etching mode is developed to prepare light-emitting porous silicon by applying and holding-up a voltage in gradient steps form periodically, between the silicon wafer and a graphite electrode. Under same equivalent etching conditions, periodic gradient steps voltage etching can yield a porous silicon layer with stronger photoluminescence intensity and blue shift than the porous silicon layer prepared by DC or pulsed voltage etching. It has been found that the holding-up of the applied voltage during the etching process for defined interval of time is another significant future of this method, which highly affects the blue shift. This can be used for tailoring a porous layer with novel properties. The actual mechanism behind the blue shift is not clear exactly, even the experimental observation of atomic force microscope and purist measurements in support with quantum confinement model. It has been seen also from Fourier Transform Infrared study that interplays between O-Si-H and Si-H bond intensities play key role in deciding the efficiency of photoluminescence emission. Study of relative humidity sensing and photonic crystal properties of pours silicon samples has confirmed the advantages of the new adopted etching mode. The sensitivity at room temperature of porous silicon prepared by periodic gradient steps voltage etching was found to be about 70% as compared to 51% and 45% for the porous silicon prepared by DC and pulsed voltage etching, respectively. (author)

  14. Formulation and catalytic performance of MOF-derived Fe@C/Al composites for high temperature Fischer–Tropsch synthesis

    KAUST Repository

    Oar-Arteta, Lide; Valero-Romero, Marí a José ; Wezendonk, Tim; Kapteijn, Freek; Gascon, Jorge

    2017-01-01

    High productivity towards C-2-C-4 olefins together with high catalyst stability are key for optimum operation in high temperature Fischer-Tropsch synthesis (HT-FTS). Here, we report the fabrication of Fe@C/Al composites that combine both the outstanding catalytic properties of the Fe-BTC MOF-derived Fe catalyst and the excellent mechanical resistance and textural properties provided by the inorganic AlOOH binder. The addition of AlOOH to Fe-BTC followed by pyrolysis in N-2 atmosphere at 500 degrees C results in composites with a large mesoporosity, a high Fe/Fe3O4 ratio, 10-35 nm average Fe crystallite size and coordinatively unsaturated Al3+ sites. In catalytic terms, the addition of AlOOH binder gives rise to enhanced C-2-C-4 selectivity and catalyst mechanical stability in HT-FTS, but at high Al contents the activity decreases. Altogether, the productivity of these Fe@C/Al composites is well above most known Fe catalysts for this process.

  15. Zeolite-like Metal–Organic Framework (MOF) Encaged Pt(II)-Porphyrin for Anion-Selective Sensing

    KAUST Repository

    Masih, Dilshad

    2018-03-26

    The selectivity and sensitivity of sensors are of great interest to the materials chemistry community, and a lot of effort is now devoted to improving these characteristics. More specifically, the selective sensing of anions is one of the largest challenges impeding the sensing-research area due to their similar physical and chemical behaviors. In this work, platinum–metalated porphyrin (Pt(II)TMPyP) was successfully encapsulated in a rho-type zeolite-like metal–organic framework (rho-ZMOF) and applied for anion-selective sensing. The sensing activity and selectivity of the MOF-encaged Pt(II)TMPyP for various anions in aqueous and methanolic media were compared to that of the free (nonencapsulated) Pt(II)TMPyP. While the photoinduced triplet-state electron transfer of Pt(II)TMPyP showed a very low detection limit for anions with no selectivity, the Pt(II)TMPyP encapsulated in the rho-ZMOF framework possessed a unique chemical structure to overcome such limitations. This new approach has the potential for use in other complex sensing applications, including biosensors, which require ion selectivity.

  16. Formulation and catalytic performance of MOF-derived Fe@C/Al composites for high temperature Fischer–Tropsch synthesis

    KAUST Repository

    Oar-Arteta, Lide

    2017-11-15

    High productivity towards C-2-C-4 olefins together with high catalyst stability are key for optimum operation in high temperature Fischer-Tropsch synthesis (HT-FTS). Here, we report the fabrication of Fe@C/Al composites that combine both the outstanding catalytic properties of the Fe-BTC MOF-derived Fe catalyst and the excellent mechanical resistance and textural properties provided by the inorganic AlOOH binder. The addition of AlOOH to Fe-BTC followed by pyrolysis in N-2 atmosphere at 500 degrees C results in composites with a large mesoporosity, a high Fe/Fe3O4 ratio, 10-35 nm average Fe crystallite size and coordinatively unsaturated Al3+ sites. In catalytic terms, the addition of AlOOH binder gives rise to enhanced C-2-C-4 selectivity and catalyst mechanical stability in HT-FTS, but at high Al contents the activity decreases. Altogether, the productivity of these Fe@C/Al composites is well above most known Fe catalysts for this process.

  17. Fe-based MOFs for efficient adsorption and degradation of acid orange 7 in aqueous solution via persulfate activation

    International Nuclear Information System (INIS)

    Li, Xianghui; Guo, Weilin; Liu, Zhonghua; Wang, Ruiqin; Liu, Hua

    2016-01-01

    Graphical abstract: - Highlights: • Fe-based MILs were prepared via the facile solvothermal method. • MILs showed efficient removal rate through adsorption and degradation processes. • A possible catalytic degradation mechanism is proposed. - Abstract: Fe-based metal–organic frameworks (MOFs) including MIL-101(Fe), MIL-100(Fe), MIL-53(Fe), and MIL-88B(Fe) prepared via a facile solvothermal process were introduced as both adsorbents and catalysts to generate powerful radicals from persulfate for acid orange 7 (AO7) removal in aqueous solution. Various catalysts were described and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and X-ray photoelectron spectra. Because of the high specific surface area of the materials, we studied the adsorption isotherms of the four MILs by the fitting of Langmuir adsorption isotherm. Meanwhile, the catalytic activities in persulfate oxidation system were investigated. The results showed that the sequence of the materials ability in the combination of adsorption and degradation was MIL-101(Fe) > MIL-100(Fe) > MIL-53(Fe) > MIL-88B(Fe), which had a close connection with the activity of metal ion in active site of the catalysts and their different cages in size. Moreover, the reactive species in MILs/persulfate system were identified as sulfate radicals and hydroxyl radicals. The reaction mechanism for persulfate activation over MILs was also studied.

  18. Effects of ligand functionalization on the photocatalytic properties of titanium-based MOF: A density functional theory study

    Science.gov (United States)

    Li, Yi; Fu, Yuqing; Ni, Bilian; Ding, Kaining; Chen, Wenkai; Wu, Kechen; Huang, Xin; Zhang, Yongfan

    2018-03-01

    The first principle calculations have been performed to investigate the geometries, band structures and optical absorptions of a series of MIL-125 MOFs, in which the 1,4-benzenedicarboxylate (BDC) linkers are modified by different types and amounts of chemical groups, including NH2, OH, and NO2. Our results indicate that new energy bands will appear in the band gap of pristine MIL-125 after introducing new group into BDC linker, but the components of these band gap states and the valence band edge position are sensitive to the type of functional group as well as the corresponding amount. Especially, only the incorporation of amino group can obviously decrease the band gap of MIL-125, and the further reduction of the band gap can be observed if the amount of NH2 is increased. Although MIL-125 functionalized by NH2 group exhibits relatively weak or no activity for the photocatalytic O2 evolution by splitting water, such ligand modification can effectively improve the efficiency in H2 production because now the optical absorption in the visible light region is significantly enhanced. Furthermore, the adsorption of water molecule becomes more favorable after introducing of amino group, which is also beneficial for the water-splitting reaction. The present study can provide theoretical insights to design new photocatalysts based on MIL-125.

  19. From red cells to soft porous lubrication.

    Science.gov (United States)

    Wu, Qianhong; Zhu, Zenghao; Nathan, Rungun

    2017-11-01

    In this paper, we report a novel experimental study to examine the lubrication theory for highly compressible porous media (Feng & Weinbaum, JFM, 422, 282, 2000), which was applied to the frictionless motion of red cells over the endothelial surface layer (ESL). The experimental setup consists of a running conveyer belt covered with a porous sheet, and an upper planar board, i.e. planing surface. The pore pressure generation was captured when the planing surface glides over the porous sheet. If the lateral leakage was eliminated, we found that the overall pore pressure's contribution to the total lift, fair 80%, and the friction coefficient η = 0.0981, when U =5 m/s, L =0.381 m, λ = h2/h0 = 1 and k =h2/h1 = 3, where U is the velocity of the conveyor belt; L is the planing surface length; h0, h1 and h2 are the undeformed, leading and trailing edge porous layer thickness, respectively. fair increases with the increase in U, λ and L, while decreases with the increase in k. η decreases with the increase in fair. If lateral pressure leakage exists, the pore pressure generation is reduced by nearly 90%. All the results agreed well with the theoretical predictions. The study here lays the foundation for applying soft porous media for new type of bearing with significantly reduced friction. This research was supported by the National Science Foundation (NSF CBET) under Award No. 1511096.

  20. Erbium doped stain etched porous silicon

    International Nuclear Information System (INIS)

    Gonzalez-Diaz, B.; Diaz-Herrera, B.; Guerrero-Lemus, R.; Mendez-Ramos, J.; Rodriguez, V.D.; Hernandez-Rodriguez, C.; Martinez-Duart, J.M.

    2008-01-01

    In this work a simple erbium doping process applied to stain etched porous silicon layers (PSLs) is proposed. This doping process has been developed for application in porous silicon solar cells, where conventional erbium doping processes are not affordable because of the high processing cost and technical difficulties. The PSLs were formed by immersion in a HF/HNO 3 solution to properly adjust the porosity and pore thickness to an optimal doping of the porous structure. After the formation of the porous structure, the PSLs were analyzed by means of nitrogen BET (Brunauer, Emmett and Teller) area measurements and scanning electron microscopy. Subsequently, the PSLs were immersed in a saturated erbium nitrate solution in order to cover the porous surface. Then, the samples were subjected to a thermal process to activate the Er 3+ ions. Different temperatures and annealing times were used in this process. The photoluminescence of the PSLs was evaluated before and after the doping processes and the composition was analyzed by Fourier transform IR spectroscopy

  1. Study of water radiolysis in porous media

    International Nuclear Information System (INIS)

    Rotureau, Patricia

    2001-08-01

    The understanding of the production of H 2 in the radiolysis of water confined into pores of concrete is important for the disposal of radioactive waste. In order to describe the mechanisms of water radiolysis in such heterogeneous porous systems we have studied the behaviour under gamma radiation of water confined in porous silica glasses with pores going from 8 to 300 nm of diameter and meso-porous molecular sieves (MCM-41). The radiolytic yields of hydroxyl radicals, hydrated electron and dihydrogen, have been determined with respect to the pore size of materials. The increase of these radiolytic yields compared to those of free water allowed us to show a charge transfer from silica to confined water. On the other hand the kinetics of hydrated electron reactions measured by pulse radiolysis are not modified. (author) [fr

  2. Iron films deposited on porous alumina substrates

    Energy Technology Data Exchange (ETDEWEB)

    Yamada, Yasuhiro, E-mail: yyasu@rs.kagu.tus.ac.jp; Tanabe, Kenichi; Nishida, Naoki [Tokyo University of Science (Japan); Kobayashi, Yoshio [The University of Electro-Communications (Japan)

    2016-12-15

    Iron films were deposited on porous alumina substrates using an arc plasma gun. The pore sizes (120 – 250 nm) of the substrates were controlled by changing the temperature during the anodic oxidation of aluminum plates. Iron atoms penetrated into pores with diameters of less than 160 nm, and were stabilized by forming γ-Fe, whereas α-Fe was produced as a flat plane covering the pores. For porous alumina substrates with pore sizes larger than 200 nm, the deposited iron films contained many defects and the resulting α-Fe had smaller hyperfine magnetic fields. In addition, only a very small amount of γ-Fe was obtained. It was demonstrated that the composition and structure of an iron film can be affected by the surface morphology of the porous alumina substrate on which the film is grown.

  3. Electromechanical Response of Conductive Porous Structure

    Directory of Open Access Journals (Sweden)

    Hye-Mi So

    2015-01-01

    Full Text Available Porous conductors with large surface-volume ratios have been applied to a variety of fields, including absorbents, flexible heaters, and electrodes for supercapacitors. In this study, we implemented sensitive pressure sensors using the mechanical and electrical characteristics of conductive porous structures manufactured by immersing sponges into a carbon nanotube solution and then measured the change in resistance. When pressure was applied to conductive sponges, carbon nanotubes were attached to each other and the resistance was reduced by up to 20%. The carbon nanotube sponges, which were soft and had superior elasticity, were quickly stabilized without any changes taking place in their shape, and they showed consistent change in resistance during experiments of repetitive pressure. The pressure devices based on conductive porous sponges were connected to single-walled carbon nanotube field effect transistors (SWCNT-FETs and changes in their characteristics were investigated according to external pressure.

  4. Porous bioresorbable magnesium as bone substitute

    Energy Technology Data Exchange (ETDEWEB)

    Wen, C.E.; Yamada, Y.; Shimojima, K.; Chino, Y.; Hosokawa, H.; Mabuchi, M. [Inst. for Structural and Engineering Materials, National Inst. of Advanced Industrial Science and Technology, Nagoya (Japan)

    2003-07-01

    Recently magnesium has been recognized as a very promising biomaterial for bone substitutes because of its excellent properties of biocompatibility, biodegradability and bioresorbability. In the present study, magnesium foams were fabricated by using a powder metallurgical process. Scanning electron microscopy equipped with energy dispersive X-ray spectrometer (EDS) and compressive tester were used to characterize the porous magnesium. Results show that the Young's modulus and the peak stress of the porous magnesium increase with decreasing porosity and pore size. This study suggests that the mechanical properties of the porous magnesium with the low porosity of 35% and/or with the small pore size of about 70 {mu}m are close to those of human cancellous bones. (orig.)

  5. Fluid dynamics in porous media with Sailfish

    International Nuclear Information System (INIS)

    Coelho, Rodrigo C V; Neumann, Rodrigo F

    2016-01-01

    In this work we show the application of Sailfish to the study of fluid dynamics in porous media. Sailfish is an open-source software based on the lattice-Boltzmann method. This application of computational fluid dynamics is of particular interest to the oil and gas industry and the subject could be a starting point for an undergraduate or graduate student in physics or engineering. We built artificial samples of porous media with different porosities and used Sailfish to simulate the fluid flow through them in order to calculate their permeability and tortuosity. We also present a simple way to obtain the specific superficial area of porous media using Python libraries. To contextualise these concepts, we analyse the applicability of the Kozeny–Carman equation, which is a well-known permeability–porosity relation, to our artificial samples. (paper)

  6. Fluid dynamics in porous media with Sailfish

    Science.gov (United States)

    Coelho, Rodrigo C. V.; Neumann, Rodrigo F.

    2016-09-01

    In this work we show the application of Sailfish to the study of fluid dynamics in porous media. Sailfish is an open-source software based on the lattice-Boltzmann method. This application of computational fluid dynamics is of particular interest to the oil and gas industry and the subject could be a starting point for an undergraduate or graduate student in physics or engineering. We built artificial samples of porous media with different porosities and used Sailfish to simulate the fluid flow through them in order to calculate their permeability and tortuosity. We also present a simple way to obtain the specific superficial area of porous media using Python libraries. To contextualise these concepts, we analyse the applicability of the Kozeny-Carman equation, which is a well-known permeability-porosity relation, to our artificial samples.

  7. Joining of porous silicon carbide bodies

    Science.gov (United States)

    Bates, Carl H.; Couhig, John T.; Pelletier, Paul J.

    1990-05-01

    A method of joining two porous bodies of silicon carbide is disclosed. It entails utilizing an aqueous slip of a similar silicon carbide as was used to form the porous bodies, including the sintering aids, and a binder to initially join the porous bodies together. Then the composite structure is subjected to cold isostatic pressing to form a joint having good handling strength. Then the composite structure is subjected to pressureless sintering to form the final strong bond. Optionally, after the sintering the structure is subjected to hot isostatic pressing to further improve the joint and densify the structure. The result is a composite structure in which the joint is almost indistinguishable from the silicon carbide pieces which it joins.

  8. Visible light emission from porous silicon carbide

    DEFF Research Database (Denmark)

    Ou, Haiyan; Lu, Weifang

    2017-01-01

    Light-emitting silicon carbide is emerging as an environment-friendly wavelength converter in the application of light-emitting diode based white light source for two main reasons. Firstly, SiC has very good thermal conductivity and therefore a good substrate for GaN growth in addition to the small...... lattice mismatch. Secondly, SiC material is abundant, containing no rear-earth element material as commercial phosphor. In this paper, fabrication of porous SiC is introduced, and their morphology and photoluminescence are characterized. Additionally, the carrier lifetime of the porous SiC is measured...... by time-resolved photoluminescence. The ultrashort lifetime in the order of ~70ps indicates porous SiC is very promising for the application in the ultrafast visible light communications....

  9. Positron annihilation spectroscopy study of porous silicon

    International Nuclear Information System (INIS)

    Britkov, O.M.; Gavrilov, S.A.; Kalugin, V.V.; Timoshenkov, S.P.; Grafutin, V.I.; Ilyukhina, O.V.; Myasishcheva, G.G.; Prokop'ev, E.P.; Funtikov, Yu.V.

    2007-01-01

    Experimental studies of porous silicon by means of a standard positron annihilation technique based on measuring the angular distribution of annihilation photons, are reported. It was shown that the spectra of angular correlation of annihilation radiation in porous silicon are approximated well by a parabola (I p ) and two Gaussians (I g1 , I g2 ). The narrow Gaussian component I g1 is most likely due to the annihilation of localized para-positronium in pores. The full width at half maximum is on the order of 0.8 mrad, a value that corresponds to the kinetic energy of an annihilating positron-electron pair (0.079 ± 0.012 eV), and its intensity is about 1.5%. The total positronium yield in porous silicon reaches 6% in this case. The particle radius determined in the study is about 10-20 A [ru

  10. Formulation of similarity porous media systems

    International Nuclear Information System (INIS)

    Anderson, R.M.; Ford, W.T.; Ruttan, A.; Strauss, M.J.

    1982-01-01

    The mathematical formulation of the Porous Media System (PMS) describing two-phase, immiscible, compressible fluid flow in linear, homogeneous porous media is reviewed and expanded. It is shown that families of common vertex, coaxial parabolas and families of parallel lines are the only families of curves on which solutions of the PMS may be constant. A coordinate transformation is used to change the partial differential equations of the PMS to a system of ordinary differential equations, referred to as a similarity Porous Media System (SPMS), in which the independent variable denotes movement from curve to curve in a selected family of curves. Properties of solutions of the first boundary value problem are developed for the SPMS

  11. Rational design of SnO2@C nanocomposites for lithium ion batteries by utilizing adsorption properties of MOFs.

    Science.gov (United States)

    Wang, Meihui; Yang, Hao; Zhou, Xianlong; Shi, Wei; Zhou, Zhen; Cheng, Peng

    2016-01-14

    A facile synthetic strategy is developed to prepare mono-dispersed SnO2 particles within three-dimensional porous carbon frameworks by utilizing the adsorption properties of metal-organic frameworks. This composite exhibits a high reversible capacity of 900 mA h g(-1) at 100 mA g(-1) after 50 cycles, with a stable capacity retention of 880 mA h g(-1) at 100 mA g(-1) even after 200 cycles.

  12. Characterization of porous tungsten by microhardness

    International Nuclear Information System (INIS)

    Selcuk, C.; Wood, J.V.; Morley, N.; Bentham, R.

    2001-01-01

    One of the applications of tungsten is as high current density dispenser cathode in the form of porous tungsten. It is used as a cathode after being impregnated with an electron emissive material so pore distribution in the part is the most important parameter for its function as a uniform and controlled porosity will lead to a better performance. In this study, application of microhardness as a characterization method for uniformity of the pore distribution and homogeneity of the structure is introduced. Optical microscopy and SEM is used to relate the results and porous tungsten structure for a better understanding of the method applied. (author)

  13. Capillary condensation of adsorbates in porous materials.

    Science.gov (United States)

    Horikawa, Toshihide; Do, D D; Nicholson, D

    2011-11-14

    Hysteresis in capillary condensation is important for the fundamental study and application of porous materials, and yet experiments on porous materials are sometimes difficult to interpret because of the many interactions and complex solid structures involved in the condensation and evaporation processes. Here we make an overview of the significant progress in understanding capillary condensation and hysteresis phenomena in mesopores that have followed from experiment and simulation applied to highly ordered mesoporous materials such as MCM-41 and SBA-15 over the last few decades. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Porous media fluid transport and pore structure

    CERN Document Server

    Dullien, F A L

    1992-01-01

    This book examines the relationship between transport properties and pore structure of porous material. Models of pore structure are presented with a discussion of how such models can be used to predict the transport properties of porous media. Portions of the book are devoted to interpretations of experimental results in this area and directions for future research. Practical applications are given where applicable, and are expected to be useful for a large number of different fields, including reservoir engineering, geology, hydrogeology, soil science, chemical process engineering, biomedica

  15. Additive Manufacturing of Hierarchical Porous Structures

    Energy Technology Data Exchange (ETDEWEB)

    Grote, Christopher John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Science and Technology Division. Polymers and Coatings

    2016-08-30

    Additive manufacturing has become a tool of choice for the development of customizable components. Developments in this technology have led to a powerful array of printers that t serve a variety of needs. However, resin development plays a crucial role in leading the technology forward. This paper addresses the development and application of printing hierarchical porous structures. Beginning with the development of a porous scaffold, which can be functionalized with a variety of materials, and concluding with customized resins for metal, ceramic, and carbon structures.

  16. Porous ceramic scaffolds with complex architectures

    Science.gov (United States)

    Munch, E.; Franco, J.; Deville, S.; Hunger, P.; Saiz, E.; Tomsia, A. P.

    2008-06-01

    This work compares two novel techniques for the fabrication of ceramic scaffolds for bone tissue engineering with complex porosity: robocasting and freeze casting. Both techniques are based on the preparation of concentrated ceramic suspensions with suitable properties for the process. In robocasting, the computer-guided deposition of the suspensions is used to build porous materials with designed three dimensional geometries and microstructures. Freeze casting uses ice crystals as a template to form porous lamellar ceramic materials. Preliminary results on the compressive strengths of the materials are also reported.

  17. Investigation of beam effect on porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Kotai, E. E-mail: kotai@rmki.kfki.hu; Paszti, F.; Szilagyi, E

    2000-03-01

    When performing Rutherford Backscattering Spectroscopy (RBS) measurements combined with channeling on 'columnar' porous silicon (PS) samples with beam aligned to the direction of the pores, a strong beam effect was observed. The minimum yield as a function of the beam dose for different porous samples was compared with the yield measured on single crystal silicon. It was demonstrated that the beam effect strongly depends on the porosity of the sample. Bombardment in the random direction caused about 10% higher change in the minimum yield than in the channel direction.

  18. Investigation of beam effect on porous silicon

    International Nuclear Information System (INIS)

    Kotai, E.; Paszti, F.; Szilagyi, E.

    2000-01-01

    When performing Rutherford Backscattering Spectroscopy (RBS) measurements combined with channeling on 'columnar' porous silicon (PS) samples with beam aligned to the direction of the pores, a strong beam effect was observed. The minimum yield as a function of the beam dose for different porous samples was compared with the yield measured on single crystal silicon. It was demonstrated that the beam effect strongly depends on the porosity of the sample. Bombardment in the random direction caused about 10% higher change in the minimum yield than in the channel direction

  19. Measurement of Emissivity of Porous Ceramic Materials

    OpenAIRE

    BÜYÜKALACA, Orhan

    1998-01-01

    In this study, measurements of spectral and total emissivities of seven different porous ceramic materials and one ceramic fibre material are reported. Measurements were made for wavelength range from 1.2 µm to 20 µm and temperature range from 200 °C to 700 °C. It was found that total emissivity increases with increase of pore size but decreases with increase of temperature. The results showed all the porous ceramic materials tested to be much better than ceramic fibre in terms of total em...

  20. Making Porous Luminescent Regions In Silicon Wafers

    Science.gov (United States)

    Fathauer, Robert W.; Jones, Eric W.

    1994-01-01

    Regions damaged by ion implantation stain-etched. Porous regions within single-crystal silicon wafers fabricated by straightforward stain-etching process. Regions exhibit visible photoluminescence at room temperature and might constitute basis of novel class of optoelectronic devices. Stain-etching process has advantages over recently investigated anodic-etching process. Process works on both n-doped and p-doped silicon wafers. Related development reported in article, "Porous Si(x)Ge(1-x) Layers Within Single Crystals of Si," (NPO-18836).