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Sample records for microporous metal-organic framework

  1. Ordered macro-microporous metal-organic framework single crystals

    Science.gov (United States)

    Shen, Kui; Zhang, Lei; Chen, Xiaodong; Liu, Lingmei; Zhang, Daliang; Han, Yu; Chen, Junying; Long, Jilan; Luque, Rafael; Li, Yingwei; Chen, Banglin

    2018-01-01

    We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional–ordered macro-microporous materials (that is, materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent–induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.

  2. Ordered macro-microporous metal-organic framework single crystals

    KAUST Repository

    Shen, Kui

    2018-01-16

    We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional-ordered macro-microporous materials (that is, materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent-induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.

  3. Ordered macro-microporous metal-organic framework single crystals

    KAUST Repository

    Shen, Kui; Zhang, Lei; Chen, Xiaodong; Liu, Lingmei; Zhang, Daliang; Han, Yu; Chen, Junying; Long, Jilan; Luque, Rafael; Li, Yingwei; Chen, Banglin

    2018-01-01

    We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional-ordered macro-microporous materials (that is, materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent-induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.

  4. Gas sorption properties of microporous metal organic frameworks

    International Nuclear Information System (INIS)

    Lee, JeongYong; Li Jing; Jagiello, Jacek

    2005-01-01

    A low-temperature gas sorption study has been carried out on four three-dimensional microporous metal organic framework (MMOF) structures and two two-dimensional layered structures. The pore characteristics are analyzed based on the argon adsorption-desorption isotherms at 87 K. The results from hydrogen sorption experiments conducted at 77 and 87 K show that all MMOFs have a relatively high hydrogen uptake, with adsorbed hydrogen densities falling in the range of liquid hydrogen. Isosteric heats of hydrogen adsorption data calculated based on the Clausius-Clapeyron equation are consistent with these observations, indicating strong sorbent-sorbate interactions. - Graphical abstract: Hydrogen adsorption isotherms measured at 77 and 87 K

  5. Light Hydrocarbons Adsorption Mechanisms in Two Calcium-based Microporous Metal Organic Frameworks

    KAUST Repository

    Plonka, Anna M.

    2016-01-25

    The adsorption mechanism of ethane, ethylene and acetylene (C2Hn; n=2, 4, 6) on two microporous metal organic frameworks (MOFs) is described here that is consistent with observations from single crystal and powder X-ray diffraction, calorimetric measurments and gas adsorption isotherm measurements. Two calcium-based MOFs, designated as SBMOF-1 and SBMOF-2 (SB: Stony Brook), form three-dimensional frameworks with one-dimensional open channels. As determined form single crystal diffraction experiments channel geometries of both SBMOF-1 and SBMOF-2 provide multiple adsorption sites for hydrocarbon molecules trough C-H…π and C-H…O interactions, similarly to interactions in the molecular and protein crystals. Both materials selectively adsorb C2 hydrocarbon gases over methane as determined with IAST and breakthrough calculations, with C2H6/CH4 selectivity as high as 74 in SBMOF-1.

  6. Improved synthesis and hydrogen storage of a microporous metal-organic framework material

    International Nuclear Information System (INIS)

    Cheng Shaojuan; Liu Shaobing; Zhao Qiang; Li Jinping

    2009-01-01

    A microporous metal-organic framework MOF-5 [Zn 4 O(BDC) 3 , BDC = 1,4-benzenedicarboxylic] was synthesized with and without H 2 O 2 by improved methods based on the previous studies. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy and nitrogen adsorption, and their hydrogen storage capacities were measured. The synthesis experiments showed that H 2 O 2 favored the growth of high quality sample, large pore volume and high specific surface area. The measurements of hydrogen storage indicated that the sample with higher specific surface area and large pore volume showed better hydrogen storage behavior than other samples. It was suggested that specific surface area and pore volume influenced the capacity of hydrogen storage for MOF-5 material.

  7. Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions

    NARCIS (Netherlands)

    Xiang, S.C.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B.

    2012-01-01

    Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve

  8. Carbon Dioxide Removal from Flue Gas Using Microporous Metal Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Lesch, David A

    2010-06-30

    UOP LLC, a Honeywell Company, in collaboration with Professor Douglas LeVan at Vanderbilt University (VU), Professor Adam Matzger at the University of Michigan (UM), Professor Randall Snurr at Northwestern University (NU), and Professor Stefano Brandani at the University of Edinburgh (UE), supported by Honeywell's Specialty Materials business unit and the Electric Power Research Institute (EPRI), have completed a three-year project to develop novel microporous metal organic frameworks (MOFs) and an associated vacuum-pressure swing adsorption (vPSA) process for the removal of CO{sub 2} from coal-fired power plant flue gas. The project leveraged the team's complementary capabilities: UOP's experience in materials development and manufacturing, adsorption process design and process commercialization; LeVan and Brandani's expertise in high-quality adsorption measurements; Matzger's experience in syntheis of MOFs and the organic components associated with MOFs; Snurr's expertise in molecular and other modeling; Honeywell's expertise in the manufacture of organic chemicals; and, EPRI's knowledge of power-generation technology and markets. The project was successful in that a selective CO{sub 2} adsorbent with good thermal stability and reasonable contaminant tolerance was discovered, and a low cost process for flue gas CO{sub 2} capture process ready to be evaluated further at the pilot scale was proposed. The team made significant progress toward the current DOE post-combustion research targets, as defined in a recent FOA issued by NETL: 90% CO{sub 2} removal with no more than a 35% increase in COE. The team discovered that favorable CO{sub 2} adsorption at more realistic flue gas conditions is dominated by one particular MOF structure type, M/DOBDC, where M designates Zn, Co, Ni, or Mg and DOBDC refers to the form of the organic linker in the resultant MOF structure, dioxybenzenedicarboxylate. The structure of the M/DOBDC MOFs

  9. Centimetre-scale micropore alignment in oriented polycrystalline metal-organic framework films via heteroepitaxial growth.

    Science.gov (United States)

    Falcaro, Paolo; Okada, Kenji; Hara, Takaaki; Ikigaki, Ken; Tokudome, Yasuaki; Thornton, Aaron W; Hill, Anita J; Williams, Timothy; Doonan, Christian; Takahashi, Masahide

    2017-03-01

    The fabrication of oriented, crystalline films of metal-organic frameworks (MOFs) is a critical step toward their application to advanced technologies such as optics, microelectronics, microfluidics and sensing. However, the direct synthesis of MOF films with controlled crystalline orientation remains a significant challenge. Here we report a one-step approach, carried out under mild conditions, that exploits heteroepitaxial growth for the rapid fabrication of oriented polycrystalline MOF films on the centimetre scale. Our methodology employs crystalline copper hydroxide as a substrate and yields MOF films with oriented pore channels on scales that primarily depend on the dimensions of the substrate. To demonstrate that an anisotropic crystalline morphology can translate to a functional property, we assembled a centimetre-scale MOF film in the presence of a dye and showed that the optical response could be switched 'ON' or 'OFF' by simply rotating the film.

  10. Adsorption of methane on Zn(bdc)(ted)0.5 microporous metal-organic framework

    Science.gov (United States)

    Krungleviciute, Vaiva; Pramanik, Sanhita; Migone, Aldo; Li, Jing

    2011-03-01

    Zn(bdc)(ted)0.5 is metal-organic framework crystallized in a tetragonal space group with a 3D porous structure containing intersecting channels of two different sizes. The larger channels are parallel to the c axis and have a cross section 7.5 × 7.5 AA. The smaller channels are along both the a- and b-axes and have a cross section of 4.8 × 3.2 AA. We measured methane adsorption isotherms at several different temperatures between 82 and 102 K. We calculated the effective specific surface area, isosteric heat and binding energy values. Two distinct substeps were observed in the isotherms corresponding to two different adsorption sites. The origin of the substeps will be discussed.

  11. Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Renjie, E-mail: kx210@cam.ac.uk, E-mail: chenrj@bit.edu.cn; Zhao, Teng [Beijing Key Laboratory of Environmental Science and Engineering, School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081 (China); Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom); Tian, Tian; Fairen-Jimenez, David [Department of Chemical Engineering and Biotechnology, University of Cambridge, Pembroke Street, Cambridge CB2 3RA (United Kingdom); Cao, Shuai; Coxon, Paul R.; Xi, Kai, E-mail: kx210@cam.ac.uk, E-mail: chenrj@bit.edu.cn; Vasant Kumar, R.; Cheetham, Anthony K. [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom)

    2014-12-01

    A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/C{sub ZIF8-D}) composite for use in a cathode for a lithium sulfur (Li-S) battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8), a typical zinc-containing metal organic framework (MOF), which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/C{sub ZIF8-D}) composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/C{sub ZIF8-D} sample, Li-S batteries with the GS-S/C{sub ZIF8-D} composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

  12. Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

    Directory of Open Access Journals (Sweden)

    Renjie Chen

    2014-12-01

    Full Text Available A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/CZIF8-D composite for use in a cathode for a lithium sulfur (Li-S battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8, a typical zinc-containing metal organic framework (MOF, which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/CZIF8-D composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/CZIF8-D sample, Li-S batteries with the GS-S/CZIF8-D composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

  13. Dynamical Effects in Metal-Organic Frameworks: The Microporous Materials as Shock Absorbers

    Science.gov (United States)

    Banlusan, Kiettipong; Strachan, Alejandro

    2017-06-01

    Metal-organic frameworks (MOFs) are a class of nano-porous crystalline solids consisting of inorganic units coordinated to organic linkers. The unique molecular structures and outstanding properties with ultra-high porosity and tunable chemical functionality by various choices of metal clusters and organic ligands make this class of materials attractive for many applications. The complex and quite unique responses of these materials to mechanical loading including void collapse make them attractive for applications in energy absorption and storage. We will present using large-scale molecular dynamics simulations to investigate shock propagation in zeolitic imidazolate framework ZIF-8 and MOF-5. We find that for shock strengths above a threshold a two-wave structure develops with a leading elastic precursor followed by a second wave of structural collapse to relax the stress. Structural transition of MOFs in response to shock waves corresponds to the transition between two Hugoniot curves, and results in abrupt change in temperature. The pore-collapse wave propagates at slower velocity than the leading wave and weakens it, resulting in shock attenuation. Increasing piston speed results in faster propagation of pore-collapse wave, but the leading elastic wave remains unchanged below the overdriven regime. We discuss how the molecular structure of the MOFs and shock propagation direction affect the response of the materials and their ability to weaken shocks. Office of Naval Research, MURI 2012 02341 01.

  14. Electrochemical Synthesis of a Microporous Conductive Polymer Based on a Metal-Organic Framework Thin Film

    KAUST Repository

    Lu, Chunjing; Ben, Teng; Xu, Shixian; Qiu, Shilun

    2014-01-01

    A new approach to preparing 3D microporous conductive polymer has been demonstrated in the electrochemical synthesis of a porous polyaniline network with the utilization of a MOF thin film supported on a conducting substrate. The prepared porous

  15. Electrochemical Synthesis of a Microporous Conductive Polymer Based on a Metal-Organic Framework Thin Film

    KAUST Repository

    Lu, Chunjing

    2014-05-22

    A new approach to preparing 3D microporous conductive polymer has been demonstrated in the electrochemical synthesis of a porous polyaniline network with the utilization of a MOF thin film supported on a conducting substrate. The prepared porous polyaniline with well-defined uniform micropores of 0.84 nm exhibits a high BET surface area of 986 m2 g−1 and a high electric conductivity of 0.125 S cm−1 when doped with I2, which is superior to existing porous conducting materials of porous MOFs, CMPs, and COFs.

  16. Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework.

    Science.gov (United States)

    Banerjee, Debasis; Wang, Hao; Plonka, Anna M; Emge, Thomas J; Parise, John B; Li, Jing

    2016-08-08

    Gate-opening is a unique and interesting phenomenon commonly observed in flexible porous frameworks, where the pore characteristics and/or crystal structures change in response to external stimuli such as adding or removing guest molecules. For gate-opening that is induced by gas adsorption, the pore-opening pressure often varies for different adsorbate molecules and, thus, can be applied to selectively separate a gas mixture. The detailed understanding of this phenomenon is of fundamental importance to the design of industrially applicable gas-selective sorbents, which remains under investigated due to the lack of direct structural evidence for such systems. We report a mechanistic study of gas-induced gate-opening process of a microporous metal-organic framework, [Mn(ina)2 ] (ina=isonicotinate) associated with commensurate adsorption, by a combination of several analytical techniques including single crystal X-ray diffraction, in situ powder X-ray diffraction coupled with differential scanning calorimetry (XRD-DSC), and gas adsorption-desorption methods. Our study reveals that the pronounced and reversible gate opening/closing phenomena observed in [Mn(ina)2 ] are coupled with a structural transition that involves rotation of the organic linker molecules as a result of interaction of the framework with adsorbed gas molecules including carbon dioxide and propane. The onset pressure to open the gate correlates with the extent of such interaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Light Hydrocarbons Adsorption Mechanisms in Two Calcium-based Microporous Metal Organic Frameworks

    KAUST Repository

    Plonka, Anna M.; Chen, Xianyin; Wang, Hao; Krishna, Rajamani; Dong, Xinglong; Banerjee, Debasis; Woerner, William R.; Han, Yu; Li, Jing; Parise, John B.

    2016-01-01

    measurments and gas adsorption isotherm measurements. Two calcium-based MOFs, designated as SBMOF-1 and SBMOF-2 (SB: Stony Brook), form three-dimensional frameworks with one-dimensional open channels. As determined form single crystal diffraction experiments

  18. Enhancing gas adsorption and separation capacity through ligand functionalization of microporous metal-organic framework structures.

    Science.gov (United States)

    Zhao, Yonggang; Wu, Haohan; Emge, Thomas J; Gong, Qihan; Nijem, Nour; Chabal, Yves J; Kong, Lingzhu; Langreth, David C; Liu, Hui; Zeng, Heping; Li, Jing

    2011-04-26

    Hydroxyl- and amino- functionalized [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O leads to two new structures, [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O (BDC=terephthalic acid, TED=triethylenediamine, BDC-OH=2-hydroxylterephthalic acid, BDC-NH(2)=2-aminoterephthalic acid). Single-crystal X-ray diffraction and powder X-ray diffraction studies confirmed that the structures of both functionalized compounds are very similar to that of their parent structure. Compound [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O can be considered a 3D porous structure with three interlacing 1D channels, whereas both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O contain only 1D open channels as a result of functionalization of the BDC ligand by the OH and NH(2) groups. A notable decrease in surface area and pore size is thus observed in both compounds. Consequently, [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O takes up the highest amount of H(2) at low temperatures. Interestingly, however, both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O show significant enhancement in CO(2) uptake at room temperature, suggesting that the strong interactions between CO(2) and the functionalized ligands, indicating that surface chemistry, rather than porosity, plays a more important role in CO(2) adsorption. A comparison of single-component CO(2), CH(4), CO, N(2), and O(2) adsorption isotherms demonstrates that the adsorption selectivity of CO(2) over other small gases is considerably enhanced through functionalization of the frameworks. Infrared absorption spectroscopic measurements and theoretical calculations are also carried out to assess the effect of functional groups on CO(2) and H(2) adsorption potentials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Direct Observation of Xe and Kr Adsorption in a Xe-Selective Microporous Metal-Organic Framework

    NARCIS (Netherlands)

    Chen, X.; Plonka, A.M.; Banerjee, D.; Krishna, R.; Schaef, H.T.; Ghose, S.; Thallapally, P.K.; Parise, J.B.

    2015-01-01

    The cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal organic frameworks (MOFs) containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid,state adsorbents, but no experimental insights

  20. 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:

  1. Separation of Acetylene from Carbon Dioxide and Ethylene by a Water-Stable Microporous Metal-Organic Framework with Aligned Imidazolium Groups inside the Channels.

    Science.gov (United States)

    Lee, Jaechul; Chuah, Chong Yang; Kim, Jaheon; Kim, Youngsuk; Ko, Nakeun; Seo, Younggyu; Kim, Kimoon; Bae, Tae Hyun; Lee, Eunsung

    2018-04-24

    Separation of acetylene from carbon dioxide and ethylene is challenging in view of their similar sizes and physical properties. Metal-organic frameworks (MOFs) in general are strong candidates for these separations owing to the presence of functional pore surfaces that can selectively capture a specific target molecule. Here, we report a novel 3D microporous cationic framework named JCM-1. This structure possesses imidazolium functional groups on the pore surfaces and pyrazolate as a metal binding group, which is well known to form strong metal-to-ligand bonds. The selective sorption of acetylene over carbon dioxide and ethylene in JCM-1 was successfully demonstrated by equilibrium gas adsorption analysis as well as dynamic breakthrough measurement. Furthermore, its excellent hydrolytic stability makes the separation processes highly recyclable without a substantial loss in acetylene uptake capacity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Lanthanide metal-organic frameworks

    International Nuclear Information System (INIS)

    Cheng, Peng

    2015-01-01

    This book contains the following nine chapters: lanthanide metal-organic frameworks: syntheses, properties, and potential applications (Stephen Fordham, Xuan Wang, Mathieu Bosch, Hong-Cai Zhou); 2. chiral lanthanide metal-organic frameworks (Weisheng Liu, Xiaoliang Tang); 3. Porous lanthanide metal-organic frameworks for gas storage and separation (Bin Li, Banglin Chen); 4. Luminescent lanthanide metal-organic frameworks (Xue-Zhi Song, Shu-Yan Song, Hong-Jie Zhang); 5. Metal-organic frameworks based on lanthanide clusters (Lian Chen, Feilong Jiang, Kang Zhou, Mingyan Wu, Maochun Hong); 6. metal-organic frameworks with d-f cyanide bridges: structural diversity, bonding regime, and magnetism (Marilena Ferbinteanu, Fanica Cimpoesu, Stefania Tanase); 7. transition-lanthanide heterometal-organic frameworks: synthesis, structures, and properties (Wei Shi, Ke Liu, Peng Cheng); 8: MOFs of uranium and the actinides (Juan Su, Jiesheng Chen); 9. Nanostructured and/or nanoscale lanthanide metal-organic frameworks (Zhonghao Zhang, Zhiping Zheng).

  3. Lanthanide metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Peng (ed.) [Nankai Univ., Tianjin (China). Dept. of Chemistry

    2015-03-01

    This book contains the following nine chapters: lanthanide metal-organic frameworks: syntheses, properties, and potential applications (Stephen Fordham, Xuan Wang, Mathieu Bosch, Hong-Cai Zhou); 2. chiral lanthanide metal-organic frameworks (Weisheng Liu, Xiaoliang Tang); 3. Porous lanthanide metal-organic frameworks for gas storage and separation (Bin Li, Banglin Chen); 4. Luminescent lanthanide metal-organic frameworks (Xue-Zhi Song, Shu-Yan Song, Hong-Jie Zhang); 5. Metal-organic frameworks based on lanthanide clusters (Lian Chen, Feilong Jiang, Kang Zhou, Mingyan Wu, Maochun Hong); 6. metal-organic frameworks with d-f cyanide bridges: structural diversity, bonding regime, and magnetism (Marilena Ferbinteanu, Fanica Cimpoesu, Stefania Tanase); 7. transition-lanthanide heterometal-organic frameworks: synthesis, structures, and properties (Wei Shi, Ke Liu, Peng Cheng); 8: MOFs of uranium and the actinides (Juan Su, Jiesheng Chen); 9. Nanostructured and/or nanoscale lanthanide metal-organic frameworks (Zhonghao Zhang, Zhiping Zheng).

  4. Microporous Metal Organic Materials for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    S. G. Sankar; Jing Li; Karl Johnson

    2008-11-30

    We have examined a number of Metal Organic Framework Materials for their potential in hydrogen storage applications. Results obtained in this study may, in general, be summarized as follows: (1) We have identified a new family of porous metal organic framework materials with the compositions M (bdc) (ted){sub 0.5}, {l_brace}M = Zn or Co, bdc = biphenyl dicarboxylate and ted = triethylene diamine{r_brace} that adsorb large quantities of hydrogen ({approx}4.6 wt%) at 77 K and a hydrogen pressure of 50 atm. The modeling performed on these materials agree reasonably well with the experimental results. (2) In some instances, such as in Y{sub 2}(sdba){sub 3}, even though the modeling predicted the possibility of hydrogen adsorption (although only small quantities, {approx}1.2 wt%, 77 K, 50 atm. hydrogen), our experiments indicate that the sample does not adsorb any hydrogen. This may be related to the fact that the pores are extremely small or may be attributed to the lack of proper activation process. (3) Some samples such as Zn (tbip) (tbip = 5-tert butyl isophthalate) exhibit hysteresis characteristics in hydrogen sorption between adsorption and desorption runs. Modeling studies on this sample show good agreement with the desorption behavior. It is necessary to conduct additional studies to fully understand this behavior. (4) Molecular simulations have demonstrated the need to enhance the solid-fluid potential of interaction in order to achieve much higher adsorption amounts at room temperature. We speculate that this may be accomplished through incorporation of light transition metals, such as titanium and scandium, into the metal organic framework materials.

  5. Chromium metal organic frameworks and synthesis of metal organic frameworks

    Science.gov (United States)

    Zhou, Hong-Cai; Liu, Tian-Fu; Lian, Xizhen; Zou, Lanfang; Feng, Dawei

    2018-04-24

    The present invention relates to monocrystalline metal organic frameworks comprising chromium ions and carboxylate ligands and the use of the same, for example their use for storing a gas. The invention also relates to methods for preparing metal organic frameworks comprising chromium, titanium or iron ions and carboxylate ligands. The methods of the invention allow such metal organic frameworks to be prepared in monocrystalline or polycrystalline forms.

  6. Pillared-layer microporous metal-organic frameworks constructed by robust hydrogen bonds. Synthesis, characterization, and magnetic and adsorption properties of 2,2'-biimidazole and carboxylate complexes.

    Science.gov (United States)

    Ding, Bing-Bing; Weng, Yan-Qin; Mao, Zong-Wan; Lam, Chi-Keung; Chen, Xiao-Ming; Ye, Bao-Hui

    2005-11-28

    Two new isostructural complexes [M(H2biim)3][M(btc)(Hbiim)].2H2O (M = Co, (1); M = Ni, (2)) (btc = 1,3,5-benzenetricarboxylate; H2biim = 2,2'-biimidazole) have been synthesized and characterized by single-crystal X-ray diffraction. They present a unique structure consisting of two distinct units: the monomeric cations [M(H2biim)3]2+ and the two-dimensional (2D) anionic polymer [M(Hbiim)(btc)]2-. In the anionic moiety, the Hbiim- monoanion is simultaneously coordinated to one metal atom in a bidentate mode and further to another metal atom in a monodentate mode. The imidazolate groups bridge the two adjacent metal ions into a helical chain which is further arranged in left- and right-handed manners. These chains are bridged by btc ligands into a 2D brick wall structure. The most interesting aspect is that the [M(H2biim)3]2+ cations act as pillars and link the anionic layers via robust heteromeric hydrogen-bonded synthons (9) and (7) formed by the uncoordinated oxygen atoms of carboxylate groups and the H2biim ligands, resulting in a microporous metal-organic framework with one-dimensional (1D) channels (ca. 11.85 angstroms x 11.85 angstroms for 1 and 11.43 angstroms x 11.43 angstroms for 2). Magnetic properties of these two complexes have also been studied in the temperature range of 2-300 K, and their magnetic susceptibilities obey the Curie-Weiss law in the temperature range of 20-300 K (for 1) and 2-300 K (for 2), respectively, showing anti-ferromagnetic coupling through imidazolate bridging. Taking into consideration the Heisenberg infinite chain model as well as the possibility of chain-to-chain and chain-to-cation interactions, the anti-ferromagnetic exchange of 2 is analyzed via a correction for the molecular field, giving the values of g(cat) = 2.296, g(Ni) = 2.564, J = -13.30 cm(-1), and zJ' = -0.017 cm(-1). The microporous frameworks are stable at ca. 350 degrees C. They do not collapse after removal of the guest water molecules in the channels, and they

  7. 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.

  8. Liquid metal-organic frameworks

    Science.gov (United States)

    Gaillac, Romain; Pullumbi, Pluton; Beyer, Kevin A.; Chapman, Karena W.; Keen, David A.; Bennett, Thomas D.; Coudert, François-Xavier

    2017-11-01

    Metal-organic frameworks (MOFs) are a family of chemically diverse materials, with applications in a wide range of fields, covering engineering, physics, chemistry, biology and medicine. Until recently, research has focused almost entirely on crystalline structures, yet now a clear trend is emerging, shifting the emphasis onto disordered states, including `defective by design’ crystals, as well as amorphous phases such as glasses and gels. Here we introduce a strongly associated MOF liquid, obtained by melting a zeolitic imidazolate framework. We combine in situ variable temperature X-ray, ex situ neutron pair distribution function experiments, and first-principles molecular dynamics simulations to study the melting phenomenon and the nature of the liquid obtained. We demonstrate from structural, dynamical, and thermodynamical information that the chemical configuration, coordinative bonding, and porosity of the parent crystalline framework survive upon formation of the MOF liquid.

  9. One-of-A-Kind: A Microporous Metal-Organic Framework Capable of Adsorptive Separation of Linear, Mono- and Di-branched Alkane Isomers via Temperature- and Adsorbate-Dependent Molecular Sieving

    KAUST Repository

    Wang, Hao

    2018-03-29

    Separation of alkane isomers represents a crucial process in the petrochemical industry in order to achieve high octane rating of gasoline. Herein, we report the first example of complete separation of linear, monobranched and dibranched alkane isomers by a single adsorbent. A calcium-based robust microporous metal-organic framework, Ca(H2tcpb) (tcpb = 1,2,4,5-tetrakis(4-carboxyphenyl)-benzene) exhibits unique molecular exclusion behavior which enables full separation of binary or ternary mixtures of alkane isomers into pure form of each isomerate. The successful separation of monobranched and dibranched hexane isomers will not only lead to the production of higher quality gasoline with maximum possible octane numbers but also fill the gap in the current separation technology. Exploration of separation mechanism indicates that structural flexibility and adsorbate-dependent structure change of the porous framework plays a vital role for the observed temperature-dependent molecular sieving property of the adsorbent.

  10. Gas adsorption on metal-organic frameworks

    Science.gov (United States)

    Willis, Richard R [Cary, IL; Low, John J. , Faheem, Syed A.; Benin, Annabelle I [Oak Forest, IL; Snurr, Randall Q [Evanston, IL; Yazaydin, Ahmet Ozgur [Evanston, IL

    2012-07-24

    The present invention involves the use of certain metal organic frameworks that have been treated with water or another metal titrant in the storage of carbon dioxide. The capacity of these frameworks is significantly increased through this treatment.

  11. Metal organic frameworks for gas storage

    KAUST Repository

    Alezi, Dalal

    2016-06-09

    Embodiments provide a method of storing a compound using a metal organic framework (MOF). The method includes contacting one or more MOFs with a fluid and sorbing one or more compounds, such as O2 and CH4. O2 and CH4 can be sorbed simultaneously or in series. The metal organic framework can be an M-soc-MOF, wherein M can include aluminum, iron, gallium, indium, vanadium, chromium, titanium, or scandium.

  12. Hydrogen adsorption in metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Senkovska, Irena; Kaskel, Stefan [Department of Inorganic Chemistry, Technical University, Dresden (Germany)

    2008-07-01

    Metal-Organic Frameworks (MOFs) have recently received considerable attention because of their high specific micropore volume and the ability to store gas molecules exceeding the storage capacity of traditional adsorbents. A variety of differences in the MOFs structures makes it difficult to analyze the influence of different factors on hydrogen uptake capabilities in MOFs. We have investigated the influence of the minor structural changes of the MOFs on their hydrogen storage capacity. The influence of the incorporated metal was shown for following isostructural compounds: Cu{sub 3}(BTC){sub 2} (BTC=1,3,5-benzenetricarboxylate) and Mo{sub 3}(BTC){sub 2}; Zn{sub 2}(BDC){sub 2}DABCO and Co{sub 2}(BDC){sub 2}DABCO (BDC=1,4-benzenedicarboxylate, DABCO=1,4-diazabicyclo[2.2.2]octane). Our research interest is directed also towards the discovery of new MOFs, as well as adjusting the pore dimensions of MOFs, using different building blocks, solvent and solvent mixtures, in order to improve gas uptake and adsorption properties. Magnesium-based MOFs were found with the same network topology, very small pore size and selective adsorption behaviour. They show a guest-induced reversible structure transformation due to the flexibility of the Mg{sub 3}-cluster and the organic linkers. This effect could be used for fitting the pore sizes and for the increase of gas sorption capability in Mg contained MOFs after all. The hydrogen adsorption was also studied in several Al-based IRMOFs.

  13. Minerals with metal-organic framework structures.

    Science.gov (United States)

    Huskić, Igor; Pekov, Igor V; Krivovichev, Sergey V; Friščić, Tomislav

    2016-08-01

    Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals.

  14. Methane storage in metal-organic frameworks.

    Science.gov (United States)

    He, Yabing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2014-08-21

    Natural gas (NG), whose main component is methane, is an attractive fuel for vehicular applications. Realization of safe, cheap and convenient means and materials for high-capacity methane storage can significantly facilitate the implementation of natural gas fuelled vehicles. The physisorption based process involving porous materials offers an efficient storage methodology and the emerging porous metal-organic frameworks have been explored as potential candidates because of their extraordinarily high porosities, tunable pore/cage sizes and easily immobilized functional sites. In this view, we provide an overview of the current status of metal-organic frameworks for methane storage.

  15. Metal organic frameworks for gas storage

    KAUST Repository

    Alezi, Dalal; Belmabkhout, Youssef; Eddaoudi, Mohamed

    2016-01-01

    Embodiments provide a method of storing a compound using a metal organic framework (MOF). The method includes contacting one or more MOFs with a fluid and sorbing one or more compounds, such as O2 and CH4. O2 and CH4 can be sorbed simultaneously

  16. 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 ...

  17. Magnetic behaviour in metal-organic frameworks

    Indian Academy of Sciences (India)

    The article describes the synthesis, structure and magnetic investigations of a series of metal-organic framework compounds formed with Mn+2 and Ni+2 ions. The structures, determined using the single crystal X-ray diffraction, indicated that the structures possess two- and three-dimensional structures with magnetically ...

  18. 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

  19. Zeolite-like metal-organic frameworks with ana topology

    KAUST Repository

    Eddaoudi, Mohamed; Mohideen, Mohamed Infas Haja; Adil, Karim; Belmabkhout, Youssef; Bhatt, Prashant M.; Shekhah, Osama; Chernikova, Valeriya

    2017-01-01

    Embodiments of the present disclosure describe a zeolite-like metal-organic framework composition comprising a metal-organic framework composition with ana topology characterized by the formula [MIII(4, 5-imidazole dicarboxylic acid)2X

  20. Metal-organic frameworks in chromatography.

    Science.gov (United States)

    Yusuf, Kareem; Aqel, Ahmad; ALOthman, Zeid

    2014-06-27

    Metal-organic frameworks (MOFs) emerged approximately two decades ago and are the youngest class of porous materials. Despite their short existence, MOFs are finding applications in a variety of fields because of their outstanding chemical and physical properties. This review article focuses on the applications of MOFs in chromatography, including high-performance liquid chromatography (HPLC), gas chromatography (GC), and other chromatographic techniques. The use of MOFs in chromatography has already had a significant impact; however, the utilisation of MOFs in chromatography is still less common than other applications, and the number of MOF materials explored in chromatography applications is limited. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Computational modeling of Metal-Organic Frameworks

    Science.gov (United States)

    Sung, Jeffrey Chuen-Fai

    In this work, the metal-organic frameworks MIL-53(Cr), DMOF-2,3-NH 2Cl, DMOF-2,5-NH2Cl, and HKUST-1 were modeled using molecular mechanics and electronic structure. The effect of electronic polarization on the adsorption of water in MIL-53(Cr) was studied using molecular dynamics simulations of water-loaded MIL-53 systems with both polarizable and non-polarizable force fields. Molecular dynamics simulations of the full systems and DFT calculations on representative framework clusters were utilized to study the difference in nitrogen adsorption between DMOF-2,3-NH2Cl and DMOF-2,5-NH 2Cl. Finally, the control of proton conduction in HKUST-1 by complexation of molecules to the Cu open metal site was investigated using the MS-EVB methodology.

  2. Hydrogen Storage in Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Long, Jeffrey R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2016-04-28

    The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing a high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H2 storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H2 at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H2 adsorption measurements, to provide a comprehensive picture of H2 adsorption at all relevant pressures. A

  3. Supercapacitors of nanocrystalline metal-organic frameworks.

    Science.gov (United States)

    Choi, Kyung Min; Jeong, Hyung Mo; Park, Jung Hyo; Zhang, Yue-Biao; Kang, Jeung Ku; Yaghi, Omar M

    2014-07-22

    The high porosity of metal-organic frameworks (MOFs) has been used to achieve exceptional gas adsorptive properties but as yet remains largely unexplored for electrochemical energy storage devices. This study shows that MOFs made as nanocrystals (nMOFs) can be doped with graphene and successfully incorporated into devices to function as supercapacitors. A series of 23 different nMOFs with multiple organic functionalities and metal ions, differing pore sizes and shapes, discrete and infinite metal oxide backbones, large and small nanocrystals, and a variety of structure types have been prepared and examined. Several members of this series give high capacitance; in particular, a zirconium MOF exhibits exceptionally high capacitance. It has the stack and areal capacitance of 0.64 and 5.09 mF cm(-2), about 6 times that of the supercapacitors made from the benchmark commercial activated carbon materials and a performance that is preserved over at least 10000 charge/discharge cycles.

  4. An Electrically Switchable Metal-Organic Framework

    Science.gov (United States)

    Fernandez, Carlos A.; Martin, Paul C.; Schaef, Todd; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-01

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  5. Text Mining Metal-Organic Framework Papers.

    Science.gov (United States)

    Park, Sanghoon; Kim, Baekjun; Choi, Sihoon; Boyd, Peter G; Smit, Berend; Kim, Jihan

    2018-02-26

    We have developed a simple text mining algorithm that allows us to identify surface area and pore volumes of metal-organic frameworks (MOFs) using manuscript html files as inputs. The algorithm searches for common units (e.g., m 2 /g, cm 3 /g) associated with these two quantities to facilitate the search. From the sample set data of over 200 MOFs, the algorithm managed to identify 90% and 88.8% of the correct surface area and pore volume values. Further application to a test set of randomly chosen MOF html files yielded 73.2% and 85.1% accuracies for the two respective quantities. Most of the errors stem from unorthodox sentence structures that made it difficult to identify the correct data as well as bolded notations of MOFs (e.g., 1a) that made it difficult identify its real name. These types of tools will become useful when it comes to discovering structure-property relationships among MOFs as well as collecting a large set of data for references.

  6. Nanomaterials derived from metal-organic frameworks

    Science.gov (United States)

    Dang, Song; Zhu, Qi-Long; Xu, Qiang

    2018-01-01

    The thermal transformation of metal-organic frameworks (MOFs) generates a variety of nanostructured materials, including carbon-based materials, metal oxides, metal chalcogenides, metal phosphides and metal carbides. These derivatives of MOFs have characteristics such as high surface areas, permanent porosities and controllable functionalities that enable their good performance in sensing, gas storage, catalysis and energy-related applications. Although progress has been made to tune the morphologies of MOF-derived structures at the nanometre scale, it remains crucial to further our knowledge of the relationship between morphology and performance. In this Review, we summarize the synthetic strategies and optimized methods that enable control over the size, morphology, composition and structure of the derived nanomaterials. In addition, we compare the performance of materials prepared by the MOF-templated strategy and other synthetic methods. Our aim is to reveal the relationship between the morphology and the physico-chemical properties of MOF-derived nanostructures to optimize their performance for applications such as sensing, catalysis, and energy storage and conversion.

  7. Microporous metal organic framework [M2(hfipbb)2(ted)] (M=Zn, Co; H2hfipbb=4,4-(hexafluoroisopropylidene)-bis(benzoic acid); ted=triethylenediamine): Synthesis, structure analysis, pore characterization, small gas adsorption and CO2/N2 separation properties

    Science.gov (United States)

    Xu, William W.; Pramanik, Sanhita; Zhang, Zhijuan; Emge, Thomas J.; Li, Jing

    2013-04-01

    Carbon dioxide is a greenhouse gas that is a major contributor to global warming. Developing methods that can effectively capture CO2 is the key to reduce its emission to the atmosphere. Recent research shows that microporous metal organic frameworks (MOFs) are emerging as a promising family of adsorbents that may be promising for use in adsorption based capture and separation of CO2 from power plant waste gases. In this work we report the synthesis, crystal structure analysis and pore characterization of two microporous MOF structures, [M2(hfipbb)2(ted)] (M=Zn (1), Co (2); H2hfipbb=4,4-(hexafluoroisopropylidene)-bis(benzoic acid); ted=triethylenediamine). The CO2 and N2 adsorption experiments and IAST calculations are carried out on [Zn2(hfipbb)2(ted)] under conditions that mimic post-combustion flue gas mixtures emitted from power plants. The results show that the framework interacts with CO2 strongly, giving rise to relatively high isosteric heats of adsorption (up to 28 kJ/mol), and high adsorption selectivity for CO2 over N2, making it promising for capturing and separating CO2 from CO2/N2 mixtures.

  8. Surface nano-architecture of a metal-organic framework.

    Science.gov (United States)

    Makiura, Rie; Motoyama, Soichiro; Umemura, Yasushi; Yamanaka, Hiroaki; Sakata, Osami; Kitagawa, Hiroshi

    2010-07-01

    The rational assembly of ultrathin films of metal-organic frameworks (MOFs)--highly ordered microporous materials--with well-controlled growth direction and film thickness is a critical and as yet unrealized issue for enabling the use of MOFs in nanotechnological devices, such as sensors, catalysts and electrodes for fuel cells. Here we report the facile bottom-up fabrication at ambient temperature of such a perfect preferentially oriented MOF nanofilm on a solid surface (NAFS-1), consisting of metalloporphyrin building units. The construction of NAFS-1 was achieved by the unconventional integration in a modular fashion of a layer-by-layer growth technique coupled with the Langmuir-Blodgett method. NAFS-1 is endowed with highly crystalline order both in the out-of-plane and in-plane orientations to the substrate, as demonstrated by synchrotron X-ray surface crystallography. The proposed structural model incorporates metal-coordinated pyridine molecules projected from the two-dimensional sheets that allow each further layer to dock in a highly ordered interdigitated manner in the growth of NAFS-1. We expect that the versatility of the solution-based growth strategy presented here will allow the fabrication of various well-ordered MOF nanofilms, opening the way for their use in a range of important applications.

  9. Zeolite-like metal-organic frameworks with ana topology

    KAUST Repository

    Eddaoudi, Mohamed

    2017-04-20

    Embodiments of the present disclosure describe a zeolite-like metal-organic framework composition comprising a metal-organic framework composition with ana topology characterized by the formula [MIII(4, 5-imidazole dicarboxylic acid)2X(solvent)a]n wherein MIII comprises a trivalent cation of a rare earth element, X comprises an alkali metal element or alkaline earth metal element, and solvent comprises a guest molecule occupying pores. Embodiments of the present disclosure describe a method of separating paraffins comprising contacting a zeolite-like metal-organic framework with ana topology with a flow of paraffins, and separating the paraffins by size.

  10. Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units

    KAUST Repository

    Yao, Zizhu; Zhang, Zhangjing; Liu, Lizhen; Li, Ziyin; Zhou, Wei; Zhao, Yunfeng; Han, Yu; Chen, Banglin; Krishna, Rajamani; Xiang, Shengchang

    2016-01-01

    Acetylene separation is a very important but challenging industrial separation task. Here, through the solvothermal reaction of CuI and 5-triazole isophthalic acid in different solvents, two metal-organic frameworks (MOFs, FJU-21 and FJU-22) with open O donor sites and controllable robustness have been obtained for acetylene separation. They contain the same paddle-wheel {Cu2(COO2)4} nodes and metal-ligand connection modes, but with different helical chains as secondary building units (SBUs), leading to different structural robustness for the MOFs. FJU-21 and FJU-22 are the first examples in which the MOFs' robustness is controlled by adjusting the helical chain SBUs. Good robustness gives the activated FJU-22 a, which has higher surface area and gas uptakes than the flexible FJU-21 a. Importantly, FJU-22 a shows extraordinary separation of acetylene mixtures under ambient conditions. The separation capacity of FJU-22 a for 50:50 C2H2/CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2H2/C2H4 mixtures containing 1 % acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2H2 molecules with the open O donors on the wall, which provide better recognition ability for C2H2 than other functional sites, including open metal sites and amino groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units

    KAUST Repository

    Yao, Zizhu

    2016-03-02

    Acetylene separation is a very important but challenging industrial separation task. Here, through the solvothermal reaction of CuI and 5-triazole isophthalic acid in different solvents, two metal-organic frameworks (MOFs, FJU-21 and FJU-22) with open O donor sites and controllable robustness have been obtained for acetylene separation. They contain the same paddle-wheel {Cu2(COO2)4} nodes and metal-ligand connection modes, but with different helical chains as secondary building units (SBUs), leading to different structural robustness for the MOFs. FJU-21 and FJU-22 are the first examples in which the MOFs\\' robustness is controlled by adjusting the helical chain SBUs. Good robustness gives the activated FJU-22 a, which has higher surface area and gas uptakes than the flexible FJU-21 a. Importantly, FJU-22 a shows extraordinary separation of acetylene mixtures under ambient conditions. The separation capacity of FJU-22 a for 50:50 C2H2/CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2H2/C2H4 mixtures containing 1 % acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2H2 molecules with the open O donors on the wall, which provide better recognition ability for C2H2 than other functional sites, including open metal sites and amino groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Fuel upgrading and reforming with metal organic framework

    KAUST Repository

    Eddaoudi, Mohamed; Belmabkhout, Youssef

    2016-01-01

    Systems and methods for separating hydrocarbons on an internal combustion powered vehicle via one or more metal organic frameworks are disclosed. Systems and methods can further include utilizing separated hydrocarbons and exhaust to generate

  13. Metal organic frameworks for removal of compounds from a fluid

    KAUST Repository

    Eddaoudi, Mohamed

    2016-03-03

    Embodiments provide a method of compound removal from a fluid. The method includes contacting one or more metal organic framework (MOF) compositions with a fluid and sorbing one or more compounds, such as CO2, H2S and condensable hydrocarbons. One or more of CO2, H2S and condensable hydrocarbons can be sorbed simultaneously or in series. The metal organic framework can be an M-soc-MOF.

  14. Fuel upgrading and reforming with metal organic framework

    KAUST Repository

    Eddaoudi, Mohamed

    2016-03-31

    Systems and methods for separating hydrocarbons on an internal combustion powered vehicle via one or more metal organic frameworks are disclosed. Systems and methods can further include utilizing separated hydrocarbons and exhaust to generate hydrogen gas for use as fuel. In one aspect, a method for separating hydrocarbons can include contacting a first component containing a first metal organic framework with a flow of hydrocarbons and separating hydrocarbons by size. In certain embodiments, the hydrocarbons can include alkanes.

  15. Metal organic frameworks for removal of compounds from a fluid

    KAUST Repository

    Eddaoudi, Mohamed; Belmabkhout, Youssef

    2016-01-01

    Embodiments provide a method of compound removal from a fluid. The method includes contacting one or more metal organic framework (MOF) compositions with a fluid and sorbing one or more compounds, such as CO2, H2S and condensable hydrocarbons. One or more of CO2, H2S and condensable hydrocarbons can be sorbed simultaneously or in series. The metal organic framework can be an M-soc-MOF.

  16. Reconfigurable electronics using conducting metal-organic frameworks

    Science.gov (United States)

    Allendorf, Mark D.; Talin, Albert Alec; Leonard, Francois; Stavila, Vitalie

    2017-07-18

    A device including a porous metal organic framework (MOF) disposed between two terminals, the device including a first state wherein the MOF is infiltrated by a guest species to form an electrical path between the terminals and a second state wherein the electrical conductivity of the MOF is less than the electrical conductivity in the first state. A method including switching a porous metal organic framework (MOF) between two terminals from a first state wherein a metal site in the MOF is infiltrated by a guest species that is capable of charge transfer to a second state wherein the MOF is less electrically conductive than in the first state.

  17. Recent Advances as Materials of Functional Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Xiao-Lan Tong

    2013-01-01

    Full Text Available Metal-organic frameworks (MOFs, also known as hybrid inorganic-organic materials, represent an emerging class of materials that have attracted the imagination of solid-state chemists because MOFs combine unprecedented levels of porosity with a range of other functional properties that occur through the metal moiety and/or the organic ligand. The purpose of this critical review is to give a representative and comprehensive overview of the arising developments in the field of functional metal-organic frameworks, including luminescence, magnetism, and porosity through presenting examples. This review will be of interest to researchers and synthetic chemists attempting to design multifunctional MOFs.

  18. 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

  19. Hydrogen storage in metal-organic frameworks: A review

    CSIR Research Space (South Africa)

    Langmi, Henrietta W

    2014-05-01

    Full Text Available Metal-organic frameworks (MOFs) for hydrogen storage have continued to receive intense interest over the past decade. MOFs are a class of organic-inorganic hybrid crystalline materials consisting of metallic moieties that are linked by strong...

  20. Neutron powder diffraction of metal-organic frameworks for ...

    Indian Academy of Sciences (India)

    We review recent structural studies that we have undertaken aimed at elucidating the fundamental properties of metal-organic framework materials and their interactions with hydrogen. We have shown that exposing coordinatively unsaturated metal centers can greatly enhance the hydrogen binding energy and that they ...

  1. Supramolecular Assembly of Calcium Metal - Organic Frameworks with Structural Transformation

    Czech Academy of Sciences Publication Activity Database

    Liang, P.-Ch.; Liu, H.-K.; Yeh, Ch.-T.; Lin, Ch.-H.; Zima, Vítězslav

    2011-01-01

    Roč. 11, č. 3 (2011), 699-708 ISSN 1528-7483 R&D Projects: GA ČR GA203/08/0208 Institutional research plan: CEZ:AV0Z40500505 Keywords : metal - organic frameworks * calcium * structure Subject RIV: CA - Inorganic Chemistry Impact factor: 4.720, year: 2011

  2. 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)

  3. An Ising model for metal-organic frameworks

    Science.gov (United States)

    Höft, Nicolas; Horbach, Jürgen; Martín-Mayor, Victor; Seoane, Beatriz

    2017-08-01

    We present a three-dimensional Ising model where lines of equal spins are frozen such that they form an ordered framework structure. The frame spins impose an external field on the rest of the spins (active spins). We demonstrate that this "porous Ising model" can be seen as a minimal model for condensation transitions of gas molecules in metal-organic frameworks. Using Monte Carlo simulation techniques, we compare the phase behavior of a porous Ising model with that of a particle-based model for the condensation of methane (CH4) in the isoreticular metal-organic framework IRMOF-16. For both models, we find a line of first-order phase transitions that end in a critical point. We show that the critical behavior in both cases belongs to the 3D Ising universality class, in contrast to other phase transitions in confinement such as capillary condensation.

  4. Supercritical processing as a route to high internal surface areas and permanent microporosity in metal-organic framework materials.

    Science.gov (United States)

    Nelson, Andrew P; Farha, Omar K; Mulfort, Karen L; Hupp, Joseph T

    2009-01-21

    Careful processing of four representative metal-organic framework (MOF) materials with liquid and supercritical carbon dioxide (ScD) leads to substantial, or in some cases spectacular (up to 1200%), increases in gas-accessible surface area. Maximization of surface area is key to the optimization of MOFs for many potential applications. Preliminary evidence points to inhibition of mesopore collapse, and therefore micropore accessibility, as the basis for the extraordinarily efficacious outcome of ScD-based activation.

  5. A Kind of Energy Storage Technology: Metal Organic Frameworks

    OpenAIRE

    Ozturk, Zeynel; Kose, D. A.; Asan, A.; Ozturk, B.

    2016-01-01

    For last fifteen years energy has been transferred by using electricity and as an energy carrier media electricity has some disadvantages like its wire need for transportation and its being non-storable for large amounts. To store more energy safely and for transportation it easily, new storing medias and devices are needed. For easy and safe energy transport there are many technologies and some of these contain hydrogen energy. Metal hydrides, carbon nanotubes, metal organic frameworks (MOFs...

  6. Controlling Thermal Expansion: A Metal?Organic Frameworks Route

    OpenAIRE

    Balestra, Salvador R. G.; Bueno-Perez, Rocio; Hamad, Said; Dubbeldam, David; Ruiz-Salvador, A. Rabdel; Calero, Sofia

    2016-01-01

    Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal?organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model m...

  7. Molecularly Imprinted Polymer/Metal Organic Framework Based Chemical Sensors

    Directory of Open Access Journals (Sweden)

    Zhenzhong Guo

    2016-10-01

    Full Text Available The present review describes recent advances in the concept of molecular imprinting using metal organic frameworks (MOF for development of chemical sensors. Two main strategies regarding the fabrication, performance and applications of recent sensors based on molecularly imprinted polymers associated with MOF are presented: molecularly imprinted MOF films and molecularly imprinted core-shell nanoparticles using MOF as core. The associated transduction modes are also discussed. A brief conclusion and future expectations are described herein.

  8. Breaking Down Chemical Weapons by Metal-Organic Frameworks.

    Science.gov (United States)

    Mondal, Suvendu Sekhar; Holdt, Hans-Jürgen

    2016-01-04

    Seek and destroy: Filtration schemes and self-detoxifying protective fabrics based on the Zr(IV)-containing metal-organic frameworks (MOFs) MOF-808 and UiO-66 doped with LiOtBu have been developed that capture and hydrolytically detoxify simulants of nerve agents and mustard gas. Both MOFs function as highly catalytic elements in these applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Nano-architecture of metal-organic frameworks

    Science.gov (United States)

    Milichko, Valentin A.; Zalogina, Anastasiia; Mingabudinova, Leila R.; Vinogradov, Alexander V.; Ubyivovk, Evgeniy; Krasilin, Andrei A.; Mukhin, Ivan; Zuev, Dmitry A.; Makarov, Sergey V.; Pidko, Evgeny A.

    2017-09-01

    Change the shape and size of materials supports new functionalities never found in the sources. This strategy has been recently applied for porous crystalline materials - metal-organic frameworks (MOFs) to create hollow nanoscale structures or mesostructures with improved functional properties. However, such structures are characterized by amorphous state or polycrystallinity which limits their applicability. Here we follow this strategy to create such nano- and mesostructures with perfect crystallinity and new photonics functionalities by laser or focused ion beam fabrication.

  10. Alkylamine functionalized metal-organic frameworks for composite gas separations

    Science.gov (United States)

    Long, Jeffrey R.; McDonald, Thomas M.; D'Alessandro, Deanna M.

    2018-01-09

    Functionalized metal-organic framework adsorbents with ligands containing basic nitrogen groups such as alkylamines and alkyldiamines appended to the metal centers and method of isolating carbon dioxide from a stream of combined gases and carbon dioxide partial pressures below approximately 1 and 1000 mbar. The adsorption material has an isosteric heat of carbon dioxide adsorption of greater than -60 kJ/mol at zero coverage using a dual-site Langmuir model.

  11. Metal organic framework MIL-101 for radioiodine capture and storage

    Science.gov (United States)

    Assaad, Thaer; Assfour, Bassem

    2017-09-01

    we report on the use of metal organic frameworks(MOFs) for radioiodine recovery and storage. One MOF (namely MIL-101) was prepared and investigated in detail to demonstrate the iodine removal efficiency and capacity of MOFs. The typical sorption kinetics and uptake isotherms were measured using radioactive iodine (123 I) for the first time. Our measurements indicate that MOFs can capture and store radioiodine in very high efficiency and fast kinetics.

  12. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks.

    Science.gov (United States)

    Feng, Liang; Yuan, Shuai; Zhang, Liang-Liang; Tan, Kui; Li, Jia-Luo; Kirchon, Angelo; Liu, Ling-Mei; Zhang, Peng; Han, Yu; Chabal, Yves J; Zhou, Hong-Cai

    2018-02-14

    Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. Herein, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal-organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal-organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

  13. Investigating cluster formation in adsorption of CO2, CH4, and Ar in zeolites and metal organic frameworks at subcritical temperatures

    NARCIS (Netherlands)

    Krishna, R.; van Baten, J.M.

    2010-01-01

    The critical temperatures, T-c, of CO2, CH4, and Ar are 304 K, 191 K, and 151 K, respectively. This paper highlights some unusual characteristics of adsorption and diffusion of these molecules in microporous structures such as zeolites and metal organic frameworks at temperatures T < T-c. Published

  14. Hydrothermal Synthesis and Characterization of a Metal-Organic Framework by Thermogravimetric Analysis, Powder X-Ray Diffraction, and Infrared Spectroscopy: An Integrative Inorganic Chemistry Experiment

    Science.gov (United States)

    Crane, Johanna L.; Anderson, Kelly E.; Conway, Samantha G.

    2015-01-01

    This advanced undergraduate laboratory experiment involves the synthesis and characterization of a metal-organic framework with microporous channels that are held intact via hydrogen bonding of the coordinated water molecules. The hydrothermal synthesis of Co[subscript 3](BTC)[subscript 2]·12H[subscript 2]O (BTC = 1,3,5-benzene tricarboxylic acid)…

  15. 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.

  16. 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.

  17. 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.

  18. Catalysis by metal-organic frameworks: fundamentals and opportunities.

    Science.gov (United States)

    Ranocchiari, Marco; van Bokhoven, Jeroen Anton

    2011-04-14

    Crystalline porous materials are extremely important for developing catalytic systems with high scientific and industrial impact. Metal-organic frameworks (MOFs) show unique potential that still has to be fully exploited. This perspective summarizes the properties of MOFs with the aim to understand what are possible approaches to catalysis with these materials. We categorize three classes of MOF catalysts: (1) those with active site on the framework, (2) those with encapsulated active species, and (3) those with active sites attached through post-synthetic modification. We identify the tunable porosity, the ability to fine tune the structure of the active site and its environment, the presence of multiple active sites, and the opportunity to synthesize structures in which key-lock bonding of substrates occurs as the characteristics that distinguish MOFs from other materials. We experience a unique opportunity to imagine and design heterogeneous catalysts, which might catalyze reactions previously thought impossible.

  19. Metal-organic frameworks with dynamic interlocked components

    Science.gov (United States)

    Vukotic, V. Nicholas; Harris, Kristopher J.; Zhu, Kelong; Schurko, Robert W.; Loeb, Stephen J.

    2012-06-01

    The dynamics of mechanically interlocked molecules such as rotaxanes and catenanes have been studied in solution as examples of rudimentary molecular switches and machines, but in this medium, the molecules are randomly dispersed and their motion incoherent. As a strategy for achieving a higher level of molecular organization, we have constructed a metal-organic framework material using a [2]rotaxane as the organic linker and binuclear Cu(II) units as the nodes. Activation of the as-synthesized material creates a void space inside the rigid framework that allows the soft macrocyclic ring of the [2]rotaxane to rotate rapidly, unimpeded by neighbouring molecular components. Variable-temperature 13C and 2H solid-state NMR experiments are used to characterize the nature and rate of the dynamic processes occurring inside this unique material. These results provide a blueprint for the future creation of solid-state molecular switches and molecular machines based on mechanically interlocked molecules.

  20. Increasing the Stability of Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Mathieu Bosch

    2014-01-01

    Full Text Available Metal-organic frameworks (MOFs are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapse upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.

  1. Ultrafast water sensing and thermal imaging by a metal-organic framework with switchable luminescence

    Science.gov (United States)

    Chen, Ling; Ye, Jia-Wen; Wang, Hai-Ping; Pan, Mei; Yin, Shao-Yun; Wei, Zhang-Wen; Zhang, Lu-Yin; Wu, Kai; Fan, Ya-Nan; Su, Cheng-Yong

    2017-06-01

    A convenient, fast and selective water analysis method is highly desirable in industrial and detection processes. Here a robust microporous Zn-MOF (metal-organic framework, Zn(hpi2cf)(DMF)(H2O)) is assembled from a dual-emissive H2hpi2cf (5-(2-(5-fluoro-2-hydroxyphenyl)-4,5-bis(4-fluorophenyl)-1H-imidazol-1-yl)isophthalic acid) ligand that exhibits characteristic excited state intramolecular proton transfer (ESIPT). This Zn-MOF contains amphipathic micropores (behaviour. The interconversion between the hydrated and dehydrated phases can turn the ligand ESIPT process on or off, resulting in sensitive two-colour photoluminescence switching over cycles. Therefore, this Zn-MOF represents an excellent PL water-sensing material, showing a fast (on the order of seconds) and highly selective response to water on a molecular level. Furthermore, paper or in situ grown ZnO-based sensing films have been fabricated and applied in humidity sensing (RH<1%), detection of traces of water (<0.05% v/v) in various organic solvents, thermal imaging and as a thermometer.

  2. Semiconductor Metal-Organic Frameworks: Future Low-Bandgap Materials.

    Science.gov (United States)

    Usman, Muhammad; Mendiratta, Shruti; Lu, Kuang-Lieh

    2017-02-01

    Metal-organic frameworks (MOFs) with low density, high porosity, and easy tunability of functionality and structural properties, represent potential candidates for use as semiconductor materials. The rapid development of the semiconductor industry and the continuous miniaturization of feature sizes of integrated circuits toward the nanometer (nm) scale require novel semiconductor materials instead of traditional materials like silicon, germanium, and gallium arsenide etc. MOFs with advantageous properties of both the inorganic and the organic components promise to serve as the next generation of semiconductor materials for the microelectronics industry with the potential to be extremely stable, cheap, and mechanically flexible. Here, a perspective of recent research is provided, regarding the semiconducting properties of MOFs, bandgap studies, and their potential in microelectronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Designing Kitaev Spin Liquids in Metal-Organic Frameworks

    Science.gov (United States)

    Yamada, Masahiko G.; Fujita, Hiroyuki; Oshikawa, Masaki

    2017-08-01

    Kitaev's honeycomb lattice spin model is a remarkable exactly solvable model, which has a particular type of spin liquid (Kitaev spin liquid) as the ground state. Although its possible realization in iridates and α -RuCl3 has been vigorously discussed recently, these materials have substantial non-Kitaev direct exchange interactions and do not have a spin liquid ground state. We propose metal-organic frameworks (MOFs) with Ru3 + (or Os3 + ), forming the honeycomb lattice as promising candidates for a more ideal realization of Kitaev-type spin models, where the direct exchange interaction is strongly suppressed. The great flexibility of MOFs allows generalization to other three-dimensional lattices for the potential realization of a variety of spin liquids, such as a Weyl spin liquid.

  4. Xenon Recovery at Room Temperature using Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Elsaidi, Sameh K. [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Chemistry Department, Faculty of Science, Alexandria University, P. O. Box 426 Ibrahimia Alexandria 21321 Egypt; Ongari, Daniele [Laboratory of Molecular Simulation, Institut des Sciences et Ingeénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l' Industrie 17 1951 Sion Valais Switzerland; Xu, Wenqian [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Mohamed, Mona H. [Chemistry Department, Faculty of Science, Alexandria University, P. O. Box 426 Ibrahimia Alexandria 21321 Egypt; Haranczyk, Maciej [IMDEA Materials Institute, c/Eric Kandel 2 28906 Getafe, Madrid Spain; Thallapally, Praveen K. [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA

    2017-07-24

    Xenon is known to be a very efficient anesthetic gas but its cost prohibits the wider use in medical industry and other potential applications. It has been shown that Xe recovery and recycle from anesthetic gas mixture can significantly reduce its cost as anesthetic. The current technology uses series of adsorbent columns followed by low temperature distillation to recover Xe, which is expensive to use in medical facilities. Herein, we propose much efficient and simpler system to recover and recycle Xe from simulant exhale anesthetic gas mixture at room temperature using metal organic frameworks. Among the MOFs tested, PCN-12 exhibits unprecedented performance with high Xe capacity, Xe/N2 and Xe/O2 selectivity at room temperature. The in-situ synchrotron measurements suggest the Xe is occupied in the small pockets of PCN-12 compared to unsaturated metal centers (UMCs). Computational modeling of adsorption further supports our experimental observation of Xe binding sites in PCN-12.

  5. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks

    KAUST Repository

    Feng, Liang

    2018-01-18

    Sufficient pore size, appropriate stability and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization and catalysis involving large molecules. Herein, we report a powerful and general strate-gy, linker thermolysis, to construct ultra-stable hierarchically porous metal−organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal-organic frameworks (MTV-MOFs) through a decarboxyla-tion process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultra-small metal oxide (MO) nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid catalyzed reactions. Most importantly, this work pro-vides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on prob-ing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

  6. 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.

  7. Anisotropic thermal expansion in a metal-organic framework.

    Science.gov (United States)

    Madsen, Solveig Røgild; Lock, Nina; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2014-06-01

    Ionothermal reaction between Mn(II)(acetate)2·4H2O and 1,3,5-benzenetricarboxylic acid (H3BTC) in either of the two ionic liquids 1-ethyl-3-methylimidazolium bromide (EMIMBr) and 1-ethyl-3-methylimidazolium tosylate (EMIMOTs) resulted in the formation of the new metal-organic framework (MOF) EMIM[Mn(II)BTC] (BTC = 1,3,5-benzenetricarboxylate). The compound crystallizes in the orthorhombic space group Pbca with unit-cell parameters of a = 14.66658 (12), b = 12.39497 (9), c = 16.63509 (14) Å at 100 K. Multi-temperature single-crystal (15-340 K) and powder X-ray diffraction studies (100-400 K) reveal strongly anisotropic thermal expansion properties. The linear thermal expansion coefficients, αL(l), attain maximum values at 400 K along the a- and b-axis, with αL(a) = 115 × 10(-6) K(-1) and αL(b) = 75 × 10(-6) K(-1). At 400 K a negative thermal expansion coefficient of -40 × 10(-6) K(-1) is observed along the c-axis. The thermal expansion is coupled to a continuous deformation of the framework, which causes the structure to expand in two directions. Due to the rigidity of the linker, the expansion in the ab plane causes the network to contract along the c-axis. Hirshfeld surface analysis has been used to describe the interaction between the framework structure and the EMIM cation that resides within the channel. This reveals a number of rather weak interactions and one governing hydrogen-bonding interactions.

  8. Fabrication of highly co2 selective metal organic framework membrane using liquid phase epitaxy approach

    KAUST Repository

    Eddaoudi, Mohamed

    2016-01-28

    Embodiments include a method of making a metal organic framework membrane comprising contacting a substrate with a solution including a metal ion and contacting the substrate with a solution including an organic ligand, sufficient to form one or more layers of a metal organic framework on a substrate. Embodiments further include a defect-free metal organic framework membrane comprising MSiF6(pyz)2, wherein M is a metal, wherein the thickness of the membrane is less than 1,000 µm, and wherein the metal organic has a growth orientation along the [110] plane relative to a substrate.

  9. Electrocatalytic Metal-Organic Frameworks for Energy Applications.

    Science.gov (United States)

    Downes, Courtney A; Marinescu, Smaranda C

    2017-11-23

    With the global energy demand expected to increase drastically over the next several decades, the development of a sustainable energy system to meet this increase is paramount. Renewable energy sources can be coupled with electrochemical conversion processes to store energy in chemical bonds. To promote these difficult transformations, electrocatalysts that operate at high conversion rates and efficiency are required. Metal-organic frameworks (MOFs) have emerged as a promising class of materials; however, the insulating nature of MOFs has limited their application as electrocatalysts. The recent development of conductive MOFs has led to several electrocatalytic MOFs that display activity comparable to that of the best-performing heterogeneous catalysts. Although many electrocatalytic MOFs exhibit low activity and stability, the few successful examples highlight the possibility of MOF electrocatalysts as replacements for noble-metal-based catalysts in commercial energy-converting devices. We review herein the use of pristine MOFs as electrocatalysts to facilitate important energy-related reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Metal-organic frameworks for lithium ion batteries and supercapacitors

    International Nuclear Information System (INIS)

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang

    2015-01-01

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m 2 g −1 ) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m 2 g −1 ), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study

  11. Humidity Detection Using Metal Organic Framework Coated on QCM

    KAUST Repository

    Kosuru, Lakshmoji

    2016-06-28

    Quartz crystal microbalance (QCM) coated with poly-4-vinylpyridine (PVP) and metal organic framework HKUST-1 are investigated and compared for humidity sensing. Drop casting method is employed to coat the PVP and HKUST-1 solutions onto the surface of a quartz crystal microbalance. The resonance frequencies of these sensors with varying relative humidity (RH) from 22% RH to 69% RH are measured using impedance analysis method. The sensitivity, humidity hysteresis, response, and recovery times of these sensors are studied. The sensitivities of uncoated, PVP, and HKUST-1 coated QCM sensors are 7 Hz, 48 Hz, and 720 Hz, respectively, in the range of 22% RH–69% RH. The extraction of desorption rate and adsorption energy associated with the adsorption and desorption of water molecules on these surfaces reveals that HKUST-1 has better sensing properties than PVP and uncoated QCM sensors. In this work, the HKUST-1 coated QCM is shown to be a promising material for moisture detection.

  12. Metal-organic frameworks for lithium ion batteries and supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang, E-mail: hdeng@whu.edu.cn

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.

  13. Controlling Thermal Expansion: A Metal-Organic Frameworks Route.

    Science.gov (United States)

    Balestra, Salvador R G; Bueno-Perez, Rocio; Hamad, Said; Dubbeldam, David; Ruiz-Salvador, A Rabdel; Calero, Sofia

    2016-11-22

    Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal-organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model material, along with three molecules of similar size and known differences in terms of the nature of host-guest interactions. It has been shown that adsorbate molecules can control, in a colligative way, the thermal expansion of the solid, so that changing the adsorbate molecules induces the solid to display positive, zero, or negative thermal expansion. We analyze in depth the distortion mechanisms, beyond the ligand metal junction, to cover the ligand distortions, and the energetic and entropic effect on the thermo-structural behavior. We provide an unprecedented atomistic insight on the effect of adsorbates on the thermal expansion of MOFs as a basic tool toward controlling the thermal expansion.

  14. Humidity Detection Using Metal Organic Framework Coated on QCM

    Directory of Open Access Journals (Sweden)

    Lakshmoji Kosuru

    2016-01-01

    Full Text Available Quartz crystal microbalance (QCM coated with poly-4-vinylpyridine (PVP and metal organic framework HKUST-1 are investigated and compared for humidity sensing. Drop casting method is employed to coat the PVP and HKUST-1 solutions onto the surface of a quartz crystal microbalance. The resonance frequencies of these sensors with varying relative humidity (RH from 22% RH to 69% RH are measured using impedance analysis method. The sensitivity, humidity hysteresis, response, and recovery times of these sensors are studied. The sensitivities of uncoated, PVP, and HKUST-1 coated QCM sensors are 7 Hz, 48 Hz, and 720 Hz, respectively, in the range of 22% RH–69% RH. The extraction of desorption rate and adsorption energy associated with the adsorption and desorption of water molecules on these surfaces reveals that HKUST-1 has better sensing properties than PVP and uncoated QCM sensors. In this work, the HKUST-1 coated QCM is shown to be a promising material for moisture detection.

  15. Functionalization of silicon nanowire surfaces with metal-organic frameworks

    KAUST Repository

    Liu, Nian

    2011-12-28

    Metal-organic frameworks (MOFs) and silicon nanowires (SiNWs) have been extensively studied due to their unique properties; MOFs have high porosity and specific surface area with well-defined nanoporous structure, while SiNWs have valuable one-dimensional electronic properties. Integration of the two materials into one composite could synergistically combine the advantages of both materials and lead to new applications. We report the first example of a MOF synthesized on surface-modified SiNWs. The synthesis of polycrystalline MOF-199 (also known as HKUST-1) on SiNWs was performed at room temperature using a step-by-step (SBS) approach, and X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy dispersive spectroscopy elemental mapping were used to characterize the material. Matching of the SiNW surface functional groups with the MOF organic linker coordinating groups was found to be critical for the growth. Additionally, the MOF morphology can by tuned by changing the soaking time, synthesis temperature and precursor solution concentration. This SiNW/MOF hybrid structure opens new avenues for rational design of materials with novel functionalities. © 2011 Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

  16. Structural versatility of Metal-organic frameworks: Synthesis and Characterization

    KAUST Repository

    Alsadun, Norah S.

    2017-05-01

    Metal-Organic Frameworks (MOFs), an emerging class of porous crystalline materials, have shown promising properties for diverse applications such as catalysis, gas storage and separation. The high degree of tunability of MOFs vs other solid materials enable the assembly of advanced materials with fascinating properties for specific applications. Nevertheless, the precise control in the construction of MOFs at the molecular level remains challenging. Particularly, the formation of pre-targeted multi-nuclear Molecular Building Block (MBB) precursors to unveil materials with targeted structural characteristics is captivating. The aim of my master project in the continuous quest of the group of Prof. Eddaoudi in exploring different synthetic pathways to control the assembly of Rare Earth (RE) based MOF. After giving a general overview about MOFs, I will discuss in this thesis the results of my work on the use of tri-topic oriented organic carboxylate building units with the aim to explore the assembly/construction of new porous RE based MOFs. In chapter 2 will discuss the assembly of 3-c linkers with RE metals was then evaluated based on symmetry and angularity of the three connected linkers. The focus of chapter 3 is cerium based MOFs and heterometallic system, based on 3-c ligands with different length and symmetry. Overall, the incompatibility of 3-c ligands with the 12-c cuo MBB did not allow to any formation of higher neuclearity (˃6), but it has resulted in affecting the connectivity of the cluster.

  17. Xenon Recovery at Room Temperature using Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Elsaidi, Sameh K. [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Chemistry Department, Faculty of Science, Alexandria University, P. O. Box 426 Ibrahimia Alexandria 21321 Egypt; Ongari, Daniele [Laboratory of Molecular Simulation, Institut des Sciences et Ingeénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l' Industrie 17 1951 Sion Valais Switzerland; Xu, Wenqian [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Mohamed, Mona H. [Chemistry Department, Faculty of Science, Alexandria University, P. O. Box 426 Ibrahimia Alexandria 21321 Egypt; Haranczyk, Maciej [IMDEA Materials Institute, c/Eric Kandel 2 28906 Getafe, Madrid Spain; Thallapally, Praveen K. [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA

    2017-07-24

    Xenon is known to be a very efficient anesthetic gas but its cost prohibits the wider use in medical industry and other potential applications. It has been shown that Xe recovery and recycle from anesthetic gas mixture can significantly reduce its cost as anesthetic. The current technology uses series of adsorbent columns followed by low temperature distillation to recover Xe, which is expensive to use in medical facilities. Herein, we propose much efficient and simpler system to recover and recycle Xe from simulant exhale anesthetic gas mixture at room temperature using metal organic frameworks. Among the MOFs tested, PCN-12 exhibits unprecedented performance with high Xe capacity, Xe/O2, Xe/N2 and Xe/CO2 selectivity at room temperature. The in-situ synchrotron measurements suggest the Xe is occupied in the small pockets of PCN-12 compared to unsaturated metal centers (UMCs). Computational modeling of adsorption further supports our experimental observation of Xe binding sites in PCN-12.

  18. Metal-organic frameworks at interfaces of hybrid perovskite solar cells for enhanced photovoltaic properties.

    Science.gov (United States)

    Shen, Deli; Pang, Aiying; Li, Yafeng; Dou, Jie; Wei, Mingdeng

    2018-01-31

    In this study, metal-organic frameworks, as an interfacial layer, were introduced into perovskite solar cells (PSCs) for the first time. An interface modified with the metal-organic framework ZIF-8 efficiently enhanced perovskite crystallinity and grain sizes, and the photovoltaic performance of the PSCs was significantly improved, resulting in a maximum PCE of 16.99%.

  19. Green methods for preparing highly co2 selective and h2s tolerant metal organic frameworks

    KAUST Repository

    Eddaoudi, Mohamed

    2015-12-23

    A green route for preparing a metal organic framework include mixing metal precursor with a ligand precursor to form a solvent-free mixture; adding droplets of water to the mixture; heating the mixture at a first temperature after adding the water; and isolating the metal organic framework material including the metal and the ligand.

  20. Metal organic frameworks for the catalytic detoxification of chemical warfare nerve agents

    Science.gov (United States)

    Hupp, Joseph T.; Farha, Omar K.; Katz, Michael J.; Mondloch, Joseph E.

    2017-04-18

    A method of using a metal organic framework (MOF) comprising a metal ion and an at least bidendate organic ligand to catalytically detoxify chemical warfare nerve agents including exposing the metal-organic-framework (MOF) to the chemical warfare nerve agent and catalytically decomposing the nerve agent with the MOF.

  1. Metal-organic frameworks for adsorption and separation of noble gases

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Greathouse, Jeffery A.; Staiger, Chad

    2017-05-30

    A method including exposing a gas mixture comprising a noble gas to a metal organic framework (MOF), including an organic electron donor and an adsorbent bed operable to adsorb a noble gas from a mixture of gases, the adsorbent bed including a metal organic framework (MOF) including an organic electron donor.

  2. 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)).

  3. Metal-organic frameworks based membranes for liquid separation.

    Science.gov (United States)

    Li, Xin; Liu, Yuxin; Wang, Jing; Gascon, Jorge; Li, Jiansheng; Van der Bruggen, Bart

    2017-11-27

    Metal-organic frameworks (MOFs) represent a fascinating class of solid crystalline materials which can be self-assembled in a straightforward manner by the coordination of metal ions or clusters with organic ligands. Owing to their intrinsic porous characteristics, unique chemical versatility and abundant functionalities, MOFs have received substantial attention for diverse industrial applications, including membrane separation. Exciting research activities ranging from fabrication strategies to separation applications of MOF-based membranes have appeared. Inspired by the marvelous achievements of MOF-based membranes in gas separations, liquid separations are also being explored for the purpose of constructing continuous MOFs membranes or MOF-based mixed matrix membranes. Although these are in an emerging stage of vigorous development, most efforts are directed towards improving the liquid separation efficiency with well-designed MOF-based membranes. Therefore, as an increasing trend in membrane separation, the field of MOF-based membranes for liquid separation is highlighted in this review. The criteria for judicious selection of MOFs in fabricating MOF-based membranes are given. Special attention is paid to rational design strategies for MOF-based membranes, along with the latest application progress in the area of liquid separations, such as pervaporation, water treatment, and organic solvent nanofiltration. Moreover, some attractive dual-function applications of MOF-based membranes in the removal of micropollutants, degradation, and antibacterial activity are also reviewed. Finally, we define the remaining challenges and future opportunities in this field. This Tutorial Review provides an overview and outlook for MOF-based membranes for liquid separations. Further development of MOF-based membranes for liquid separation must consider the demands of strict separation standards and environmental safety for industrial application.

  4. Metal organic frameworks as a drug delivery system for flurbiprofen.

    Science.gov (United States)

    Al Haydar, Muder; Abid, Hussein Rasool; Sunderland, Bruce; Wang, Shaobin

    2017-01-01

    Metal organic frameworks (MOFs) have attracted more attention in the last decade because of a suitable pore size, large surface area, and high pore volume. Developing biocompatible MOFs such as the MIL family as a drug delivery system is possible. Flurbiprofen (FBP), a nonsteroidal anti-inflammatory agent, is practically insoluble in aqueous solution, and, therefore, needs suitable drug delivery systems. Different biocompatible MOFs such as Ca-MOF and Fe-MILs (53, 100, and 101) were synthesized and employed for FBP delivery. A sample of 50 mg of each MOF was mixed and stirred for 24 h with 10 mL of 5 mg FBP in acetonitrile (40%) in a sealed container. The supernatant of the mixture after centrifuging was analyzed by high-performance liquid chromatography to determine the loaded quantity of FBP on the MOF. The overnight-dried solid material after centrifuging the mixture was analyzed for loading percent using X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, nuclear magnetic resonance, and FBP release profile. The loading values of FBP were achieved at 10.0%±1%, 20%±0.8%, 37%±2.3%, and 46%±3.1% on Ca-MOF, Fe-MIL-53, Fe-MIL-101, and Fe-MIL-100, respectively. The FBP release profiles were investigated in a phosphate buffer solution at pH 7.4. The total release of the FBP after 2 days was obtained at 72.9, 75.2, 78.3, and 90.3% for Ca-MOF, Fe-MIL-100, Fe-MIL-53, and Fe-MIL-101, respectively. The MOFs are shown to be a promising drug delivery option for FBP with a significant loading percent and relatively prolonged drug release.

  5. Ultrafast rotation in an amphidynamic crystalline metal organic framework.

    Science.gov (United States)

    Vogelsberg, Cortnie S; Uribe-Romo, Fernando J; Lipton, Andrew S; Yang, Song; Houk, K N; Brown, Stuart; Garcia-Garibay, Miguel A

    2017-12-26

    Amphidynamic crystals are an emergent class of condensed phase matter designed with a combination of lattice-forming elements linked to components that display engineered dynamics in the solid state. Here, we address the design of a crystalline array of molecular rotors with inertial diffusional rotation at the nanoscale, characterized by the absence of steric or electronic barriers. We solved this challenge with 1,4-bicyclo[2.2.2]octane dicarboxylic acid (BODCA)-MOF, a metal-organic framework (MOF) built with a high-symmetry bicyclo[2.2.2]octane dicarboxylate linker in a Zn 4 O cubic lattice. Using spin-lattice relaxation 1 H solid-state NMR at 29.49 and 13.87 MHz in the temperature range of 2.3-80 K, we showed that internal rotation occurs in a potential with energy barriers of 0.185 kcal mol -1 These results were confirmed with 2 H solid-state NMR line-shape analysis and spin-lattice relaxation at 76.78 MHz obtained between 6 and 298 K, which, combined with molecular dynamics simulations, indicate that inertial diffusional rotation is characterized by a broad range of angular displacements with no residence time at any given site. The ambient temperature rotation of the bicyclo[2.2.2]octane (BCO) group in BODCA-MOF constitutes an example where engineered rotational dynamics in the solid state are as fast as they would be in a high-density gas or in a low-density liquid phase.

  6. Ultrafast rotation in an amphidynamic crystalline metal organic framework

    Energy Technology Data Exchange (ETDEWEB)

    Vogelsberg, Cortnie S.; Uribe-Romo, Fernando J.; Lipton, Andrew S.; Yang, Song; Houk, K. N.; Brown, Stuart; Garcia-Garibay, Miguel A.

    2017-12-11

    Amphidynamic crystals are an emergent class of condensed phase matter designed with a combination of lattice-forming elements linked to components that display engineered dynamics in the solid state. Here, we address the design of a crystalline array of molecular rotors with inertial diffusional rotation at the nanoscale, characterized by the absence of steric or electronic barriers. We solved this challenge with 1,4-bicyclo[2.2.2]octane dicarboxylic acid (BODCA)-MOF, a metal-organic framework (MOF) built with a high-symmetry bicyclo[2.2.2]octane dicarboxylate linker in a Zn4O cubic lattice. Using spin-lattice relaxation 1H solid-state NMR at 29.49 and 13.87 MHz in the temperature range of 2.3–80 K, we showed that internal rotation occurs in a potential with energy barriers of 0.185 kcal mol-1. These results were confirmed with 2H solid-state NMR line-shape analysis and spin-lattice relaxation at 76.78 MHz obtained between 6 and 298 K, which, combined with molecular dynamics simulations, indicate that inertial diffusional rotation is characterized by a broad range of angular displacements with no residence time at any given site. The ambient temperature rotation of the bicyclo[2.2.2]octane (BCO) group in BODCA-MOF constitutes an example where engineered rotational dynamics in the solid state are as fast as they would be in a high-density gas or in a low-density liquid phase.

  7. A fine-tuned Metal-Organic Framework for Autonomous Indoor Moisture Control .

    KAUST Repository

    Abdul Halim, Racha Ghassan

    2017-06-29

    Conventional adsorbents, namely zeolites and silica gel, are often used to control humidity by adsorbing water; however, adsorbents capable of dual functionality of humidification and dehumidification, offering the desired control of the moisture level at room temperature, has yet to be explored. Here we report Y-shp-MOF-5, a hybrid microporous highly-connected Rare-Earth based metal-organic framework (MOF), with dual functionality for moisture control within the recommended range of relative humidity (45% to 65% RH) set by the American Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASHRAE). Y-shp-MOF-5 exhibits exceptional structural integrity, robustness and unique humidity-control performance as confirmed by the large number (thousand) of conducted water vapor adsorption-desorption cycles. The retained structural integrity and the mechanism of water sorption were corroborated using in situ single crystal X-ray diffraction (SCXRD) studies. The resultant working water uptake of 0.45 g.g-1 is solely regulated by a simple adjustment of the relative humidity, positioning this hydrolytically stable MOF as a prospective adsorbent for humidity control in confined spaces such as space shuttles, aircraft cabins and air-conditioned buildings.

  8. Isolated Fe sites in Metal Organic Framework catalyze the direct conversion of methane to methanol

    KAUST Repository

    Osadchii, Dmitrii

    2018-05-10

    Hybrid materials bearing organic and inorganic motives have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal Metal Organic Framework that mimics the reactivity of soluble methane monooxygenase enzyme reactivity and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterisation of an Fe-containing MOF that comprises the desired antiferromagnetically cou-pled high spin species in a coordination environment closely resembling that of the enzyme. An electrochemi-cal synthesis method is used to build the microporous MOF matrix while integrating, with an exquisite con-trol, the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behaviour of the enzyme to produce methanol, and shows that the key to this reactivity is the for-mation of isolated oxo-bridged Fe units.

  9. Isolated Fe sites in Metal Organic Framework catalyze the direct conversion of methane to methanol

    KAUST Repository

    Osadchii, Dmitrii; Olivos Suarez, Alma Itzel; Szé csé nyi, Á gnes; Li, Guanna; Nasalevich, Maxim A.; Dugulan, A Iulian; Serra-Crespo, Pablo; Hensen, Emiel J. M.; Veber, Sergey L.; Fedin, Matvey V.; Sankar, Gopinathan; Pidko, Evgeny A; Gascon, Jorge

    2018-01-01

    Hybrid materials bearing organic and inorganic motives have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal Metal Organic Framework that mimics the reactivity of soluble methane monooxygenase enzyme reactivity and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterisation of an Fe-containing MOF that comprises the desired antiferromagnetically cou-pled high spin species in a coordination environment closely resembling that of the enzyme. An electrochemi-cal synthesis method is used to build the microporous MOF matrix while integrating, with an exquisite con-trol, the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behaviour of the enzyme to produce methanol, and shows that the key to this reactivity is the for-mation of isolated oxo-bridged Fe units.

  10. Metal organic frameworks as a drug delivery system for flurbiprofen

    Directory of Open Access Journals (Sweden)

    AL Haydar M

    2017-09-01

    Full Text Available Muder AL Haydar,1,2 Hussein Rasool Abid,3,4 Bruce Sunderland,2 Shaobin Wang5,6 1Pharmaceutics Department, College of the Pharmacy, University of Kerbala, Kerbala, Iraq; 2Pharmaceutics Department, School of Pharmacy, Faculty of Health Sciences, Curtin University, Perth, WA, Australia; 3Department of Chemical Engineering, Curtin University, Perth, WA, Australia; 4College of Applied Medical Sciences, University of Kerbala, Kerbala, Iraq; 5School of Pharmacy, Faculty of Health Sciences, Curtin University, Perth, WA, Australia; 6Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Faculty of Science and Engineering, Curtin University, Perth, WA, Australia Background: Metal organic frameworks (MOFs have attracted more attention in the last decade because of a suitable pore size, large surface area, and high pore volume. Developing biocompatible MOFs such as the MIL family as a drug delivery system is possible. Purpose: Flurbiprofen (FBP, a nonsteroidal anti-inflammatory agent, is practically insoluble in aqueous solution, and, therefore, needs suitable drug delivery systems. Different biocompatible MOFs such as Ca-MOF and Fe-MILs (53, 100, and 101 were synthesized and employed for FBP delivery. Patients and methods: A sample of 50 mg of each MOF was mixed and stirred for 24 h with 10 mL of 5 mg FBP in acetonitrile (40% in a sealed container. The supernatant of the mixture after centrifuging was analyzed by high-performance liquid chromatography to determine the loaded quantity of FBP on the MOF. The overnight-dried solid material after centrifuging the mixture was analyzed for loading percent using X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, nuclear magnetic resonance, and FBP release profile. Results: The loading values of FBP were achieved at 10.0%±1%, 20%±0.8%, 37%±2.3%, and 46%±3.1% on Ca-MOF, Fe-MIL-53, Fe-MIL-101, and Fe-MIL-100, respectively. The FBP release

  11. Construction of acylhydrazidate-extended metal-organic frameworks.

    Science.gov (United States)

    Wang, Yan-Ning; Yang, Qing-Feng; Li, Guang-Hua; Zhang, Ping; Yu, Jie-Hui; Xu, Ji-Qing

    2014-08-14

    Under hydrothermal conditions, the reactions of Ba(2+)/Zn(2+), aromatic polycarboxylic acids and N2H4 with or without oxalic acid were carried out, affording four new acylhydrazidate-extended metal-organic frameworks (MOFs) [Ba(pmdh)] (pmdh = pyromellitdihydrazidate) 1, [Ba(sdpth)(H2O)2]·0.5H2O (sdpth = 4,4'-sulfoyldiphthalhydrazidate) 2, [Ba2(cpth)2(H2O)2] (cpth = 4-carboxylphthalhydrazidate) 3 and [Zn2(pdh)2(ox)]·H2O (ox = oxalate, pdh = pyridine-2,3-dicarboxylhydrazidate) 4. The acylhydrazidate molecules pmdh, sdpth, cpth and pdh in compounds 1-4 derived from the hydrothermal in situ acylation of N2H4 with aromatic polycarboxylic acids. X-ray single-crystal diffraction analysis revealed that (i) in compound 1, the pmdh I molecules link the Ba(2+) ions into a two-dimensional (2D) layer with a (4,4) topology, and then the pmdh II molecules extend these layers into a three-dimensional (3D) network; (ii) in compound 2, the sdpth molecules link the Ba(2+) ions to form a one-dimensional (1D) square tube. Interestingly, the tubes are further linked into a 3D supramolecular network via the N-H···O interactions, creating synchronously big channels; (iii) in compound 3, the cpth I molecules link the Ba1 ions into a 3D network with a (10,3) topology. Ba2 and cpth II are distributed on the channels; (iv) in compound 4, Zn(2+) and pdh aggregate to form two types of Zn4(pdh)4 clusters. The ox molecules act as the secondary linkers, extending the Zn4(pdh)4 secondary building units (SBUs) into a 3D network with a 6(6) topology. The photoluminescence analysis indicates that compounds 3 and 4 emit green light with maxima at 495 nm for 3 (λ(ex) = 397 nm), and 522 nm for 4 (λ(ex) = 395 nm), respectively. At 77 K, the activated 2 and 4 can adsorb N2 in amounts of 58.31 cm(3) g(-1) for 2 and 38.38 cm(3) g(-1) for 4, respectively.

  12. Postsynthetic Tuning of Metal-Organic Frameworks for Targeted Applications.

    Science.gov (United States)

    Islamoglu, Timur; Goswami, Subhadip; Li, Zhanyong; Howarth, Ashlee J; Farha, Omar K; Hupp, Joseph T

    2017-04-18

    Metal-organic frameworks (MOFs) are periodic, hybrid, atomically well-defined porous materials that typically form by self-assembly and consist of inorganic nodes (metal ions or clusters) and multitopic organic linkers. MOFs as a whole offer many intriguing properties, including ultrahigh porosity, tunable chemical functionality, and low density. These properties point to numerous potential applications, including gas storage, chemical separations, catalysis, light harvesting, and chemical sensing, to name a few. Reticular chemistry, or the linking of molecular building blocks into predetermined network structures, has been employed to synthesize thousands of MOFs. Given the vast library of candidate nodes and linkers, the number of potentially synthetically accessible MOFs is enormous. Nevertheless, a powerful complementary approach to obtain specific structures with desired chemical functionality is to modify known MOFs after synthesis. This approach is particularly useful when incorporation of particular chemical functionalities via direct synthesis is challenging or impossible. The challenges may stem from limited stability or solubility of precursors, unwanted secondary reactivity of precursors, or incompatibility of functional groups with the conditions needed for direct synthesis. MOFs can be postsynthetically modified by replacing the metal nodes and/or organic linkers or via functionalization of the metal nodes and/or organic linkers. Here we describe some of our efforts toward the development and application of postsynthetic strategies for imparting desired chemical functionalities in MOFs of known topology. The techniques include methods for functionalizing MOF nodes, i.e., solvent-assisted ligand incorporation (SALI) and atomic layer deposition in MOFs (AIM) as well as a method to replace structural linkers, termed solvent-assisted linker exchange (SALE), also known as postsynthethic exchange (PSE). For each functionalization strategy, we first describe

  13. Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

    Science.gov (United States)

    DeCoste, Jared B.; Peterson, Gregory W.

    2013-01-01

    Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high surface area microporous materials, such as metal-organic frameworks (MOFs), unique challenges present themselves for PECVD treatments. Herein the protocol for development of a MOF that was previously unstable to humid conditions is presented. The protocol describes the synthesis of Cu-BTC (also known as HKUST-1), the treatment of Cu-BTC with PECVD of perfluoroalkanes, the aging of materials under humid conditions, and the subsequent ammonia microbreakthrough experiments on milligram quantities of microporous materials. Cu-BTC has an extremely high surface area (~1,800 m2/g) when compared to most materials or surfaces that have been previously treated by PECVD methods. Parameters such as chamber pressure and treatment time are extremely important to ensure the perfluoroalkane plasma penetrates to and reacts with the inner MOF surfaces. Furthermore, the protocol for ammonia microbreakthrough experiments set forth here can be utilized for a variety of test gases and microporous materials. PMID:24145623

  14. Design, Synthesis and Characterization of Functional Metal-Organic Framework Materials

    KAUST Repository

    Alamer, Badriah

    2015-01-01

    are known as Metal Organic Framework (MOFs). This exceptional new family of porous materials is fabricated by linkage of metal ions or clusters and organic linkers via strong bonds. MOFs have been awarded with remarkable interest and widely studied due

  15. 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

  16. Fabrication of highly co2 selective metal organic framework membrane using liquid phase epitaxy approach

    KAUST Repository

    Eddaoudi, Mohamed; Shekhah, Osama; Belmabkhout, Youssef

    2016-01-01

    Embodiments include a method of making a metal organic framework membrane comprising contacting a substrate with a solution including a metal ion and contacting the substrate with a solution including an organic ligand, sufficient to form one

  17. Synthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supports

    KAUST Repository

    Barankova, Eva

    2017-01-01

    Since the discovery of size-selective metal-organic frameworks (MOF) researchers have tried to manufacture them into gas separation membranes. ZIF-8 became the most studied MOF for membrane applications mainly because of its simple synthesis, good

  18. Rapidly assessing the activation conditions and porosity of metal-organic frameworks using thermogravimetric analysis.

    Science.gov (United States)

    McDonald, Thomas M; Bloch, Eric D; Long, Jeffrey R

    2015-03-25

    A methodology utilizing a thermogravimetric analyzer to monitor propane uptake following incremental increases of the temperature is demonstrated as a means of rapidly identifying porous materials and determining the optimum activation conditions of metal-organic frameworks.

  19. A porous Cd(II) metal-organic framework with high adsorption selectivity for CO2 over CH4

    Science.gov (United States)

    Zhu, Chunlan

    2017-05-01

    Metal-organic frameworks (MOFs) have attracted a lot of attention in recent decades. We applied a semi-rigid four-carboxylic acid linker to assemble with Cd(II) ions to generate a novel microporous Cd(II) MOF material. Single crystal X-ray diffraction study reveals the different two dimension (2D) layers can be further packed together with an AB fashion by hydrogen bonds (O4sbnd H4⋯O7 = 1.863 Å) to construct a three dimension (3D) supermolecular architecture. The resulting sample can be synthesized under solvothermal reactions successfully, which exhibits high selectivity adsorption of CO2 over CH4 at room temperature. In addition, the obtained sample was characterized by thermal gravimetric analyses (TGA), Fourier-transform infrared spectra (FT-IR), elemental analysis (CHN) and powder X-ray diffraction (PXRD).

  20. Chemical principles underpinning the performance of the metal-organic framework HKUST-1.

    Science.gov (United States)

    Hendon, Christopher H; Walsh, Aron

    2015-07-15

    A common feature of multi-functional metal-organic frameworks is a metal dimer in the form of a paddlewheel, as found in the structure of Cu 3 ( btc ) 2 (HKUST-1). The HKUST-1 framework demonstrates exceptional gas storage, sensing and separation, catalytic activity and, in recent studies, unprecedented ionic and electrical conductivity. These results are a promising step towards the real-world application of metal-organic materials. In this perspective, we discuss progress in the understanding of the electronic, magnetic and physical properties of HKUST-1, representative of the larger family of Cu···Cu containing metal-organic frameworks. We highlight the chemical interactions that give rise to its favourable properties, and which make this material well suited to a range of technological applications. From this analysis, we postulate key design principles for tailoring novel high-performance hybrid frameworks.

  1. Exploiting large-pore metal-organic frameworks for separations through entropic molecular mechanisms

    NARCIS (Netherlands)

    Torres-Knoop, A.; Dubbeldam, D.

    2015-01-01

    We review the molecular mechanisms behind adsorption and the separations of mixtures in metal-organic frameworks and zeolites. Separation mechanisms can be based on differences in the affinity of the adsorbate with the framework and on entropic effects. To develop next-generation adsorbents, the

  2. Melt-quenched glasses of metal-organic frameworks

    DEFF Research Database (Denmark)

    Bennett, T.D.; Yue, Yuanzheng; Li, P.

    2016-01-01

    Crystalline solids dominate the field of metal−organic frameworks (MOFs), with access to the liquid and glass states of matter usually prohibited by relatively low temperatures of thermal decomposition. In this work, we give due consideration to framework chemistry and topology to expand...... of other MOFs. The glasses formed upon vitrification are chemically and structurally distinct from the three other existing categories of melt-quenched glasses (inorganic nonmetallic, organic, and metallic), and retain the basic metal−ligand connectivity of crystalline MOFs, which connects their mechanical...... the phenomenon of the melting of 3D MOFs, linking crystal chemistry to framework melting temperature and kinetic fragility of the glass-forming liquids. Here we show that melting temperatures can be lowered by altering the chemistry of the crystalline MOF state, which provides a route to facilitate the melting...

  3. A pillar-layered metal-organic framework as luminescent sensor for selective and reversible response of chloroform

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Kun; Li, Shuni; Jiang, Yucheng; Hu, Mancheng; Zhai, Quan-Guo, E-mail: zhaiqg@snnu.edu.cn

    2017-03-15

    A new 3D metal-organic framework, namely, (Zn{sub 4}(H{sub 2}BPTC){sub 2}(HCOO){sub 4}){sub n} (SNNU-1, H{sub 4}BPTC=biphenyl-3,3',5,5'-tetracarboxylic acid, SNNU=Shaanxi Normal University) has been solvothermal synthesized. Four independent tetrahedral Zn atoms are connected by organic ligands to form a 2D Zn-H{sub 2}BPTC layer, which is further bridged by in-situ generated HCOO{sup -} to give the 3D pillar-layered framework of SNNU-1. Unique Zn and H{sub 2}BPTC all act as 4-connected nodes leading to a new 4,4,4-connected topological net with point symbol of (4·5·6{sup 2}·8{sup 2})(4·5{sup 2}·6{sup 2}·8)(5{sup 2}·6{sup 3}·7). Notably, intense blue emission band is observed for SNNU-1, which exhibits solvent-dependent effect. Compared to other common organic solvents, chloroform can specially improve the photoluminescent intensity of SNNU-1. Further repeated response and release experiments clearly showed that SNNU-1 can act as luminescent sensor for selective and reversible detection of chloroform. - Graphical abstract: Zn{sup 2+} ions are bridged by aromatic tetracarboxylate ligands and inorganic formate anions to give a microporous pillar layered open-framework, which exhibits not only strong photoluminescence but also selective and reversible luminescent sensing for chloroform. - Highlights: • Novel Zn-tetracarboxylate-formate microporous pillar layered open-framework. • New 4,4,4-connected topology and rod-packing net. • Solvent-dependent photoluminescent intensity. • Selective and reversible response for chloroform.

  4. A new metal-organic framework for separation of C2H2/CH4 and CO2/CH4 at room temperature

    Science.gov (United States)

    Duan, Xing; Zhou, You; Lv, Ran; Yu, Ben; Chen, Haodong; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2018-04-01

    A 3D microporous metal-organic framework with open Cu2+ sites and suitable pore space, [Cu2(L)(H2O)2]·(H2O)4(DMF)8 (ZJU-15, H4L = 5,5‧-(9H-carbazole-2,7-diyl)diisophthalic acid; DMF = N,N-dimethylformamide; ZJU = Zhejiang University), has been constructed and characterized. The activated ZJU-15a has three different types of cages and exhibits BET surface area of 1660 m2 g-1, and can separate gas mixture of C2H2/CH4 and CO2/CH4 at room temperature.

  5. Multirate delivery of multiple therapeutic agents from metal-organic frameworks

    Directory of Open Access Journals (Sweden)

    Alistair C. McKinlay

    2014-12-01

    Full Text Available The highly porous nature of metal-organic frameworks (MOFs offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-organic frameworks can be used to deliver multiple therapeutic agents—a biologically active gas, an antibiotic drug molecule, and an active metal ion—simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria.

  6. Synthesis, structural characterization and selectively catalytic properties of metal-organic frameworks with nano-sized channels: A modular design strategy

    International Nuclear Information System (INIS)

    Qiu Lingguang; Gu Lina; Hu Gang; Zhang Lide

    2009-01-01

    Modular design method for designing and synthesizing microporous metal-organic frameworks (MOFs) with selective catalytical activity was described. MOFs with both nano-sized channels and potential catalytic activities could be obtained through self-assembly of a framework unit and a catalyst unit. By selecting hexaaquo metal complexes and the ligand BTC (BTC=1,3,5-benzenetricarboxylate) as framework-building blocks and using the metal complex [M(phen) 2 (H 2 O) 2 ] 2+ (phen=1,10-phenanthroline) as a catalyst unit, a series of supramolecular MOFs 1-7 with three-dimensional nano-sized channels, i.e. [M 1 (H 2 O) 6 ].[M 2 (phen) 2 (H 2 O) 2 ] 2 .2(BTC).xH 2 O (M 1 , M 2 =Co(II), Ni(II), Cu(II), Zn(II), or Mn(II), phen=1,10-phenanthroline, BTC=1,3,5-benzenetricarboxylate, x=22-24), were synthesized through self-assembly, and their structures were characterized by IR, elemental analysis, and single-crystal X-ray diffraction. These supramolecular microporous MOFs showed significant size and shape selectivity in the catalyzed oxidation of phenols, which is due to catalytic reactions taking place in the channels of the framework. Design strategy, synthesis, and self-assembly mechanism for the construction of these porous MOFs were discussed. - Grapical abstract: A modular design strategy has been developed to synthesize microporous metal-organic frameworks with potential catalytic activity by self-assembly of the framework-building blocks and the catalyst unit

  7. Hydrogen storage for fuel cell applications: Challenges, opportunities and prospects for metal-organic frameworks

    CSIR Research Space (South Africa)

    Langmi, Henrietta W

    2013-07-01

    Full Text Available and release, and cycle life of the materials. In the past decade, there has been growing interest in metal organic frameworks (MOFs) as hydrogen storage materials and significant progress has been made in this regard. The challenges, opportunities...

  8. On-board co2 capture and storage with metal organic framework

    KAUST Repository

    Eddaoudi, Mohamed; Belmabkhout, Youssef; Shekhah, Osama

    2016-01-01

    In general, this disclosure describes method of capturing and storing CO2 on a vehicle. The method includes contacting an vehicle exhaust gas with one or more of a first metal organic framework (MOF) composition sufficient to separate CO2 from

  9. Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

    KAUST Repository

    Cadiau, Amandine; Belmabkhout, Youssef; Adil, Karim; Bhatt, Prashant; Pillai, Renjith S.; Shkurenko, Aleksander; Martineau-Corcos, Charlotte; Maurin, Guillaume; Eddaoudi, Mohamed

    2017-01-01

    fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas

  10. Lipase-supported metal-organic framework bioreactor catalyzes warfarin synthesis.

    Science.gov (United States)

    Liu, Wan-Ling; Yang, Ni-Shin; Chen, Ya-Ting; Lirio, Stephen; Wu, Cheng-You; Lin, Chia-Her; Huang, Hsi-Ya

    2015-01-02

    A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase-supported metal-organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Gas Phase Sensing of Alcohols by Metal Organic Framework-Polymer Composite Materials

    NARCIS (Netherlands)

    Sachdeva, S.; Koper, S.J.H.; Sabetghadam Esfahani, A.; Soccol, Dimitri; Gravesteijn, Dirk J.; Kapteijn, F.; Sudholter, E.J.R.; Gascon Sabate, J.; de Smet, L.C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al)

  12. Gas Phase Sensing of Alcohols by Metal Organic Framework-Polymer Composite Materials

    NARCIS (Netherlands)

    Sachdeva, Sumit; Koper, Sander J.H.; Sabetghadam, Anahid; Soccol, Dimitri; Gravesteijn, Dirk J.; Kapteijn, Freek; Sudhölter, Ernst J.R.; Gascon, Jorge; Smet, De Louis C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in

  13. Gas phase sensing of alcohols by Metal Organic Framework – polymer composite materials

    NARCIS (Netherlands)

    Sachdeva, S.; Koper, Sander J.H.; Sabetghadam, Anahid; Soccol, D.; Gravesteijn, Dirk J; Kapteijn, Freek; Sudholter, Ernst J.R.; Gascon, Jorge; de Smet, Louis C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in

  14. 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

  15. Metal-Organic Frameworks as Active Materials in Electronic Sensor Devices.

    Science.gov (United States)

    Campbell, Michael G; Dincă, Mircea

    2017-05-12

    In the past decade, advances in electrically conductive metal-organic frameworks (MOFs) and MOF-based electronic devices have created new opportunities for the development of next-generation sensors. Here we review this rapidly-growing field, with a focus on the different types of device configurations that have allowed for the use of MOFs as active components of electronic sensor devices.

  16. Green methods for preparing highly co2 selective and h2s tolerant metal organic frameworks

    KAUST Repository

    Eddaoudi, Mohamed; Shekhah, Osama; Belmabkhout, Youssef

    2015-01-01

    A green route for preparing a metal organic framework include mixing metal precursor with a ligand precursor to form a solvent-free mixture; adding droplets of water to the mixture; heating the mixture at a first temperature after adding the water

  17. Methane storage in porous solids: From Activated Carbons to Metal Organic Frameworks

    OpenAIRE

    Ramos-Fernández, E. V.

    2014-01-01

    [EN]This paper reviews the most promising Metal Organic frameworks for storing natural gas. I discuss the features that make these materials promising for the application. Furthermore, it also indicates how these materials are evaluated and what requirements need to fulfil for being finally applied.

  18. Light-enhanced acid catalysis over a metal-organic framework.

    Science.gov (United States)

    Xu, Caiyun; Sun, Keju; Zhou, Yu-Xiao; Ma, Xiao; Jiang, Hai-Long

    2018-03-06

    A Brønsted acid-functionalized metal-organic framework (MOF), MIL-101-SO 3 H, was prepared for acid-engaged esterification reactions. Strikingly, for the first time, the MOF exhibits significantly light-enhanced activity and possesses excellent activity and recyclability, with even higher activity than H 2 SO 4 under light irradiation.

  19. Separation of polar compounds using a flexible metal-organic framework

    NARCIS (Netherlands)

    Motkuri, R.K.; Thallapally, P.K.; Annapureddy, H.V.R.; Dang, L.X.; Krishna, R.; Nune, S.K.; Fernandez, C.A.; Liu, J.; McGrail, B.P.

    2015-01-01

    A flexible metal-organic framework constructed from a flexible linker is shown to possess the capability of separating mixtures of polar compounds (propanol isomers) by exploiting the differences in the saturation capacities of the constituents. Transient breakthrough simulations show that these

  20. Catalytic behavior of metal-organic frameworks and zeolites: Rationalization and comparative analysis

    Czech Academy of Sciences Publication Activity Database

    Opanasenko, Maksym

    2015-01-01

    Roč. 243, APR 2015 (2015), s. 2-9 ISSN 0920-5861 R&D Projects: GA ČR GA14-07101S Institutional support: RVO:61388955 Keywords : Metal -organic frameworks * Zeolites * heterogeneous catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.312, year: 2015

  1. Hybrid Glasses from Strong and Fragile Metal-Organic Framework Liquids

    DEFF Research Database (Denmark)

    Bennett, T.D.; Tan, J.C.; Yue, Yuanzheng

    2015-01-01

    Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship betwee...

  2. Metal-Organic Frameworks For Adsorption Driven Energy Transformation : From Fundamentals To Applications

    NARCIS (Netherlands)

    De Lange, M.F.

    2015-01-01

    A novel class of materials, i.e. Metal-Organic Frameworks (MOFs), has successfully been developed that is extremely suited for application in heat pumps and chillers. They have a superior performance over commercial sorbents and may potentially contribute to considerable energy savings worldwide.

  3. 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

  4. Small-angle X-ray scattering documents the growth of metal-organic frameworks

    NARCIS (Netherlands)

    Goesten, M.G.; Stavitski, I.; Juan-Alcañiz, J.; Martinez-Joaristi, A.; Petukhov, A.V.; Kapteijn, F.; Gascon, J.

    2013-01-01

    We present a combined in situ small- and wide-angle scattering (SAXS/WAXS) study on the crystallization of two topical metal-organic frameworks synthesized from similar metal and organic precursors: NH2-MIL-53(Al) and NH2-MIL-101(Al). A thorough analysis of SAXS data reveals the most important

  5. Functionalised metal-organic frameworks : A novel approach to stabilising single metal atoms

    NARCIS (Netherlands)

    Szilagyi, P.A.; Rogers, D. M.; Zaiser, I.; Callini, E; Turner, Stuart; Borgschulte, A; Züttel, A.; Geerlings, J.J.C.; Hirscher, M; Dam, B.

    2017-01-01

    We have investigated the potential of metal-organic frameworks for immobilising single atoms of transition metals using a model system of Pd supported on NH2-MIL-101(Cr). Our transmission electron microscopy and in situ Raman spectroscopy results give evidence for the first time that

  6. Metal-Organic Frameworks with d-f Cyanide Bridges: Structural Diversity, Bonding Regime, and Magnetism

    NARCIS (Netherlands)

    Ferbinteanu, M.; Cimpoesu, F.; Tanase, S.; Cheng, P.

    2015-01-01

    We present a selection of metal-organic frameworks based on d-f and f-f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the

  7. Lanthanide-Based Metal Organic Frameworks: Synthetic Strategies and Catalytic Applications

    NARCIS (Netherlands)

    Pagis, C.; Ferbinteanu, M.; Rothenberg, G.; Grecea, S.

    2016-01-01

    This short critical review outlines the main synthetic strategies used in the designed synthesis of lanthanide-based metal organic frameworks (Ln-MOFs). It explains the impact of the choice of organic linker on the final network topology, and it highlights the applications of Ln-MOFs in the

  8. Metal organic frameworks as precursors for the manufacture of advanced catalytic materials

    NARCIS (Netherlands)

    Oar-Arteta Gonzalez, L.; Wezendonk, T.A.; Sun, X.; Kapteijn, F.; Gascon Sabate, J.

    The use of metal organic frameworks as hard templates for the preparation of heterogeneous catalysts is thoroughly reviewed. In this critical article, the main factors to consider when using a MOF as a sacrificial template are first discussed. Then, the existing literature on the topic is reviewed,

  9. 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...

  10. 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.

  11. Giant negative linear compression positively coupled to massive thermal expansion in a metal-organic framework.

    Science.gov (United States)

    Cai, Weizhao; Katrusiak, Andrzej

    2014-07-04

    Materials with negative linear compressibility are sought for various technological applications. Such effects were reported mainly in framework materials. When heated, they typically contract in the same direction of negative linear compression. Here we show that this common inverse relationship rule does not apply to a three-dimensional metal-organic framework crystal, [Ag(ethylenediamine)]NO3. In this material, the direction of the largest intrinsic negative linear compression yet observed in metal-organic frameworks coincides with the strongest positive thermal expansion. In the perpendicular direction, the large linear negative thermal expansion and the strongest crystal compressibility are collinear. This seemingly irrational positive relationship of temperature and pressure effects is explained and the mechanism of coupling of compressibility with expansivity is presented. The positive coupling between compression and thermal expansion in this material enhances its piezo-mechanical response in adiabatic process, which may be used for designing new artificial composites and ultrasensitive measuring devices.

  12. Metal-organic frameworks: structure, properties, methods of synthesis and characterization

    International Nuclear Information System (INIS)

    Butova, V V; Soldatov, M A; Guda, A A; Lomachenko, K A; Lamberti, C

    2016-01-01

    This review deals with key methods of synthesis and characterization of metal-organic frameworks (MOFs). The modular structure affords a wide variety of MOFs with different active metal sites and organic linkers. These compounds represent a new stage of development of porous materials in which the pore size and the active site structure can be modified within wide limits. The set of experimental methods considered in this review is sufficient for studying the short-range and long-range order of the MOF crystal structure, determining the morphology of samples and elucidating the processes that occur at the active metal site in the course of chemical reactions. The interest in metal-organic frameworks results, first of all, from their numerous possible applications, ranging from gas separation and storage to chemical reactions within the pores. The bibliography includes 362 references

  13. Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Ogut, Serdar [Univ. of Illinois, Chicago, IL (United States)

    2017-09-11

    The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyes and metal-organic frameworks.

  14. Synthesis of novel cellulose- based antibacterial composites of Ag nanoparticles@ metal-organic frameworks@ carboxymethylated fibers.

    Science.gov (United States)

    Duan, Chao; Meng, Jingru; Wang, Xinqi; Meng, Xin; Sun, Xiaole; Xu, Yongjian; Zhao, Wei; Ni, Yonghao

    2018-08-01

    A novel cellulose-based antibacterial material, namely silver nanoparticles@ metal-organic frameworks@ carboxymethylated fibers composites (Ag NPs@ HKUST-1@ CFs), was synthesized. The results showed that the metal-organic frameworks (HKUST-1) were uniformly anchored on the fiber's surfaces by virtue of complexation between copper ions in HKUST-1 and carboxyl groups on the carboxymethylated fibers (CFs). The silver nanoparticles (Ag NPs) were immobilized and well-dispersed into the pores and/or onto the surfaces of HKUST-1 via in situ microwave reduction, resulting in the formation of novel Ag NPs@ HKUST-1@ CFs composites. The antibacterial assays showed that the as-prepared composites exhibited a much higher antibacterial activity than Ag NPs@ CFs or HKUST-1@ CFs samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Metal-organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents.

    Science.gov (United States)

    Bobbitt, N Scott; Mendonca, Matthew L; Howarth, Ashlee J; Islamoglu, Timur; Hupp, Joseph T; Farha, Omar K; Snurr, Randall Q

    2017-06-06

    Owing to the vast diversity of linkers, nodes, and topologies, metal-organic frameworks can be tailored for specific tasks, such as chemical separations or catalysis. Accordingly, these materials have attracted significant interest for capture and/or detoxification of toxic industrial chemicals and chemical warfare agents. In this paper, we review recent experimental and computational work pertaining to the capture of several industrially-relevant toxic chemicals, including NH 3 , SO 2 , NO 2 , H 2 S, and some volatile organic compounds, with particular emphasis on the challenging issue of designing materials that selectively adsorb these chemicals in the presence of water. We also examine recent research on the capture and catalytic degradation of chemical warfare agents such as sarin and sulfur mustard using metal-organic frameworks.

  16. Preparation Methods of Metal Organic Frameworks and Their Capture of CO2

    Science.gov (United States)

    Zhang, Linjian; Liand, Fangqin; Luo, Liangfei

    2018-01-01

    The increasingly serious greenhouse effect makes people pay more attention to the capture and storage technology of CO2. Metal organic frameworks (MOFs) have the advantages of high specific surface area, porous structure and controllable structure, and become the research focus of CO2 emission reduction technology in recent years. In this paper, the characteristics, preparation methods and application of MOFs in the field of CO2 adsorption and separation are discussed, especially the application of flue gas environment in power plants.

  17. A high rotational barrier for physisorbed hydrogen in an fcu-metal-organic framework

    KAUST Repository

    Pham, Tony T.; Forrest, Katherine A.; Georgiev, Peter A L; Lohstroh, Wiebke; Xue, Dongxu; Hogan, Adam; Eddaoudi, Mohamed; Space, Brian; Eckert, Juergen

    2014-01-01

    A combined inelastic neutron scattering (INS) and theoretical study of H2 sorption in Y-FTZB, a recently reported metal-organic framework (MOF) with fcu topology, reveals that the strongest binding site in the MOF causes a high barrier to rotation on the sorbed H2. This rotational barrier for H2 is the highest yet of reported MOF materials based on physisorption. This journal is

  18. ENHANCEMENT OF ACIDITY AND CATALYTIC ACTIVITY OF ALUMINA BASED METAL ORGANIC FRAMEWORK (MIL-53 Al)

    OpenAIRE

    Yilmaz, Esra; Sert, Emine; Atalay, Ferhan Sami

    2017-01-01

    Metal organic frameworks are highly porous materials which are formed bycombination of metal precursor and salts as inorganic part and ligand asorganic part. They have many advantages such as low density, high surface area,tunable pore size and high porosity. Due to peculiar features, such asunsaturated metal active sites, high surface area and easily functionalization,its usage as catalyst are promising.  The MIL-53(Al) structure contains chains of transcorner-sharing [AlO4(OH)2] oc...

  19. Metal-organic framework tethering PNIPAM for ON-OFF controlled release in solution.

    Science.gov (United States)

    Nagata, Shunjiro; Kokado, Kenta; Sada, Kazuki

    2015-05-21

    A smart metal-organic framework (MOF) exhibiting controlled release was achieved by modification with a thermoresponsive polymer (PNIPAM) via a surface-selective post-synthetic modification technique. Simple temperature variation readily switches "open" (lower temperature) and "closed" (higher temperature) states of the polymer-modified MOF through conformational change of PNIPAM grafted onto the MOF, resulting in controlled release of the included guest molecules such as resorufin, caffeine, and procainamide.

  20. Nano- and microsized cubic gel particles from cyclodextrin metal-organic frameworks.

    Science.gov (United States)

    Furukawa, Yuki; Ishiwata, Takumi; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

    2012-10-15

    Sweet cube o' mine: Bottom-up control of gel particles has been regarded as a great challenge. By employing internal cross-linking of cyclodextrin metal-organic frameworks, cubic sugar gels were formed with sharp edges that reflect the shape of the crystals. This enabled the fabrication of shape- and size-controlled polymer gels from porous crystals (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Photoswitchable nanoporous films by loading azobenzene in metal-organic frameworks of type HKUST-1.

    Science.gov (United States)

    Müller, Kai; Wadhwa, Jasmine; Singh Malhi, Jasleen; Schöttner, Ludger; Welle, Alexander; Schwartz, Heidi; Hermann, Daniela; Ruschewitz, Uwe; Heinke, Lars

    2017-07-13

    Photoswitchable metal-organic frameworks (MOFs) enable the dynamic remote control of their key properties. Here, a readily producible approach is presented where photochromic molecules, i.e. azobenzene (AB) and o-tetrafluoroazobenzene (tfAB), are loaded in MOF films of type HKUST-1. These nanoporous films, which can be reversibly switched with UV/visible or only visible light, have remote-controllable guest uptake properties.

  2. Graphene inclusion controlling conductivity and gas sorption of metal-organic framework

    OpenAIRE

    Lamagni, Paolo; Pedersen, Birgitte Lodberg; Godiksen, Anita; Mossin, Susanne; Hu, Xin Ming; Pedersen, Steen Uttrup; Daasbjerg, Kim; Lock, Nina

    2018-01-01

    A general approach to prepare composite films of metal-organic frameworks and graphene has been developed. Films of copper(ii)-based HKUST-1 and HKUST-1/graphene composites were grown solvothermally on glassy carbon electrodes. The films were chemically tethered to the substrate by diazonium electrografting resulting in a large electrode coverage and good stability in solution for electrochemical studies. HKUST-1 has poor electrical conductivity, but we demonstrate that the addition of graphe...

  3. Surfactant media to grow new crystalline cobalt 1,3,5-benzenetricarboxylate metal-organic frameworks

    KAUST Repository

    Lu, Haisheng; Bai, Linlu; Xiong, Weiwei; Li, Peizhou; Ding, Junfeng; Zhang, Guodong; Wu, Tao; Zhao, Yanli; Lee, Jongmin; Yang, Yanhui; Geng, Baoyou; Zhang, Qichun

    2014-01-01

    In this report, three new metal-organic frameworks (MOFs), [Co 3(μ3-OH)(HBTC)(BTC)2Co(HBTC)]·(HTEA) 3·H2O (NTU-Z30), [Co(BTC)] ·HTEA·H2O (NTU-Z31), [Co3(BTC) 4]·(HTEA)4 (NTU-Z32), where H3BTC = 1,3,5-benzenetricarboxylic acid, TEA = triethylamine

  4. Metal-Organic Framework-Stabilized CO2/Water Interfacial Route for Photocatalytic CO2 Conversion.

    Science.gov (United States)

    Luo, Tian; Zhang, Jianling; Li, Wei; He, Zhenhong; Sun, Xiaofu; Shi, Jinbiao; Shao, Dan; Zhang, Bingxing; Tan, Xiuniang; Han, Buxing

    2017-11-29

    Here, we propose a CO 2 /water interfacial route for photocatalytic CO 2 conversion by utilizing a metal-organic framework (MOF) as both an emulsifier and a catalyst. The CO 2 reduction occurring at the CO 2 /water interface produces formate with remarkably enhanced efficiency as compared with that in conventional solvent. The route is efficient, facile, adjustable, and environmentally benign, which is applicable for the CO 2 transformation photocatalyzed by different kinds of MOFs.

  5. Copper Benzenetricarboxylate Metal-Organic Framework Nucleation Mechanisms on Metal Oxide Powders and Thin Films formed by Atomic Layer Deposition.

    Science.gov (United States)

    Lemaire, Paul C; Zhao, Junjie; Williams, Philip S; Walls, Howard J; Shepherd, Sarah D; Losego, Mark D; Peterson, Gregory W; Parsons, Gregory N

    2016-04-13

    Chemically functional microporous metal-organic framework (MOF) crystals are attractive for filtration and gas storage applications, and recent results show that they can be immobilized on high surface area substrates, such as fiber mats. However, fundamental knowledge is still lacking regarding initial key reaction steps in thin film MOF nucleation and growth. We find that thin inorganic nucleation layers formed by atomic layer deposition (ALD) can promote solvothermal growth of copper benzenetricarboxylate MOF (Cu-BTC) on various substrate surfaces. The nature of the ALD material affects the MOF nucleation time, crystal size and morphology, and the resulting MOF surface area per unit mass. To understand MOF nucleation mechanisms, we investigate detailed Cu-BTC MOF nucleation behavior on metal oxide powders and Al2O3, ZnO, and TiO2 layers formed by ALD on polypropylene substrates. Studying both combined and sequential MOF reactant exposure conditions, we find that during solvothermal synthesis ALD metal oxides can react with the MOF metal precursor to form double hydroxy salts that can further convert to Cu-BTC MOF. The acidic organic linker can also etch or react with the surface to form MOF from an oxide metal source, which can also function as a nucleation agent for Cu-BTC in the mixed solvothermal solution. We discuss the implications of these results for better controlled thin film MOF nucleation and growth.

  6. Surfactant-thermal method to prepare two new cobalt metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xianglin [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430074 (China); Toh, Yong Siang [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Zhao, Jun [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Nie, Lina [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Ye, Kaiqi; Wang, Yue [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012 (China); Li, Dongsheng [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Zhang, Qichun, E-mail: qczhang@ntu.edu.sg [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)

    2015-12-15

    Employing surfactants as reaction media, two new metal-organic frameworks (MOFs):(HTEA){sub 3}[Co{sub 3}(BTC){sub 3}] (NTU-Z33) and (HTEA)[Co{sub 3}(HBTC){sub 2}(BTC)] (NTU-Z34) (H{sub 3}BTC=1,3,5-benzenetricarboxylic acid, TEA=trimethylamine, and NTU=Nanyang Technological University), have been successfully synthesized and fully characterized. Note that NTU-Z33 has an unusual trimeric [Co{sub 3}(COO){sub 9}] secondary building unit (SBU). Magnetic characterization suggests that both compounds have weak antiferromagnetic behaviors. Our success in preparing new crystalline Co-BTC based MOFs under different surfactant media could provide a new road to prepare new diverse MOFs through various combinations of surfactants. - Graphical abstract: Employing surfactants as reaction media, two new metal-organic frame-works (MOFs) have been successfully synthesized and magnetic study suggests that both compounds have weak antiferromagnetic behaviors. - Highlights: • Two novel metal-organic frame-works (MOFs). • Synthesis through surfactant-thermal condition. • weak antiferromagnetic behaviors for both compounds.

  7. Capture of organic iodides from nuclear waste by metal-organic framework-based molecular traps.

    Science.gov (United States)

    Li, Baiyan; Dong, Xinglong; Wang, Hao; Ma, Dingxuan; Tan, Kui; Jensen, Stephanie; Deibert, Benjamin J; Butler, Joseph; Cure, Jeremy; Shi, Zhan; Thonhauser, Timo; Chabal, Yves J; Han, Yu; Li, Jing

    2017-09-07

    Effective capture of radioactive organic iodides from nuclear waste remains a significant challenge due to the drawbacks of current adsorbents such as low uptake capacity, high cost, and non-recyclability. We report here a general approach to overcome this challenge by creating radioactive organic iodide molecular traps through functionalization of metal-organic framework materials with tertiary amine-binding sites. The molecular trap exhibits a high CH 3 I saturation uptake capacity of 71 wt% at 150 °C, which is more than 340% higher than the industrial adsorbent Ag 0 @MOR under identical conditions. These functionalized metal-organic frameworks also serve as good adsorbents at low temperatures. Furthermore, the resulting adsorbent can be recycled multiple times without loss of capacity, making recyclability a reality. In combination with its chemical and thermal stability, high capture efficiency and low cost, the adsorbent demonstrates promise for industrial radioactive organic iodides capture from nuclear waste. The capture mechanism was investigated by experimental and theoretical methods.Capturing radioactive organic iodides from nuclear waste is important for safe nuclear energy usage, but remains a significant challenge. Here, Li and co-workers fabricate a stable metal-organic framework functionalized with tertiary amine groups that exhibits high capacities for radioactive organic iodides uptake.

  8. Surfactant-thermal method to prepare two new cobalt metal-organic frameworks

    International Nuclear Information System (INIS)

    Yu, Xianglin; Toh, Yong Siang; Zhao, Jun; Nie, Lina; Ye, Kaiqi; Wang, Yue; Li, Dongsheng; Zhang, Qichun

    2015-01-01

    Employing surfactants as reaction media, two new metal-organic frameworks (MOFs):(HTEA)_3[Co_3(BTC)_3] (NTU-Z33) and (HTEA)[Co_3(HBTC)_2(BTC)] (NTU-Z34) (H_3BTC=1,3,5-benzenetricarboxylic acid, TEA=trimethylamine, and NTU=Nanyang Technological University), have been successfully synthesized and fully characterized. Note that NTU-Z33 has an unusual trimeric [Co_3(COO)_9] secondary building unit (SBU). Magnetic characterization suggests that both compounds have weak antiferromagnetic behaviors. Our success in preparing new crystalline Co-BTC based MOFs under different surfactant media could provide a new road to prepare new diverse MOFs through various combinations of surfactants. - Graphical abstract: Employing surfactants as reaction media, two new metal-organic frame-works (MOFs) have been successfully synthesized and magnetic study suggests that both compounds have weak antiferromagnetic behaviors. - Highlights: • Two novel metal-organic frame-works (MOFs). • Synthesis through surfactant-thermal condition. • weak antiferromagnetic behaviors for both compounds.

  9. Capture of organic iodides from nuclear waste by metal-organic framework-based molecular traps

    KAUST Repository

    Li, Baiyan

    2017-09-01

    Effective capture of radioactive organic iodides from nuclear waste remains a significant challenge due to the drawbacks of current adsorbents such as low uptake capacity, high cost, and non-recyclability. We report here a general approach to overcome this challenge by creating radioactive organic iodide molecular traps through functionalization of metal-organic framework materials with tertiary amine-binding sites. The molecular trap exhibits a high CH3I saturation uptake capacity of 71 wt% at 150 °C, which is more than 340% higher than the industrial adsorbent Ag0@MOR under identical conditions. These functionalized metal-organic frameworks also serve as good adsorbents at low temperatures. Furthermore, the resulting adsorbent can be recycled multiple times without loss of capacity, making recyclability a reality. In combination with its chemical and thermal stability, high capture efficiency and low cost, the adsorbent demonstrates promise for industrial radioactive organic iodides capture from nuclear waste. The capture mechanism was investigated by experimental and theoretical methods.Capturing radioactive organic iodides from nuclear waste is important for safe nuclear energy usage, but remains a significant challenge. Here, Li and co-workers fabricate a stable metal-organic framework functionalized with tertiary amine groups that exhibits high capacities for radioactive organic iodides uptake.

  10. Dubinin-Astakhov model for acetylene adsorption on metal-organic frameworks

    International Nuclear Information System (INIS)

    Cheng, Peifu; Hu, Yun Hang

    2016-01-01

    Graphical abstract: It was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model for C2H2 adsorption on metal-organic frameworks (MOFs), including MOF-5, ZIF-8, HKUST-1, and MIL-53. - Highlights: • Dubinin-Astakhov equation is demonstrated to be a general model for C_2H_2 adsorption on metal-organic frameworks (MOFs). • Surface areas obtained with Dubinin-Astakhov equation from C_2H_2 adsorption on MOFs are consistent with BET surface areas from N_2 adsorption. • C_2H_2 on MOF-5, ZIF-8, and MIL-53 is a physical adsorption, whereas its adsorption on HKUST-1 is due to a chemical bonding. - Abstract: Acetylene (C_2H_2) is explosive at a pressure above 29 psi, causing a safety issue for its storage and applications. C_2H_2 adsorption on metal-organic frameworks (MOFs) has been explored to solve the issue. However, a suitable isotherm equation for C_2H_2 adsorption on various MOFs has not been found. In this paper, it was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model to depict C_2H_2 adsorption on MOF-5, ZIF-8, HKUST-1, and MIL-53. In contrast, commonly used Langmuir and BET models exhibited their inapplicability for C_2H_2 adsorption on those MOFs.

  11. Impact of metal and anion substitutions on the hydrogen storage properties of M-BTT metal-organic frameworks.

    Science.gov (United States)

    Sumida, Kenji; Stück, David; Mino, Lorenzo; Chai, Jeng-Da; Bloch, Eric D; Zavorotynska, Olena; Murray, Leslie J; Dincă, Mircea; Chavan, Sachin; Bordiga, Silvia; Head-Gordon, Martin; Long, Jeffrey R

    2013-01-23

    Microporous metal-organic frameworks are a class of materials being vigorously investigated for mobile hydrogen storage applications. For high-pressure storage at ambient temperatures, the M(3)[(M(4)Cl)(3)(BTT)(8)](2) (M-BTT; BTT(3-) = 1,3,5-benzenetristetrazolate) series of frameworks are of particular interest due to the high density of exposed metal cation sites on the pore surface. These sites give enhanced zero-coverage isosteric heats of adsorption (Q(st)) approaching the optimal value for ambient storage applications. However, the Q(st) parameter provides only a limited insight into the thermodynamics of the individual adsorption sites, the tuning of which is paramount for optimizing the storage performance. Here, we begin by performing variable-temperature infrared spectroscopy studies of Mn-, Fe-, and Cu-BTT, allowing the thermodynamics of H(2) adsorption to be probed experimentally. This is complemented by a detailed DFT study, in which molecular fragments representing the metal clusters within the extended solid are simulated to obtain a more thorough description of the structural and thermodynamic aspects of H(2) adsorption at the strongest binding sites. Then, the effect of substitutions at the metal cluster (metal ion and anion within the tetranuclear cluster) is discussed, showing that the configuration of this unit indeed plays an important role in determining the affinity of the framework toward H(2). Interestingly, the theoretical study has identified that the Zn-based analogs would be expected to facilitate enhanced adsorption profiles over the compounds synthesized experimentally, highlighting the importance of a combined experimental and theoretical approach to the design and synthesis of new frameworks for H(2) storage applications.

  12. Metal-organic frameworks for analytical chemistry: from sample collection to chromatographic separation.

    Science.gov (United States)

    Gu, Zhi-Yuan; Yang, Cheng-Xiong; Chang, Na; Yan, Xiu-Ping

    2012-05-15

    In modern analytical chemistry researchers pursue novel materials to meet analytical challenges such as improvements in sensitivity, selectivity, and detection limit. Metal-organic frameworks (MOFs) are an emerging class of microporous materials, and their unusual properties such as high surface area, good thermal stability, uniform structured nanoscale cavities, and the availability of in-pore functionality and outer-surface modification are attractive for diverse analytical applications. This Account summarizes our research on the analytical applications of MOFs ranging from sampling to chromatographic separation. MOFs have been either directly used or engineered to meet the demands of various analytical applications. Bulk MOFs with microsized crystals are convenient sorbents for direct application to in-field sampling and solid-phase extraction. Quartz tubes packed with MOF-5 have shown excellent stability, adsorption efficiency, and reproducibility for in-field sampling and trapping of atmospheric formaldehyde. The 2D copper(II) isonicotinate packed microcolumn has demonstrated large enhancement factors and good shape- and size-selectivity when applied to on-line solid-phase extraction of polycyclic aromatic hydrocarbons in water samples. We have explored the molecular sieving effect of MOFs for the efficient enrichment of peptides with simultaneous exclusion of proteins from biological fluids. These results show promise for the future of MOFs in peptidomics research. Moreover, nanosized MOFs and engineered thin films of MOFs are promising materials as novel coatings for solid-phase microextraction. We have developed an in situ hydrothermal growth approach to fabricate thin films of MOF-199 on etched stainless steel wire for solid-phase microextraction of volatile benzene homologues with large enhancement factors and wide linearity. Their high thermal stability and easy-to-engineer nanocrystals make MOFs attractive as new stationary phases to fabricate MOF

  13. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    Energy Technology Data Exchange (ETDEWEB)

    Annapureddy, HVR; Motkuri, RK; Nguyen, PTM; Truong, TB; Thallapally, PK; McGrail, BP; Dang, LX

    2014-02-05

    In this review, we describe recent efforts to systematically study nano-structured metal organic frameworks (MOFs), also known as metal organic heat carriers, with particular emphasis on their application in heating and cooling processes. We used both molecular dynamics and grand canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a. We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available measurements from experiments, thus validating our potential models and approaches. In addition, we investigated the structural, diffusive and adsorption properties of different hydrocarbons in Ni-2(dhtp). Finally, to elucidate the mechanism of nanoparticle dispersion in condensed phases, we studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol.

  14. Chiral metal-organic frameworks bearing free carboxylic acids for organocatalyst encapsulation.

    Science.gov (United States)

    Liu, Yan; Xi, Xiaobing; Ye, Chengcheng; Gong, Tengfei; Yang, Zhiwei; Cui, Yong

    2014-12-08

    Two chiral carboxylic acid functionalized micro- and mesoporous metal-organic frameworks (MOFs) are constructed by the stepwise assembly of triple-stranded heptametallic helicates with six carboxylic acid groups. The mesoporous MOF with permanent porosity functions as a host for encapsulation of an enantiopure organic amine catalyst by combining carboxylic acids and chiral amines in situ through acid-base interactions. The organocatalyst-loaded framework is shown to be an efficient and recyclable heterogeneous catalyst for the asymmetric direct aldol reactions with significantly enhanced stereoselectivity in relative to the homogeneous organocatalyst. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Tunable photoluminescent metal-organic-frameworks and method of making the same

    Energy Technology Data Exchange (ETDEWEB)

    Nenoff, Tina M.; Sava Gallis, Dorina Florentina; Rohwer, Lauren E.S.

    2017-08-22

    The present disclosure is directed to new photoluminescent metal-organic frameworks (MOFs). The newly developed MOFs include either non rare earth element (REE) transition metal atoms or limited concentrations of REE atoms, including: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Ru, Ag, Cd, Sn, Sb, Ir, Pb, Bi, that are located in the MOF framework in site isolated locations, and have emission colors ranging from white to red, depending on the metal concentration levels and/or choice of ligand.

  16. Design, Synthesis and Characterization of Functional Metal-Organic Framework Materials

    KAUST Repository

    Alamer, Badriah

    2015-06-01

    Over the past few decades, vast majority of industrial and academic research throughout the world has witnessed the emergence of materials that can serve as ideal candidates for potential utility in desired applications, and these materials are known as Metal Organic Framework (MOFs). This exceptional new family of porous materials is fabricated by linkage of metal ions or clusters and organic linkers via strong bonds. MOFs have been awarded with remarkable interest and widely studied due to their inherent structural methodology (e.g. use of various metals, expanded library of organic building blocks with different geometry and functionality particularly frameworks designed from carboxylate organic linkers) and unquestionably unique structural and chemical features for many practical applications. (i.e. gas storage/separation, catalysis, drug delivery etc). Simply, metal organic frameworks epitomize the beauty of porous chemical structures. From a design perspective, the introduction of the Molecular Building Block (MBB) approach is actively being pursued pathway by researchers toward the construction of MOFs by employing inorganic building blocks and organic linkers and taking advantage of not only their multiple coordination modes and geometries but also the way in which they are reticulated to generate final framework. In this thesis, research studies will be directed toward (i) the investigation of the relationship between experimental parameters and synthesis of well-known fcu –MOF, (ii) rational design and synthesis of new rare earth (RE) based MOFs, (ii) isoreticular materials based on particular MBB ([M3O(RCO2)6]), M= p-and d-block metals, and (iv) zeolite- like metal organic framework assembled from single-metal ion based MBB ([MN2(CO2)4]) via 2-, 3-,and 4-connected organic linkers. Consequently, the porosity, chemical and thermal stability, and gas sorption properties will be evaluated and detailed.

  17. 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.

  18. 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.

  19. Highly stable [mambf6-n(o/h2o)n(ligand)2(solvent)x]n metal organic frameworks

    KAUST Repository

    Eddaoudi, Mohamed

    2016-10-13

    Provided herein are metal organic frameworks having high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Metal organic frameworks can comprise metal nodes and N-donor organic ligands. Further provided are methods of making metal organic frameworks.

  20. Reticular Chemistry and Metal-Organic Frameworks: Design and Synthesis of Functional Materials for Clean Energy Applications

    KAUST Repository

    Alezi, Dalal

    2017-01-01

    Gaining control over the assembly of crystalline solid-state materials has been significantly advanced through the field of reticular chemistry and metal organic frameworks (MOFs). MOFs have emerged as a unique modular class of porous materials

  1. 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...

  2. Missing Linker Defects in a Homochiral Metal-Organic Framework: Tuning the Chiral Separation Capacity.

    Science.gov (United States)

    Slater, Benjamin; Wang, Zeru; Jiang, Shanxue; Hill, Matthew R; Ladewig, Bradley P

    2017-12-20

    Efficient chiral separation remains a very challenging task due to the identical physical and chemical properties of the enantiomers of a molecule. Enantiomers only behave differently from each other in the presence of other chiral species. Homochiral metal-organic frameworks (MOFs) have received much attention for their promising enantioseparation properties. However, there are still challenges to overcome in this field such as high enantiomeric separation. Structural defects play an important role in the properties of MOFs and can significantly change the pore architecture. In this work, we introduced missing linker defects into a homochiral metal-organic framework [Zn 2 (bdc)(l-lac)(dmf)] (ZnBLD; bdc = 1,4-benzenedicarboxylic acid, l-lac = l-lactic acid, dmf = N,N'-dimethylformamide) and observed an increase in enantiomeric excess for 1-phenylethanol of 35% with the defective frameworks. We adjusted the concentration of monocarboxylic acid ligand l-lactic acid by varying the ratio of Zn 2+ to ligand from 0.5 to 0.85 mmol. Additionally, a defective framework was synthesized with propanoic acid as modulator. In order to elucidate the correlation between defects and enantiomeric excess, five characterization techniques (FTIR, TGA, 1 H NMR, ICP, and PXRD) were employed. Full width at half-maximum analysis (fwhm) was performed on the powder X-ray diffraction traces and showed that the higher concentration of monocarboxylic acid MOFs were isostructural but suffered from increased fwhm values.

  3. CFA-7: an interpenetrated metal-organic framework of the MFU-4 family.

    Science.gov (United States)

    Schmieder, Phillip; Grzywa, Maciej; Denysenko, Dmytro; Hambach, Manuel; Volkmer, Dirk

    2015-08-07

    The novel interpenetrated metal-organic framework CFA-7 (Coordination Framework Augsburg University-7), [Zn5Cl4(tqpt)3], has been synthesized containing the organic linker {H2-tqpt = 6,6,14,14-tetramethyl-6,14-dihydroquinoxalino[2,3-b]phenazinebistriazole}. Reaction of H2-tqpt and anhydrous ZnCl2 in N,N-dimethylformamide (DMF) yields CFA-7 as pseudo-cubic crystals. CFA-7 serves as precursor for the synthesis of isostructural frameworks with redox-active metal centers, which is demonstrated by postsynthetic metal exchange of Zn(2+) by different M(2+) (M = Co, Ni, Cu) ions. The novel framework is robust upon solvent removal and has been structurally characterized by single-crystal X-ray diffraction, TGA and IR spectroscopy, as well as gas sorption (Ar, CO2 and H2).

  4. Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution.

    Science.gov (United States)

    Liu, Shaohong; Wang, Zhiyu; Zhou, Si; Yu, Fengjiao; Yu, Mengzhou; Chiang, Chang-Yang; Zhou, Wuzong; Zhao, Jijun; Qiu, Jieshan

    2017-08-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO 2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Structure-Property of Metal Organic Frameworks Calcium Terephthalates Anodes for Lithium-ion Batteries

    International Nuclear Information System (INIS)

    Wang, Liping; Mou, Chengxu; Sun, Yang; Liu, Wei; Deng, Qijiu; Li, Jingze

    2015-01-01

    Graphical Abstract: Effects of hydration water in calcium terephthalates anodes on the structure, operational voltage and electrochemical performance are systematically studied. Display Omitted -- Highlights: •Metal organic frameworks CaC 8 H 4 O 4 ·3H 2 O and CaC 8 H 4 O 4 are applied as anodes for lithium ion batteries. •Appearance of hydration water leads different crystallography structures and electrochemical performance. •Anhydrous CaC 8 H 4 O 4 has a spacious ordered layer structure, a higher Ca-O chemical bonding interaction and a higher transparent lithium ion diffusion coefficient, delivering a higher capacity, better cycling performance and rate performance than CaC 8 H 4 O 4 ·3H 2 O. -- Abstract: Metal organic frameworks have attracted considerable interest as electrode materials for lithium ion batteries. In this paper, the metal organic frameworks hydrated calcium terephthalate (CaC 8 H 4 O 4 ·3H 2 O) and anhydrous calcium terephthalate (CaC 8 H 4 O 4 ) as anodes for lithium ion batteries are comparatively studied. Crystallography and local chemical bond analysis are combined to interpret the structure-property of calcium terephthalates. Results show that the anhydrous CaC 8 H 4 O 4 has a spacious ordered layer structure and a higher Ca-O chemical bonding interaction, delivering a higher capacity, better cycling performance and rate performance than CaC 8 H 4 O 4 ·3H 2 O

  6. Dubinin-Astakhov model for acetylene adsorption on metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Peifu; Hu, Yun Hang, E-mail: yunhangh@mtu.edu

    2016-07-30

    Graphical abstract: It was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model for C2H2 adsorption on metal-organic frameworks (MOFs), including MOF-5, ZIF-8, HKUST-1, and MIL-53. - Highlights: • Dubinin-Astakhov equation is demonstrated to be a general model for C{sub 2}H{sub 2} adsorption on metal-organic frameworks (MOFs). • Surface areas obtained with Dubinin-Astakhov equation from C{sub 2}H{sub 2} adsorption on MOFs are consistent with BET surface areas from N{sub 2} adsorption. • C{sub 2}H{sub 2} on MOF-5, ZIF-8, and MIL-53 is a physical adsorption, whereas its adsorption on HKUST-1 is due to a chemical bonding. - Abstract: Acetylene (C{sub 2}H{sub 2}) is explosive at a pressure above 29 psi, causing a safety issue for its storage and applications. C{sub 2}H{sub 2} adsorption on metal-organic frameworks (MOFs) has been explored to solve the issue. However, a suitable isotherm equation for C{sub 2}H{sub 2} adsorption on various MOFs has not been found. In this paper, it was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model to depict C{sub 2}H{sub 2} adsorption on MOF-5, ZIF-8, HKUST-1, and MIL-53. In contrast, commonly used Langmuir and BET models exhibited their inapplicability for C{sub 2}H{sub 2} adsorption on those MOFs.

  7. The direct heat measurement of mechanical energy storage metal-organic frameworks.

    Science.gov (United States)

    Rodriguez, Julien; Beurroies, Isabelle; Loiseau, Thierry; Denoyel, Renaud; Llewellyn, Philip L

    2015-04-07

    In any process, the heat exchanged is an essential property required in its development. Whilst the work related to structural transitions of some flexible metal-organic frameworks (MOFs) has been quantified and linked with potential applications such as molecular springs or shock absorbers, the heat related to such transitions has never been directly measured. This has now been carried out with MIL-53(Al) using specifically devised calorimetry experiments. We project the importance of these heats in devices such as molecular springs or dampers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Metal-Organic-Framework-Mediated Nitrogen-Doped Carbon for CO2 Electrochemical Reduction

    KAUST Repository

    Wang, Riming; Sun, Xiaohui; Ould-Chikh, Samy; Osadchii, Dmitrii; Bai, Fan; Kapteijn, Freek; Gascon, Jorge

    2018-01-01

    A nitrogen-doped carbon was synthesized through the pyrolysis of the well-known metal-organic framework ZIF-8, followed by a subsequent acid treatment, and has been applied as a catalyst in the electrochemical reduction of carbon dioxide. The resulting electrode shows Faradaic efficiencies to carbon monoxide as high as ∼78%, with hydrogen being the only byproduct. The pyrolysis temperature determines the amount and the accessibility of N species in the carbon electrode, in which pyridinic-N and quaternary-N species play key roles in the selective formation of carbon monoxide.

  9. A highly stable zeotype mesoporous zirconium metal-organic framework with ultralarge pores.

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Dawei; Wang, Kecheng; Su, Jie; Liu, Tian-Fu; Park, Jihye; Wei, Zhangwen; Bosch, Mathieu; Yakovenko, Andrey; Zou, Xiaodong; Zhou, Hong-Cai

    2015-01-02

    Through topological rationalization, a zeotype mesoporous Zr-containing metal-organic framework (MOF), namely PCN-777, has been designed and synthesized. PCN-777 exhibits the largest cage size of 3.8nm and the highest pore volume of 2.8cm(3)g(-1) among reported Zr-MOFs. Moreover, PCN-777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN-777 and different guests can be varied to realize efficient immobilization

  10. Metal-organic frameworks and their applications in catalysis; Redes metalorganicas e suas aplicacoes em catalise

    Energy Technology Data Exchange (ETDEWEB)

    Ramos, Andre Luis Dantas, E-mail: aldramos@ufs.br [Universidade Federal de Sergipe (UFSE), Sao Cristovao, SE (Brazil). Departamento de Engenharia Quimica; Tanase, Stefania; Rothenberg, Gadi [Van' t Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam (Netherlands)

    2014-07-01

    Metal-organic frameworks (MOFs) form a new class of materials with well-defined yet tunable properties. These are crystalline, highly porous and exhibit strong metal-ligand interactions. Importantly, their physical and chemical properties, including pore size, pore structure, acidity, and magnetic and optical characteristics, can be tailored by choosing the appropriate ligands and metal precursors. Here we review the key aspects of synthesis and characterization of MOFs, focusing on lanthanide-based and vanadium-based materials. We also outline some of their applications in catalysis and materials science. (author)

  11. Versatile, High Quality and Scalable Continuous Flow Production of Metal-Organic Frameworks

    Science.gov (United States)

    Rubio-Martinez, Marta; Batten, Michael P.; Polyzos, Anastasios; Carey, Keri-Constanti; Mardel, James I.; Lim, Kok-Seng; Hill, Matthew R.

    2014-01-01

    Further deployment of Metal-Organic Frameworks in applied settings requires their ready preparation at scale. Expansion of typical batch processes can lead to unsuccessful or low quality synthesis for some systems. Here we report how continuous flow chemistry can be adapted as a versatile route to a range of MOFs, by emulating conditions of lab-scale batch synthesis. This delivers ready synthesis of three different MOFs, with surface areas that closely match theoretical maxima, with production rates of 60 g/h at extremely high space-time yields. PMID:24962145

  12. Metal-Organic-Framework-Mediated Nitrogen-Doped Carbon for CO2 Electrochemical Reduction

    KAUST Repository

    Wang, Riming

    2018-04-11

    A nitrogen-doped carbon was synthesized through the pyrolysis of the well-known metal-organic framework ZIF-8, followed by a subsequent acid treatment, and has been applied as a catalyst in the electrochemical reduction of carbon dioxide. The resulting electrode shows Faradaic efficiencies to carbon monoxide as high as ∼78%, with hydrogen being the only byproduct. The pyrolysis temperature determines the amount and the accessibility of N species in the carbon electrode, in which pyridinic-N and quaternary-N species play key roles in the selective formation of carbon monoxide.

  13. A Redox-Active Bistable Molecular Switch Mounted inside a Metal-Organic Framework.

    Science.gov (United States)

    Chen, Qishui; Sun, Junling; Li, Peng; Hod, Idan; Moghadam, Peyman Z; Kean, Zachary S; Snurr, Randall Q; Hupp, Joseph T; Farha, Omar K; Stoddart, J Fraser

    2016-11-02

    We describe the incorporation of a bistable mechanically interlocked molecule (MIM) into a robust Zr-based metal-organic framework (MOF), NU-1000, by employing a post-synthetic functionalization protocol. On average, close to two bistable [2]catenanes can be incorporated per repeating unit of the hexagonal channels of NU-1000. The reversible redox-switching of the bistable [2]catenanes is retained inside the MOF, as evidenced by solid-state UV-vis-NIR reflectance spectroscopy and cyclic voltammetry. This research demonstrates that bistable MIMs are capable of exhibiting robust dynamics inside the nanopores of a MOF.

  14. Electrodeposition of WO3 nanoparticles into surface mounted metal-organic framework HKUST-1 thin films

    Science.gov (United States)

    Yoo, Hyeonseok; Welle, Alexander; Guo, Wei; Choi, Jinsub; Redel, Engelbert

    2017-03-01

    We describe a novel procedure to fabricate WO3@surface-mounted metal-organic framework (SURMOF) hybrid materials by electrodeposition of WO3 nanoparticles into HKUST-1, also termed Cu3(BTC)2 SURMOFs. These materials have been characterized using x-ray diffraction, time-of-flight secondary ion mass spectrometry, scanning electron microscopy, x-ray photoelectron spectroscopy as well as linear sweep voltammetry. The WO3 semiconductor/SURMOF heterostructures were further tested as hybrid electrodes in their performance for hydrogen evolution reaction from water.

  15. Transient Mass and Thermal Transport during Methane Adsorption into the Metal-Organic Framework HKUST-1.

    Science.gov (United States)

    Babaei, Hasan; McGaughey, Alan J H; Wilmer, Christopher E

    2018-01-24

    Methane adsorption into the metal-organic framework (MOF) HKUST-1 and the resulting heat generation and dissipation are investigated using molecular dynamics simulations. Transient simulations reveal that thermal transport in the MOF occurs two orders of magnitude faster than gas diffusion. A large thermal resistance at the MOF-gas interface (equivalent to 127 nm of bulk HKUST-1), however, prevents fast release of the generated heat. The mass transport resistance at the MOF-gas interface is equivalent to 1 nm of bulk HKUST-1 and does not present a bottleneck in the adsorption process. These results provide important insights into the application of MOFs for gas storage applications.

  16. Mechanical properties of metal-organic frameworks: An indentation study on epitaxial thin films

    Science.gov (United States)

    Bundschuh, S.; Kraft, O.; Arslan, H. K.; Gliemann, H.; Weidler, P. G.; Wöll, C.

    2012-09-01

    We have determined the hardness and Young's modulus of a highly porous metal-organic framework (MOF) using a standard nanoindentation technique. Despite the very low density of these films, 1.22 g cm-3, Young's modulus reaches values of almost 10 GPa for HKUST-1, demonstrating that this porous coordination polymer is substantially stiffer than normal polymers. This progress in characterizing mechanical properties of MOFs has been made possible by the use of high quality, oriented thin films grown using liquid phase epitaxy on modified Au substrates.

  17. On-board co2 capture and storage with metal organic framework

    KAUST Repository

    Eddaoudi, Mohamed

    2016-03-17

    In general, this disclosure describes method of capturing and storing CO2 on a vehicle. The method includes contacting an vehicle exhaust gas with one or more of a first metal organic framework (MOF) composition sufficient to separate CO2 from the exhaust gas, contacting the separated CO2 with one or more of a second MOF composition sufficient to store the CO2 and wherein the one or more first MOF composition comprises one or more SIFSIX-n-M MOF and wherein M is a metal and n is 2 or 3. Embodiments also describe an apparatus or system for capturing and storing CO2 onboard a vehicle.

  18. The Functionalization, Size Control and Properties of Metal-Organic Frameworks

    DEFF Research Database (Denmark)

    Xu, Hui; Iversen, Bo Brummerstedt

    Recent years, Metal-Organic Framework (MOF) materials have drawn great attentions due to their potential applications in gas sorption/separation and luminescent sensing. In this dissertation, the recent progress of MOF materials is reviewed, with specific focus on the functionalization, size....... A nanoscale MOF material with controllable size was realized whose morphology has been simulated base on the BFDH method, and the sensing of bacteria endospores was research in detail. We also report the synthesis and sensing of nitroaromatic explosives of a nanoscale MOF material....

  19. Sensing and capture of toxic and hazardous gases and vapors by metal-organic frameworks.

    Science.gov (United States)

    Wang, Hao; Lustig, William P; Li, Jing

    2018-03-13

    Toxic and hazardous chemical species are ubiquitous, predominantly emitted by anthropogenic activities, and pose serious risks to human health and the environment. Thus, the sensing and subsequent capture of these chemicals, especially in the gas or vapor phase, are of extreme importance. To this end, metal-organic frameworks have attracted significant interest, as their high porosity and wide tunability make them ideal for both applications. These tailorable framework materials are particularly promising for the specific sensing and capture of targeted chemicals, as they can be designed to fit a diverse range of required conditions. This review will discuss the advantages of metal-organic frameworks in the sensing and capture of harmful gases and vapors, as well as principles and strategies guiding the design of these materials. Recent progress in the luminescent detection of aromatic and aliphatic volatile organic compounds, toxic gases, and chemical warfare agents will be summarized, and the adsorptive removal of fluorocarbons/chlorofluorocarbons, volatile radioactive species, toxic industrial gases and chemical warfare agents will be discussed.

  20. Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

    Science.gov (United States)

    Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

    2013-04-10

    Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

  1. A spin transition mechanism for cooperative adsorption in metal-organic frameworks

    Science.gov (United States)

    Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia; Mason, Jarad A.; Runčevski, Tomče; Xiao, Dianne J.; Darago, Lucy E.; Crocellà, Valentina; Bordiga, Silvia; Long, Jeffrey R.

    2017-10-01

    Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents, but few guidelines currently exist for the design of such materials. In principle, metal-organic frameworks that contain coordinatively unsaturated metal centres could act as both selective and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal-organic frameworks featuring coordinatively unsaturated iron(II) sites. Functioning via a mechanism by which neighbouring iron(II) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer-Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

  2. Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials

    International Nuclear Information System (INIS)

    Gao Yi; Zeng, X C

    2007-01-01

    We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio Moeller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems

  3. Bi2O3 nanoparticles encapsulated in surface mounted metal-organic framework thin films

    Science.gov (United States)

    Guo, Wei; Chen, Zhi; Yang, Chengwu; Neumann, Tobias; Kübel, Christian; Wenzel, Wolfgang; Welle, Alexander; Pfleging, Wilhelm; Shekhah, Osama; Wöll, Christof; Redel, Engelbert

    2016-03-01

    We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye.We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00532b

  4. Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture

    KAUST Repository

    Shekhah, Osama

    2014-06-25

    Direct air capture is regarded as a plausible alternate approach that, if economically practical, can mitigate the increasing carbon dioxide emissions associated with two of the main carbon polluting sources, namely stationary power plants and transportation. Here we show that metal-organic framework crystal chemistry permits the construction of an isostructural metal-organic framework (SIFSIX-3-Cu) based on pyrazine/copper(II) two-dimensional periodic 4 4 square grids pillared by silicon hexafluoride anions and thus allows further contraction of the pore system to 3.5 versus 3.84 for the parent zinc(II) derivative. This enhances the adsorption energetics and subsequently displays carbon dioxide uptake and selectivity at very low partial pressures relevant to air capture and trace carbon dioxide removal. The resultant SIFSIX-3-Cu exhibits uniformly distributed adsorption energetics and offers enhanced carbon dioxide physical adsorption properties, uptake and selectivity in highly diluted gas streams, a performance, to the best of our knowledge, unachievable with other classes of porous materials. 2014 Macmillan Publishers Limited.

  5. Coordination Polymers and Metal Organic Frameworks Derived from 1,2,4-Triazole Amino Acid Linkers

    Directory of Open Access Journals (Sweden)

    Yann Garcia

    2011-10-01

    Full Text Available The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs and metal-organic frameworks (MOFs are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has been established for amine derivatization in amino acids into 1,2,4-triazoles. A set of novel 1,2,4-triazole derivatized amino acids were introduced as superlative precursors in the design of 1D coordination polymers, 2D chiral helicates and 3D metal-organic frameworks. Applications associated with these compounds are diverse and include gas adsorption-porosity partitioning, soft sacrificial matrix for morphology and phase selective cadmium oxide synthesis, FeII spin crossover materials, zinc-b-lactamases inhibitors, logistics for generation of chiral/non-centrosymmetric networks; and thus led to a foundation of a new family of functional CPs and MOFs that are reviewed in this invited contribution.

  6. Effects of ultrasound on properties of ni-metal organic framework nanostructures

    Directory of Open Access Journals (Sweden)

    Abbas Pardakhty

    2016-10-01

    Full Text Available Objective(s: According to the unique properties of magnetic nanoparticles, Nickel Metal-Organic Frameworks (MOF was synthesized successfully by ultrasound irradiation. Metal-organic frameworks (MOFs are organic–inorganic hybrid extended networks that are constructed via covalent linkages between metal ions/metal clusters and organic ligands called a linker. Materials and Methods: The nanoparticles were synthesized by Ultrasound  Method Under a synthesis conditions, All chemicals were used as received without further purification. Scanning electron microscopy (SEM images were obtained on LEO- 1455VP equipped with an energy dispersive X-ray spectroscopy at university of Kashan in Iran. Transition electron microscopy (TEM images were obtained on EM208 Philips transmission electron microscope with an accelerating voltage of 200 kV. Results: Results showed that Ni-MOF synthesized by this method, had smaller particle size distribution and It was found that the different kinds of ligand leads to preparation products with different morphologies and textural properties. Moreover, ultrasound irradiation method has significant effect on microstructures of as-synthesized MOFs and can improve their textural properties compared to method without using hydrothermal route.The XRD patterns of the samples obtained from ultrasound irradiation was well matched with that of as-prepared Ni-MOF by solvothermal method. Conclusion: This rapid method of ultrasonic radiation as compared to the classical solvothermal synthesis, showed promising results in terms of size distribution, surface area, pore diameter and pore volume.

  7. Photothermal Activation of Metal-Organic Frameworks Using a UV-Vis Light Source.

    Science.gov (United States)

    Espín, Jordi; Garzón-Tovar, Luis; Carné-Sánchez, Arnau; Imaz, Inhar; Maspoch, Daniel

    2018-03-21

    Metal-organic frameworks (MOFs) usually require meticulous removal of the solvent molecules to unlock their potential porosity. Herein, we report a novel one-step method for activating MOFs based on the photothermal effect induced by directly irradiating them with a UV-vis lamp. The localized light-to-heat conversion produced in the MOF crystals upon irradiation enables a very fast solvent removal, thereby significantly reducing the activation time to as low as 30 min and suppressing the need for time-consuming solvent-exchange procedures and vacuum conditions. This approach is successful for a broad range of MOFs, including HKUST-1, UiO-66-NH 2 , ZIF-67, CPO-27-M (M = Zn, Ni, and Mg), Fe-MIL-101-NH 2 , and IRMOF-3, all of which exhibit absorption bands in the light emission range. In addition, we anticipate that this photothermal activation can also be used to activate covalent organic frameworks (COFs).

  8. Lithium inclusion in indium metal-organic frameworks showing increased surface area and hydrogen adsorption

    Directory of Open Access Journals (Sweden)

    Mathieu Bosch

    2014-12-01

    Full Text Available Investigation of counterion exchange in two anionic In-Metal-Organic Frameworks (In-MOFs showed that partial replacement of disordered ammonium cations was achieved through the pre-synthetic addition of LiOH to the reaction mixture. This resulted in a surface area increase of over 1600% in {Li [In(1,3 − BDC2]}n and enhancement of the H2 uptake of approximately 275% at 80 000 Pa at 77 K. This method resulted in frameworks with permanent lithium content after repeated solvent exchange as confirmed by inductively coupled plasma mass spectrometry. Lithium counterion replacement appears to increase porosity after activation through replacement of bulkier, softer counterions and demonstrates tuning of pore size and properties in MOFs.

  9. Magnetic phase transition induced by electrostatic gating in two-dimensional square metal-organic frameworks

    Science.gov (United States)

    Wang, Yun-Peng; Li, Xiang-Guo; Liu, Shuang-Long; Fry, James N.; Cheng, Hai-Ping

    2018-03-01

    We investigate theoretically magnetism and magnetic phase transitions induced by electrostatic gating of two-dimensional square metal-organic framework compounds. We find that electrostatic gating can induce phase transitions between homogeneous ferromagnetic and various spin-textured antiferromagnetic states. Electronic structure and Wannier function analysis can reveal hybridizations between transition-metal d orbitals and conjugated π orbitals in the organic framework. Mn-containing compounds exhibit a strong d -π hybridization that leads to partially occupied spin-minority bands, in contrast to compounds containing transition-metal ions other than Mn, for which electronic structure around the Fermi energy is only slightly spin split due to weak d -π hybridization and the magnetic interaction is of the Ruderman-Kittel-Kasuya-Yosida type. We use a ferromagnetic Kondo lattice model to understand the phase transition in Mn-containing compounds in terms of carrier density and illuminate the complexity and the potential to control two-dimensional magnetization.

  10. Mechanical tunability via hydrogen bonding in metal-organic frameworks with the perovskite architecture.

    Science.gov (United States)

    Li, Wei; Thirumurugan, A; Barton, Phillip T; Lin, Zheshuai; Henke, Sebastian; Yeung, Hamish H-M; Wharmby, Michael T; Bithell, Erica G; Howard, Christopher J; Cheetham, Anthony K

    2014-06-04

    Two analogous metal-organic frameworks (MOFs) with the perovskite architecture, [C(NH2)3][Mn(HCOO)3] (1) and [(CH2)3NH2][Mn(HCOO)3] (2), exhibit significantly different mechanical properties. The marked difference is attributed to their distinct modes of hydrogen bonding between the A-site amine cation and the anionic framework. The stronger cross-linking hydrogen bonding in 1 gives rise to Young's moduli and hardnesses that are up to twice those in 2, while the thermal expansion is substantially smaller. This study presents clear evidence that the mechanical properties of MOF materials can be substantially tuned via hydrogen-bonding interactions.

  11. Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Wencai Zhou

    2015-06-01

    Full Text Available The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs, is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM, the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1, whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

  12. Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks

    Science.gov (United States)

    Zhou, Wencai; Wöll, Christof; Heinke, Lars

    2015-01-01

    The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs), is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM), the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1), whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

  13. Microporous metal-organic frameworks for storage and separation of small hydrocarbons

    NARCIS (Netherlands)

    He, Y.; Zhou, W.; Krishna, R.; Chen, B.

    2012-01-01

    Hydrocarbons are very important energy resources and raw materials for some industrially important products and fine chemicals. There is a need for the discovery of better materials that offer enhanced capacities for safe storage of hydrocarbons. Furthermore, the development of improved separation

  14. Homochiral metal-organic frameworks and their application in chromatography enantioseparations.

    Science.gov (United States)

    Peluso, Paola; Mamane, Victor; Cossu, Sergio

    2014-10-10

    The last frontier in the chiral stationary phases (CSPs) field for chromatography enantioseparations is represented by homochiral metal-organic frameworks (MOFs), a class of organic-inorganic hybrid materials built from metal-connecting nodes and organic-bridging ligands. The modular nature of these materials allows to design focused structures by combining properly metal, organic ligands and rigid polytopic spacers. Intriguingly, chiral ligands introduce molecular chirality in the MOF-network as well as homochirality in the secondary structure of materials (such as homohelicity) producing homochiral nets in a manner mimicking biopolymers (proteins, polysaccharides) which are characterized by a definite helical sense associated with the chirality of their building blocks (amino acids or sugars). Nowadays, robust and flexible materials characterized by high porosity and surface area became available by using preparative procedures typical of the so-called reticular synthesis. This review focuses on recent developments in the synthesis and applications of homochiral MOFs as supports for chromatography enantioseparations. Indeed, despite this field is in its infancy, interesting results have been produced and a critical overview of the 12 reported applications for gas chromatography (GC) and high-performance liquid chromatography (HPLC) can orient the reader approaching the field. Mechanistic aspects are shortly discussed and a view regarding future trends in this field is provided. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Antifungal activity of water-stable copper-containing metal-organic frameworks

    Science.gov (United States)

    Bouson, Supaporn; Krittayavathananon, Atiweena; Phattharasupakun, Nutthaphon; Siwayaprahm, Patcharaporn; Sawangphruk, Montree

    2017-10-01

    Although metal-organic frameworks (MOFs) or porous coordination polymers have been widely studied, their antimicrobial activities have not yet been fully investigated. In this work, antifungal activity of copper-based benzene-tricarboxylate MOF (Cu-BTC MOF), which is water stable and industrially interesting, is investigated against Candida albicans, Aspergillus niger, Aspergillus oryzae and Fusarium oxysporum. The Cu-BTC MOF can effectively inhibit the growth rate of C. albicans and remarkably inhibit the spore growth of A. niger, A. oryzae and F. oxysporum. This finding shows the potential of using Cu-BTC MOF as a strong biocidal material against representative yeasts and moulds that are commonly found in the food and agricultural industries.

  16. 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.

  17. Compositions and methods of making and using metal-organic framework compositions

    KAUST Repository

    Mohideen, Mohamed Infas Haja; Adil, Karim; Belmabkhout, Youssef; Eddaoudi, Mohamed; Bhatt, Prashant M.

    2017-01-01

    Embodiments of the present disclosure include a metal-organic framework (MOF) composition comprising one or more metal ions, a plurality of organic ligands, and a solvent, wherein the one or more metal ions associate with the plurality of organic ligands sufficient to form a MOF with kag topology. Embodiments of the present disclosure further include a method of making a MOF composition comprising contacting one or more metal ions with a plurality of organic ligands in the presence of a solvent, sufficient to form a MOF with kag topology, wherein the solvent comprises water only. Embodiments of the present disclosure also describe a method of capturing chemical species from a fluid composition comprising contacting a MOF composition with kag topology and pore size of about 3.4Å to 4.8Å with a fluid composition comprising two or more chemical species and capturing one or more captured chemical species from the fluid composition.

  18. Mechanized azobenzene-functionalized zirconium metal-organic framework for on-command cargo release.

    Science.gov (United States)

    Meng, Xiangshi; Gui, Bo; Yuan, Daqiang; Zeller, Matthias; Wang, Cheng

    2016-08-01

    Stimuli-responsive metal-organic frameworks (MOFs) have gained increasing attention recently for their potential applications in many areas. We report the design and synthesis of a water-stable zirconium MOF (Zr-MOF) that bears photoresponsive azobenzene groups. This particular MOF can be used as a reservoir for storage of cargo in water, and the cargo-loaded MOF can be further capped to construct a mechanized MOF through the binding of β-cyclodextrin with the azobenzene stalks on the MOF surface. The resulting mechanized MOF has shown on-command cargo release triggered by ultraviolet irradiation or addition of competitive agents without premature release. This study represents a simple approach to the construction of stimuli-responsive mechanized MOFs, and considering mechanized UiO-68-azo made from biocompatible components, this smart system may provide a unique MOF platform for on-command drug delivery in the future.

  19. Efficient photocatalytic degradation of rhodamine 6G with a quantum dot-metal organic framework nanocomposite.

    Science.gov (United States)

    Kaur, Rajnish; Vellingiri, Kowsalya; Kim, Ki-Hyun; Paul, A K; Deep, Akash

    2016-07-01

    The hybrid structures of metal organic frameworks (MOFs) and nanoparticles may offer the realization of effective photocatalytic materials due to combined benefits of the porous and molecular sieving properties of MOF matrix and the functional characteristics of encapsulated nanoparticles. In this study, cadmium telluride (CdTe) quantum dots (QD) are conjugated with a europium-MOF for the synthesis of a novel nanocomposite material with photocatalytic properties. Successful synthesis of a QD/Eu-MOF nanocomposite was characterized with various spectroscopic and microscopic techniques. This QD/Eu-MOF is found to be an effective catalyst to complete the degradation of Rhodamine 6G dye within 50 min. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Pristine Metal-Organic Frameworks and their Composites for Energy Storage and Conversion.

    Science.gov (United States)

    Liang, Zibin; Qu, Chong; Guo, Wenhan; Zou, Ruqiang; Xu, Qiang

    2017-11-22

    Metal-organic frameworks (MOFs), a new class of crystalline porous organic-inorganic hybrid materials, have recently attracted increasing interest in the field of energy storage and conversion. Herein, recent progress of MOFs and MOF composites for energy storage and conversion applications, including photochemical and electrochemical fuel production (hydrogen production and CO 2 reduction), water oxidation, supercapacitors, and Li-based batteries (Li-ion, Li-S, and Li-O 2 batteries), is summarized. Typical development strategies (e.g., incorporation of active components, design of smart morphologies, and judicious selection of organic linkers and metal nodes) of MOFs and MOF composites for particular energy storage and conversion applications are highlighted. A broad overview of recent progress is provided, which will hopefully promote the future development of MOFs and MOF composites for advanced energy storage and conversion applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

    Science.gov (United States)

    Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

    2016-01-01

    Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

  2. A metal-organic framework-based splitter for separating propylene from propane

    KAUST Repository

    Cadiau, Amandine

    2016-07-07

    The chemical industry is dependent on the olefin/paraffin separation, which is mainly accomplished by using energy-intensive processes. We report the use of reticular chemistry for the fabrication of a chemically stable fluorinated metal-organic framework (MOF) material (NbOFFIVE-1-Ni, also referred to as KAUST-7). The bridging of Ni(II)-pyrazine square-grid layers with (NbOF5)2- pillars afforded the construction of a three-dimensional MOF, enclosing a periodic array of fluoride anions in contracted square-shaped channels. The judiciously selected bulkier (NbOF5)2- caused the looked-for hindrance of the previously free-rotating pyrazine moieties, delimiting the pore system and dictating the pore aperture size and its maximum opening. The restricted MOF window resulted in the selective molecular exclusion of propane from propylene at atmospheric pressure, as evidenced through multiple cyclic mixed-gas adsorption and calorimetric studies.

  3. A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

    Science.gov (United States)

    Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

    2014-03-17

    This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A Simple Approach to Enhance the Water Stability of a Metal-Organic Framework.

    Science.gov (United States)

    Shih, Yung-Han; Kuo, Yu-Ching; Lirio, Stephen; Wang, Kun-Yun; Lin, Chia-Her; Huang, Hsi-Ya

    2017-01-01

    A facile method to improve the feasibility of water-unstable metal-organic frameworks in an aqueous environment has been developed that involves imbedding in a polymer monolith. The effect of compartment type during polymerization plays a significant role in maintaining the crystalline structure and thermal stability of the MOFs, which was confirmed by powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA), respectively. The MOF-polymer composite prepared in a narrow compartment (column, ID 0.8 mm) has better thermal and chemical stability than that prepared in a broad compartment (vial, ID 7 mm). The developed MOF-polymer composite was applied as an adsorbent in solid-phase microextraction of nine non-steroidal anti-inflammatory drugs (NSAIDs) and could be used for extraction more than 30 times, demonstrating that the proposed approach has potential for industrial applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Nanosheets of Nonlayered Aluminum Metal-Organic Frameworks through a Surfactant-Assisted Method

    KAUST Repository

    Pustovarenko, Alexey

    2018-05-18

    During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application. Surfactant-assisted preorganization of the metallic precursor prior to MOF synthesis enables the manufacture of nonlayered Al-containing MOF lamellae. These MOF nanosheets are shown to exhibit a superior performance over other crystal morphologies for both chemical sensing and gas separation. As revealed by electron microscopy and diffraction, this superior performance arises from the shorter diffusion pathway in the MOF nanosheets, whose 1D channels are oriented along the shortest particle dimension.

  6. Recent Progress in Metal-Organic Frameworks and Their Derived Nanostructures for Energy and Environmental Applications.

    Science.gov (United States)

    Xie, Zhiqiang; Xu, Wangwang; Cui, Xiaodan; Wang, Ying

    2017-04-22

    Metal-organic frameworks (MOFs), as a very promising category of porous materials, have attracted increasing interest from research communities due to their extremely high surface areas, diverse nanostructures, and unique properties. In recent years, there is a growing body of evidence to indicate that MOFs can function as ideal templates to prepare various nanostructured materials for energy and environmental cleaning applications. Recent progress in the design and synthesis of MOFs and MOF-derived nanomaterials for particular applications in lithium-ion batteries, sodium-ion batteries, supercapacitors, dye-sensitized solar cells, and heavy-metal-ion detection and removal is reviewed herein. In addition, the remaining major challenges in the above fields are discussed and some perspectives for future research efforts in the development of MOFs are also provided. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Remote stabilization of copper paddlewheel based molecular building blocks in metal-organic frameworks

    KAUST Repository

    Gao, Wenyang

    2015-03-24

    Copper paddlewheel based molecular building blocks (MBBs) are ubiquitous and have been widely employed for the construction of highly porous metal-organic frameworks (MOFs). However, most copper paddlewheel based MOFs fail to retain their structural integrity in the presence of water. This instability is directly correlated to the plausible displacement of coordinating carboxylates in the copper paddlewheel MBB, [Cu2(O2C-)4], by the strongly coordinating water molecules. In this comprehensive study, we illustrate the chemical stability control in the rht-MOF platform via strengthening the coordinating bonds within the triangular inorganic MBB, [Cu3O(N4-x(CH)xC-)3] (x = 0, 1, or 2). Remotely, the chemical stabilization propagated into the paddlewheel MBB to afford isoreticular rht-MOFs with remarkably enhanced water/chemical stabilities compared to the prototypal rht-MOF-1. © 2015 American Chemical Society.

  8. Experimental comparison of chiral metal-organic framework used as stationary phase in chromatography.

    Science.gov (United States)

    Xie, Sheng-Ming; Zhang, Mei; Fei, Zhi-Xin; Yuan, Li-Ming

    2014-10-10

    Chiral metal-organic frameworks (MOFs) are a new class of multifunctional material, which possess diverse structures and unusual properties such as high surface area, uniform and permanent cavities, as well as good chemical and thermal stability. Their chiral functionality makes them attractive as novel enantioselective adsorbents and stationary phases in separation science. In this paper, the experimental comparison of a chiral MOF [In₃O(obb)₃(HCO₂)(H₂O)] solvent used as a stationary phase was investigated in gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The potential relationship between the structure and components of chiral MOFs with their chiral recognition ability and selectivity are presented. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Thermodynamics of Pore Filling Metal Clusters in Metal Organic Frameworks: Pd in UiO-66

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Sholl, David S.

    2012-01-01

    Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory...... calculations to predict the structure of Pd clusters in UiO-66. The cluster sizes examined are far larger than those in any previous modeling studies of metal clusters in MOFs and allow us to test the hypothesis that the physically separated cavities in UiO-66 could stabilize isolated Pd clusters. Our...... calculations show that Pd clusters in UiO-66 are, at best, metastable and will aggregate into connected pore filling structures at equilibrium....

  10. Computational design of metal-organic frameworks with paddlewheel-type secondary building units

    Science.gov (United States)

    Schwingenschlogl, Udo; Peskov, Maxim V.; Masghouni, Nejib

    We employ the TOPOS package to study 697 coordination polymers containing paddlewheel-type secondary building units. The underlying nets are analyzed and 3 novel nets are chosen as potential topologies for paddlewheel-type metal organic frameworks (MOFs). Dicarboxylate linkers are used to build basic structures for novel isoreticular MOF series, aiming at relatively compact structures with a low number of atoms per unit cell. The structures are optimized using density functional theory. Afterwards the Grand Canonical Monte Carlo approach is employed to generate adsorption isotherms for CO2, CO, and CH4 molecules. We utilize the universal forcefield for simulating the interaction between the molecules and hosting MOF. The diffusion behavior of the molecules inside the MOFs is analyzed by molecular dynamics simulations.

  11. Chiral Recognition and Separation by Chirality-Enriched Metal-Organic Frameworks.

    Science.gov (United States)

    Das, Saikat; Xu, Shixian; Ben, Teng; Qiu, Shilun

    2018-05-16

    Endowed with chiral channels and pores, chiral metal-organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality-enriched MOFs with accessible pores. The ability of the materials to form host-guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed-matrix membranes (MMMs) composed of chirality-enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

    Energy Technology Data Exchange (ETDEWEB)

    Du, Pei-Yao [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China); Liao, Sheng-Yun [Department of Applied Chemistry, Tianjin University of Technology, Tianjin 300384 (China); Gu, Wen, E-mail: guwen68@nankai.edu.cn [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China); Liu, Xin, E-mail: liuxin64@nankai.edu.cn [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China)

    2016-12-15

    A 3D lanthanide MOF with formula [Sm{sub 2}(abtc){sub 1.5}(H{sub 2}O){sub 3}(DMA)]·H{sub 2}O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol. - Highlights: • A three-dimensional lanthanide metal-organic framework has been synthesized. • Complex 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. • Complex 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules.

  13. Rapid and Accurate Machine Learning Recognition of High Performing Metal Organic Frameworks for CO2 Capture.

    Science.gov (United States)

    Fernandez, Michael; Boyd, Peter G; Daff, Thomas D; Aghaji, Mohammad Zein; Woo, Tom K

    2014-09-04

    In this work, we have developed quantitative structure-property relationship (QSPR) models using advanced machine learning algorithms that can rapidly and accurately recognize high-performing metal organic framework (MOF) materials for CO2 capture. More specifically, QSPR classifiers have been developed that can, in a fraction of a section, identify candidate MOFs with enhanced CO2 adsorption capacity (>1 mmol/g at 0.15 bar and >4 mmol/g at 1 bar). The models were tested on a large set of 292 050 MOFs that were not part of the training set. The QSPR classifier could recover 945 of the top 1000 MOFs in the test set while flagging only 10% of the whole library for compute intensive screening. Thus, using the machine learning classifiers as part of a high-throughput screening protocol would result in an order of magnitude reduction in compute time and allow intractably large structure libraries and search spaces to be screened.

  14. Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

    Science.gov (United States)

    Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

    2016-01-01

    Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes. PMID:26796523

  15. Sensitive resonant gas sensor operating in air with metal organic frameworks coating

    KAUST Repository

    Jaber, Nizar; Ilyas, Saad; Shekhah, Osama; Eddaoudi, Mohamed; Younis, Mohammad I.

    2017-01-01

    We report a practical resonant gas sensor that is uniformly coated with metal organic frameworks (MOFs) and excited near the higher order modes for a higher attained sensitivity. The resonator is based on an electrostatically excited clamped-clamped microbeam. The microbeam is fabricated from a polyimide layer coated from the top with Cr/Au and from the bottom with Cr/Au/Cr layer. The geometry of the resonator is optimized to reduce the effect of the squeeze film damping, thereby allowing operation under atmospheric pressure. The electrostatic force electrode is designed to enhance the excitation of the second mode of vibration with the minimum power required. Significant frequency shift (kHz) is demonstrated for the first time upon water vapor, acetone, and ethanol exposure due to the MOFs functionalization and the higher order modes excitation. Also, the adsorption dynamics and MOF selectivity is investigated by studying the decaying time constants of the response upon gas exposure.

  16. Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

    KAUST Repository

    Cadiau, Amandine

    2017-05-18

    Natural gas must be dehydrated before it can be transported and used, but conventional drying agents such as activated alumina or inorganic molecular sieves require an energy-intensive desiccant-regeneration step. We report a hydrolytically stable fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas streams containing CO2, N2, CH4, and higher hydrocarbons typical of natural gas, as well as selectively removed both H2O and CO2 in N2-containing streams. The complete desorption of the adsorbed water molecules contained by the AlFFIVE-1-Ni sorbent requires relatively moderate temperature (~105°C) and about half the energy input for commonly used desiccants.

  17. Adsorptive removal of naproxen and clofibric acid from water using metal-organic frameworks.

    Science.gov (United States)

    Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

    2012-03-30

    Adsorptive removal of naproxen and clofibric acid, two typical PPCPs (pharmaceuticals and personal care products), has been studied using metal-organic frameworks (MOFs) for the first time. The removal efficiency decreases in the order of MIL-101>MIL-100-Fe>activated carbon both in adsorption rate and adsorption capacity. The adsorption kinetics and capacity of PPCPs generally depend on the average pore size and surface area (or pore volume), respectively, of the adsorbents. The adsorption mechanism may be explained with a simple electrostatic interaction between PPCPs and the adsorbent. Finally, it can be suggested that MOFs having high porosity and large pore size can be potential adsorbents to remove harmful PPCPs in contaminated water. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Single Pt Atoms Confined into a Metal-Organic Framework for Efficient Photocatalysis.

    Science.gov (United States)

    Fang, Xinzuo; Shang, Qichao; Wang, Yu; Jiao, Long; Yao, Tao; Li, Yafei; Zhang, Qun; Luo, Yi; Jiang, Hai-Long

    2018-02-01

    It is highly desirable yet remains challenging to improve the dispersion and usage of noble metal cocatalysts, beneficial to charge transfer in photocatalysis. Herein, for the first time, single Pt atoms are successfully confined into a metal-organic framework (MOF), in which electrons transfer from the MOF photosensitizer to the Pt acceptor for hydrogen production by water splitting under visible-light irradiation. Remarkably, the single Pt atoms exhibit a superb activity, giving a turnover frequency of 35 h -1 , ≈30 times that of Pt nanoparticles stabilized by the same MOF. Ultrafast transient absorption spectroscopy further unveils that the single Pt atoms confined into the MOF provide highly efficient electron transfer channels and density functional theory calculations indicate that the introduction of single Pt atoms into the MOF improves the hydrogen binding energy, thus greatly boosting the photocatalytic H 2 production activity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Application of Two Cobalt-Based Metal-Organic Frameworks as Oxidative Desulfurization Catalysts.

    Science.gov (United States)

    Masoomi, Mohammad Yaser; Bagheri, Minoo; Morsali, Ali

    2015-12-07

    Two new porous cobalt-based metal-organic frameworks, [Co6(oba)5(OH)2(H2O)2(DMF)4]n · 5DMF (TMU-10) and [Co3(oba)3(O) (Py)0.5] n · 4DMF · Py (TMU-12) have been synthesized by solvothermal method using a nonlinear dicarboxylate ligand. Under mild reaction conditions, these compounds exhibited good catalytic activity and reusability in oxidative desulfurization (ODS) reaction of model oil which was prepared by dissolving dibenzothiophene (DBT) in n-hexane. FT-IR and Mass analysis showed that the main product of DBT oxidation is its corresponding sulfone, which was adsorbed on the surfaces of catalysts. The activation energy was obtained as 13.4 kJ/mol.

  20. Condensation of Methane in the Metal-Organic Framework IRMOF-1: Evidence for Two Critical Points.

    Science.gov (United States)

    Höft, Nicolas; Horbach, Jürgen

    2015-08-19

    Extensive grand canonical Monte Carlo simulations in combination with successive umbrella sampling are used to investigate the condensation of methane in the nanoporous crystalline material IRMOF-1. Two different types of novel condensation transitions are found, each of them ending in a critical point: (i) a fluid-fluid transition at higher densities (the analog of the liquid-gas transition in the bulk) and (ii) a phase transition at low densities on the surface of the IRMOF-1 structure. The nature of these transitions is different from the usual capillary condensation in thin films and cylindrical pores where the coexisting phases are confined in one or two of the three spatial dimensions. In contrast to that, in IRMOF-1 the different phases can be described as bulk phases that are inhomogeneous due to the presence of the metal-organic framework. As a consequence, the condensation transitions in IRMOF-1 belong to the three-dimensional (3D) Ising universality class.

  1. Remote stabilization of copper paddlewheel based molecular building blocks in metal-organic frameworks

    KAUST Repository

    Gao, Wenyang; Cai, Rong; Pham, Tony T.; Forrest, Katherine A.; Hogan, Adam; Nugent, Patrick S.; Williams, Kia R.; Wojtas, Łukasz; Luebke, Ryan; Weselinski, Lukasz Jan; Zaworotko, Michael J.; Space, Brian; Chen, Yusheng; Eddaoudi, Mohamed; Shi, Xiaodong; Ma, Shengqian

    2015-01-01

    Copper paddlewheel based molecular building blocks (MBBs) are ubiquitous and have been widely employed for the construction of highly porous metal-organic frameworks (MOFs). However, most copper paddlewheel based MOFs fail to retain their structural integrity in the presence of water. This instability is directly correlated to the plausible displacement of coordinating carboxylates in the copper paddlewheel MBB, [Cu2(O2C-)4], by the strongly coordinating water molecules. In this comprehensive study, we illustrate the chemical stability control in the rht-MOF platform via strengthening the coordinating bonds within the triangular inorganic MBB, [Cu3O(N4-x(CH)xC-)3] (x = 0, 1, or 2). Remotely, the chemical stabilization propagated into the paddlewheel MBB to afford isoreticular rht-MOFs with remarkably enhanced water/chemical stabilities compared to the prototypal rht-MOF-1. © 2015 American Chemical Society.

  2. Direct Synthesis of 7 nm Thick Zinc(II)-Benzimidazole-Acetate Metal-Organic Framework Nanosheets

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Feng; Kumar, Prashant; Xu, Wenqian; Mkhoyan, K. Andre; Tsapatsis, Michael

    2018-01-09

    Two-dimensional metal-organic frameworks (MOFs) are promising candidates for high performance gas sepa-ration membranes. Currently, MOF nanosheets are mostly fabricated through delamination of layered MOFs, which often re-sults in a low yield of intact free-standing nanosheets. In this work, we present a direct synthesis method for zinc(II)-benzimidazole-acetate (Zn(Bim)OAc) MOF nanosheets. The obtained nanosheets have a lateral dimension of 600 nm when synthesized at room temperature. By adjusting the synthesis temperature, the morphology of obtained nanosheets can be readily tuned from nanosheets to nanobelts. A thickness of 7 nm is determined for Zn(Bim)OAc using high-angle annular dark-field scanning transmission electron microscopy, which makes these nanosheets promising building blocks of gas sepa-ration membranes.

  3. Titanium-Phosphonate-Based Metal-Organic Frameworks with Hierarchical Porosity for Enhanced Photocatalytic Hydrogen Evolution

    KAUST Repository

    Li, Hui

    2018-02-01

    Photocatalytic hydrogen production is crucial for solar-to-chemical conversion process, wherein high-efficiency photocatalysts lie in the heart of this area. Herein a new photocatalyst of hierarchically mesoporous titanium-phosphonate-based metal-organic frameworks, featuring well-structured spheres, periodic mesostructure and large secondary mesoporosity, are rationally designed with the complex of polyelectrolyte and cathodic surfactant serving as the template. The well-structured hierarchical porosity and homogeneously incorporated phosphonate groups can favor the mass transfer and strong optical absorption during the photocatalytic reactions. Correspondingly, the titanium phosphonates exhibit significantly improved photocatalytic hydrogen evolution rate along with impressive stability. This work can provide more insights into designing advanced photocatalysts for energy conversion and render a tunable platform in photoelectrochemical field.

  4. A novel series of isoreticular metal organic frameworks: Realizing metastable structures by liquid phase epitaxy

    KAUST Repository

    Liu, Jinxuan

    2012-12-04

    A novel class of metal organic frameworks (MOFs) has been synthesized from Cu-acetate and dicarboxylic acids using liquid phase epitaxy. The SURMOF-2 isoreticular series exhibits P4 symmetry, for the longest linker a channel-size of 3 3 nm2 is obtained, one of the largest values reported for any MOF so far. High quality, ab-initio electronic structure calculations confirm the stability of a regular packing of (Cu++) 2-carboxylate paddle-wheel planes with P4 symmetry and reveal, that the SURMOF-2 structures are in fact metastable, with a fairly large activation barrier for the transition to the bulk MOF-2 structures exhibiting a lower, twofold (P2 or C2) symmetry. The theoretical calculations also allow identifying the mechanism for the low-temperature epitaxial growth process and to explain, why a synthesis of this highly interesting, new class of high-symmetry, metastable MOFs is not possible using the conventional solvothermal process.

  5. A novel series of isoreticular metal organic frameworks: Realizing metastable structures by liquid phase epitaxy

    KAUST Repository

    Liu, Jinxuan; Lukose, Binit; Shekhah, Osama; Arslan, Hasan Kemal; Weidler, Peter; Gliemann, Hartmut; Brä se, Stefan; Grosjean, Sylvain; Godt, Adelheid; Feng, Xinliang; Mü llen, Klaus; Magdau, Ioan-Bogdan; Heine, Thomas; Wö ll, Christof

    2012-01-01

    A novel class of metal organic frameworks (MOFs) has been synthesized from Cu-acetate and dicarboxylic acids using liquid phase epitaxy. The SURMOF-2 isoreticular series exhibits P4 symmetry, for the longest linker a channel-size of 3 3 nm2 is obtained, one of the largest values reported for any MOF so far. High quality, ab-initio electronic structure calculations confirm the stability of a regular packing of (Cu++) 2-carboxylate paddle-wheel planes with P4 symmetry and reveal, that the SURMOF-2 structures are in fact metastable, with a fairly large activation barrier for the transition to the bulk MOF-2 structures exhibiting a lower, twofold (P2 or C2) symmetry. The theoretical calculations also allow identifying the mechanism for the low-temperature epitaxial growth process and to explain, why a synthesis of this highly interesting, new class of high-symmetry, metastable MOFs is not possible using the conventional solvothermal process.

  6. Metal-organic framework based highly selective fluorescence turn-on probe for hydrogen sulphide

    Science.gov (United States)

    Nagarkar, Sanjog S.; Saha, Tanmoy; Desai, Aamod V.; Talukdar, Pinaki; Ghosh, Sujit K.

    2014-11-01

    Hydrogen sulphide (H2S) is known to play a vital role in human physiology and pathology which stimulated interest in understanding complex behaviour of H2S. Discerning the pathways of H2S production and its mode of action is still a challenge owing to its volatile and reactive nature. Herein we report azide functionalized metal-organic framework (MOF) as a selective turn-on fluorescent probe for H2S detection. The MOF shows highly selective and fast response towards H2S even in presence of other relevant biomolecules. Low cytotoxicity and H2S detection in live cells, demonstrate the potential of MOF towards monitoring H2S chemistry in biological system. To the best of our knowledge this is the first example of MOF that exhibit fast and highly selective fluorescence turn-on response towards H2S under physiological conditions.

  7. Applications of Total Scattering & Pair Distribution Function Analysis in Metal-Organic Framework Materials

    DEFF Research Database (Denmark)

    Xu, Hui; Birgisson, Steinar; Sommer, Sanna

    structure. At the same time, there is an ongoing debate on whether the SBU is present prior, or during MOF crystallization in MOF chemistry. However, little is known about MOFs formation mechanism. Currently techniques to study the in situ MOF formation process mainly focused on after......-crystallization process, for example in situ XRD and SAXS/WAXS study on MOF formation. However, the pre-crystallization process in the early stage of MOF formation is still unexplored. In this project, total scattering and PDF study will be carried out to explore the MOF formation process in early stage. This includes......Metal-Organic Frameworks (MOFs) is constructed by metal-oxide nodes and organic ligands. The formation of different structures of metal-oxide nodes (also called secondary building units, SBU) is crucial for MOF final structures, because the connectivity of SBU greatly influence the final MOF...

  8. A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

    International Nuclear Information System (INIS)

    Du, Pei-Yao; Liao, Sheng-Yun; Gu, Wen; Liu, Xin

    2016-01-01

    A 3D lanthanide MOF with formula [Sm 2 (abtc) 1.5 (H 2 O) 3 (DMA)]·H 2 O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol. - Highlights: • A three-dimensional lanthanide metal-organic framework has been synthesized. • Complex 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. • Complex 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules.

  9. Synthesis, functionalization, and applications of metal-organic frameworks in biomedicine.

    Science.gov (United States)

    Chen, Wei; Wu, Chunsheng

    2018-02-13

    Metal-organic frameworks (MOFs), also known as coordination polymers, have attracted extensive research interest in the past few decades due to their unique physical structures and potentially vast applications. In this review, we outline the recent progress in the synthesis, functionalization and applications of MOFs in biomedicine, mainly focusing on two promising, yet challenging areas, i.e., drug delivery and biosensing applications. A major challenge is the proper functionalization of MOFs with demanding properties suitable for biomedical applications. Extensive studies on MOFs in biomedicine have led to substantial progress in the control of key properties of MOFs such as toxicity, size and shape, and biological stability. Due to their flexible composition, pore size and easy functionalization properties, MOFs can be utilized as key components for the development of various functional systems, and their applications in drug delivery and biosensing are reviewed. Future trends and perspectives in these research areas are also outlined.

  10. Compositions and methods of making and using metal-organic framework compositions

    KAUST Repository

    Mohideen, Mohamed Infas Haja

    2017-05-04

    Embodiments of the present disclosure include a metal-organic framework (MOF) composition comprising one or more metal ions, a plurality of organic ligands, and a solvent, wherein the one or more metal ions associate with the plurality of organic ligands sufficient to form a MOF with kag topology. Embodiments of the present disclosure further include a method of making a MOF composition comprising contacting one or more metal ions with a plurality of organic ligands in the presence of a solvent, sufficient to form a MOF with kag topology, wherein the solvent comprises water only. Embodiments of the present disclosure also describe a method of capturing chemical species from a fluid composition comprising contacting a MOF composition with kag topology and pore size of about 3.4Å to 4.8Å with a fluid composition comprising two or more chemical species and capturing one or more captured chemical species from the fluid composition.

  11. A Stable Metal-Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation.

    Science.gov (United States)

    He, Hongming; Sun, Qi; Gao, Wenyang; Perman, Jason A; Sun, Fuxing; Zhu, Guangshan; Aguila, Briana; Forrest, Katherine; Space, Brian; Ma, Shengqian

    2018-04-16

    A majority of metal-organic frameworks (MOFs) fail to preserve their physical and chemical properties after exposure to acidic, neutral, or alkaline aqueous solutions, therefore limiting their practical applications in many areas. The strategy demonstrated herein is the design and synthesis of an organic ligand that behaves as a buffer to drastically boost the aqueous stability of a porous MOF (JUC-1000), which maintains its structural integrity at low and high pH values. The local buffer environment resulting from the weak acid-base pairs of the custom-designed organic ligand also greatly facilitates the performance of JUC-1000 in the chemical fixation of carbon dioxide under ambient conditions, outperforming a series of benchmark catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Sensitive resonant gas sensor operating in air with metal organic frameworks coating

    KAUST Repository

    Jaber, Nizar

    2017-08-09

    We report a practical resonant gas sensor that is uniformly coated with metal organic frameworks (MOFs) and excited near the higher order modes for a higher attained sensitivity. The resonator is based on an electrostatically excited clamped-clamped microbeam. The microbeam is fabricated from a polyimide layer coated from the top with Cr/Au and from the bottom with Cr/Au/Cr layer. The geometry of the resonator is optimized to reduce the effect of the squeeze film damping, thereby allowing operation under atmospheric pressure. The electrostatic force electrode is designed to enhance the excitation of the second mode of vibration with the minimum power required. Significant frequency shift (kHz) is demonstrated for the first time upon water vapor, acetone, and ethanol exposure due to the MOFs functionalization and the higher order modes excitation. Also, the adsorption dynamics and MOF selectivity is investigated by studying the decaying time constants of the response upon gas exposure.

  13. Nucleation and Early Stages of Layer-by-Layer Growth of Metal Organic Frameworks on Surfaces

    Science.gov (United States)

    2015-01-01

    High resolution atomic force microscopy (AFM) is used to resolve the evolution of crystallites of a metal organic framework (HKUST-1) grown on Au(111) using a liquid-phase layer-by-layer methodology. The nucleation and faceting of individual crystallites is followed by repeatedly imaging the same submicron region after each cycle of growth and we find that the growing surface is terminated by {111} facets leading to the formation of pyramidal nanostructures for [100] oriented crystallites, and triangular [111] islands with typical lateral dimensions of tens of nanometres. AFM images reveal that crystallites can grow by 5–10 layers in each cycle. The growth rate depends on crystallographic orientation and the morphology of the gold substrate, and we demonstrate that under these conditions the growth is nanocrystalline with a morphology determined by the minimum energy surface. PMID:26709359

  14. Dubinin-Astakhov model for acetylene adsorption on metal-organic frameworks

    Science.gov (United States)

    Cheng, Peifu; Hu, Yun Hang

    2016-07-01

    Acetylene (C2H2) is explosive at a pressure above 29 psi, causing a safety issue for its storage and applications. C2H2 adsorption on metal-organic frameworks (MOFs) has been explored to solve the issue. However, a suitable isotherm equation for C2H2 adsorption on various MOFs has not been found. In this paper, it was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model to depict C2H2 adsorption on MOF-5, ZIF-8, HKUST-1, and MIL-53. In contrast, commonly used Langmuir and BET models exhibited their inapplicability for C2H2 adsorption on those MOFs.

  15. Surface Termination of the Metal-Organic Framework HKUST-1: A Theoretical Investigation.

    Science.gov (United States)

    Amirjalayer, Saeed; Tafipolsky, Maxim; Schmid, Rochus

    2014-09-18

    The surface morphology and termination of metal-organic frameworks (MOF) is of critical importance in many applications, but the surface properties of these soft materials are conceptually different from those of other materials like metal or oxide surfaces. Up to now, experimental investigations are scarce and theoretical simulations have focused on the bulk properties. The possible surface structure of the archetypal MOF HKUST-1 is investigated by a first-principles derived force field in combination with DFT calculations of model systems. The computed surface energies correctly predict the [111] surface to be most stable and allow us to obtain an unprecedented atomistic picture of the surface termination. Entropic factors are identified to determine the preferred surface termination and to be the driving force for the MOF growth. On the basis of this, reported strategies like employing "modulators" during the synthesis to tailor the crystal morphology are discussed.

  16. Hydrogen storage in Pd nanocrystals covered with a metal-organic framework

    Science.gov (United States)

    Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M.; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

    2014-08-01

    Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

  17. Graphene inclusion controlling conductivity and gas sorption of metal-organic framework

    DEFF Research Database (Denmark)

    Lamagni, Paolo; Pedersen, Birgitte Lodberg; Godiksen, Anita

    2018-01-01

    A general approach to prepare composite films of metal-organic frameworks and graphene has been developed. Films of copper(ii)-based HKUST-1 and HKUST-1/graphene composites were grown solvothermally on glassy carbon electrodes. The films were chemically tethered to the substrate by diazonium...... electrografting resulting in a large electrode coverage and good stability in solution for electrochemical studies. HKUST-1 has poor electrical conductivity, but we demonstrate that the addition of graphene to HKUST-1 partially restores the electrochemical activity of the electrodes. The enhanced activity......, however, does not result in copper(ii) to copper(i) reduction in HKUST-1 at negative potentials. The materials were characterised in-depth: microscopy and grazing incidence X-ray diffraction demonstrate uniform films of crystalline HKUST-1, and Raman spectroscopy reveals that graphene is homogeneously...

  18. Adsorption of silver nanoparticles from aqueous solution on copper-based metal organic frameworks (HKUST-1).

    Science.gov (United States)

    Conde-González, J E; Peña-Méndez, E M; Rybáková, S; Pasán, J; Ruiz-Pérez, C; Havel, J

    2016-05-01

    Silver nanoparticles (AgNP) are emerging pollutants. The use of novel materials such as Cu-(benzene 1,3,5-tricarboxylate, BTC) Metal-Organic Framework (MOFs), for AgNP adsorption and their removal from aqueous solutions has been studied. The effect of different parameters was followed and isotherm model was suggested. MOFs adsorbed fast and efficiently AgNP in the range C0 < 10 mg L(-1), being Freundlich isotherm (R = 0.993) these data fitted to. Among studied parameters a remarkable effect of chloride on sorption was found, thus their possible interactions were considered. The high adsorption efficiency of AgNP was achieved and it was found to be very fast. The feasibility of adsorption on Cu-(BTC) was proved in spiked waters. The results showed the potential interest of new material as adsorbent for removing AgNP from environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. MOFwich: Sandwiched Metal-Organic Framework-Containing Mixed Matrix Composites for Chemical Warfare Agent Removal.

    Science.gov (United States)

    Peterson, Gregory W; Lu, Annie X; Hall, Morgan G; Browe, Matthew A; Tovar, Trenton; Epps, Thomas H

    2018-02-28

    This work describes a new strategy for fabricating mixed matrix composites containing layered metal-organic framework (MOF)/polymer films as functional barriers for chemical warfare agent protection. Through the use of mechanically robust polymers as the top and bottom encasing layers, a high-MOF-loading, high-performance-core layer can be sandwiched within. We term this multifunctional composite "MOFwich". We found that the use of elastomeric encasing layers enabled core layer reformation after breakage, an important feature for composites and membranes alike. The incorporation of MOFs into the core layer led to enhanced removal of chemical warfare agents while simultaneously promoting moisture vapor transport through the composite, showcasing the promise of these composites for protection applications.

  20. Textile/metal-organic-framework composites as self-detoxifying filters for chemical-warfare agents.

    Science.gov (United States)

    López-Maya, Elena; Montoro, Carmen; Rodríguez-Albelo, L Marleny; Aznar Cervantes, Salvador D; Lozano-Pérez, A Abel; Cenís, José Luis; Barea, Elisa; Navarro, Jorge A R

    2015-06-01

    The current technology of air-filtration materials for protection against highly toxic chemicals, that is, chemical-warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self-cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal-organic framework (MOF) materials to develop advanced self-detoxifying adsorbents of chemical-warfare agents containing hydrolysable P-F, P-O, and C-Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air-permeation properties of the textiles with the self-detoxifying properties of the MOF material. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

    Energy Technology Data Exchange (ETDEWEB)

    Read, Douglas [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Sillerud, Colin Halliday [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-01-01

    The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

  2. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Kim, In Soo [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Nanophotonics Center, Korea Institute of Science and Technology, Seoul 02792 South Korea; Li, Zhanyong [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Zheng, Jian [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Platero-Prats, Ana E. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Mavrandonakis, Andreas [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Pellizzeri, Steven [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Ferrandon, Magali [Chemical Sciences and Engineering Division, Argonne National Lab, 9700 S. Cass Ave. Argonne IL 60439 USA; Vjunov, Aleksei [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Gallington, Leighanne C. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Webber, Thomas E. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Vermeulen, Nicolaas A. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Penn, R. Lee [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Getman, Rachel B. [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Cramer, Christopher J. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Chapman, Karena W. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Fulton, John L. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, Technische Universität München, Lichtenbergstrasse 4 85748 Garching Germany; Farha, Omar K. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Hupp, Joseph T. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Martinson, Alex B. F. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA

    2018-01-02

    Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.

  3. Diffusion of Vitamin B12 Across a Mesoporous Metal Organic Framework

    Directory of Open Access Journals (Sweden)

    Veronica Valencia

    2013-01-01

    Full Text Available We measure the rate of uptake and the rate of release of a Vitamin B12 solution (dissolved in water at 2 different temperatures (room temperature and 37°C by the mesoporous metal organic framework TbMOF-100 at 1-hour intervals using a spectrophotometer. Using the Beer-Lambert law, we calculate the concentration of the stock solution based on the absorbance values obtained with the spectrophotometer. These values allow for the quantification of the initial rate of uptake and the rate of uptake at a random incubation time of the Vitamin B12 by the TbMOF-100. We also calculate the value of the coefficient of diffusion for this 2-phase system using Fick’s laws of diffusion.

  4. Titanium-Phosphonate-Based Metal-Organic Frameworks with Hierarchical Porosity for Enhanced Photocatalytic Hydrogen Evolution

    KAUST Repository

    Li, Hui; Sun, Ying; Yuan, Zhong-Yong; Zhu, Yun-Pei; Ma, Tianyi

    2018-01-01

    Photocatalytic hydrogen production is crucial for solar-to-chemical conversion process, wherein high-efficiency photocatalysts lie in the heart of this area. Herein a new photocatalyst of hierarchically mesoporous titanium-phosphonate-based metal-organic frameworks, featuring well-structured spheres, periodic mesostructure and large secondary mesoporosity, are rationally designed with the complex of polyelectrolyte and cathodic surfactant serving as the template. The well-structured hierarchical porosity and homogeneously incorporated phosphonate groups can favor the mass transfer and strong optical absorption during the photocatalytic reactions. Correspondingly, the titanium phosphonates exhibit significantly improved photocatalytic hydrogen evolution rate along with impressive stability. This work can provide more insights into designing advanced photocatalysts for energy conversion and render a tunable platform in photoelectrochemical field.

  5. Applications of Immobilized Bio-Catalyst in Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Qi Wang

    2018-04-01

    Full Text Available Immobilization of bio-catalysts in solid porous materials has attracted much attention in the last few decades due to its vast application potential in ex vivo catalysis. Despite the high efficiency and selectivity of enzymatic catalytic processes, enzymes may suffer from denaturation under industrial production conditions, which, in turn, diminish their catalytic performances and long-term recyclability. Metal-organic frameworks (MOFs, as a growing type of hybrid materials, have been identified as promising platforms for enzyme immobilization owing to their enormous structural and functional tunability, and extraordinary porosity. This review mainly focuses on the applications of enzyme@MOFs hybrid materials in catalysis, sensing, and detection. The improvements of catalytic activity and robustness of encapsulated enzymes over the free counterpart are discussed in detail.

  6. Metal-Organic Framework of Lanthanoid Dinuclear Clusters Undergoes Slow Magnetic Relaxation

    Directory of Open Access Journals (Sweden)

    Hikaru Iwami

    2017-01-01

    Full Text Available Lanthanoid metal-organic frameworks (Ln-MOFs can adopt a variety of new structures due to the large coordination numbers of Ln metal ions, and Ln-MOFs are expected to show new luminescence and magnetic properties due to the localized f electrons. In particular, some Ln metal ions, such as Dy(III and Tb(III ions, work as isolated quantum magnets when they have magnetic anisotropy. In this work, using 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB as a ligand, two new Ln-MOFs, [Dy(TATB(DMF2] (1 and [Tb(TATB(DMF2] (2, were obtained. The Ln-MOFs contain Ln dinuclear clusters as secondary building units, and 1 underwent slow magnetic relaxation similar to single-molecule magnets.

  7. Sonochemical Synthesis of Photoluminescent Nanoscale Eu(III-Containing Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Cheng-an TAO

    2015-11-01

    Full Text Available Nanoscale lanthanide-containing metal-organic frameworks (MOFs have more and more interest due to their great properties and potential applications, but how to construct them easily is still challenging. Here, we present a facile and rapid synthesis of Eu(III-containing Nanoscale MOF (denoted as NMOF under ultrasonic irradiation. The effect of the ratio and the addition order of metal ions and linkers on the morphology and size of MOFs was investigated. It is found that both of the ratio and the addition order can affect the morphology and size of 1.4-benzenedicarboxylic acid(H2BDC -based MOFs, but they show no evident influence on that of H2aBDC-based MOFs. The former exhibit typical emission bands of Eu(III ions, while the latter only show the photoluminescent properties of ligands.DOI: http://dx.doi.org/10.5755/j01.ms.21.4.9695

  8. CFA-1: the first chiral metal-organic framework containing Kuratowski-type secondary building units.

    Science.gov (United States)

    Schmieder, Phillip; Denysenko, Dmytro; Grzywa, Maciej; Baumgärtner, Benjamin; Senkovska, Irena; Kaskel, Stefan; Sastre, German; van Wüllen, Leo; Volkmer, Dirk

    2013-08-14

    The novel homochiral metal-organic framework CFA-1 (Coordination Framework Augsburg-1), [Zn5(OAc)4(bibta)3], containing the achiral linker {H2-bibta = 1H,1'H-5,5'-bibenzo[d][1,2,3]triazole}, has been synthesised. The reaction of H2-bibta and Zn(OAc)2·2H2O in N-methylformamide (NMF) (90 °C, 3 d) yields CFA-1 as trigonal prismatic single crystals. CFA-1 serves as a convenient precursor for the synthesis of isostructural frameworks with redox-active metal centres, which is demonstrated by the postsynthetic exchange of Zn(2+) by Co(2+) ions. The framework is robust to solvent removal and has been structurally characterized by synchrotron single-crystal X-ray diffraction and solid state NMR measurements ((13)C MAS- and (1)H MAS-NMR at 10 kHz). Results from MAS-NMR and IR spectroscopy studies are corroborated by cluster and periodic DFT calculations performed on CFA-1 cluster fragments.

  9. Unexpected crystallization patterns of zinc boron imidazolate framework ZBIF-1: NMR crystallography of integrated metal-organic frameworks

    Czech Academy of Sciences Publication Activity Database

    Kobera, Libor; Rohlíček, Jan; Czernek, Jiří; Abbrent, Sabina; Strečková, M.; Sopčák, T.; Brus, Jiří

    2017-01-01

    Roč. 18, č. 24 (2017), s. 3576-3582 ISSN 1439-4235 R&D Projects: GA ČR(CZ) GA16-04109S; GA ČR(CZ) GA16-13778S Institutional support: RVO:61389013 ; RVO:68378271 Keywords : density functional calculations * metal-organic frameworks * NMR spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry; CF - Physical ; Theoretical Chemistry (FZU-D) OBOR OECD: Physical chemistry; Physical chemistry (FZU-D) Impact factor: 3.075, year: 2016

  10. Recent advances in metal-organic frameworks and covalent organic frameworks for sample preparation and chromatographic analysis.

    Science.gov (United States)

    Wang, Xuan; Ye, Nengsheng

    2017-12-01

    In the field of analytical chemistry, sample preparation and chromatographic separation are two core procedures. The means by which to improve the sensitivity, selectivity and detection limit of a method have become a topic of great interest. Recently, porous organic frameworks, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), have been widely used in this research area because of their special features, and different methods have been developed. This review summarizes the applications of MOFs and COFs in sample preparation and chromatographic stationary phases. The MOF- or COF-based solid-phase extraction (SPE), solid-phase microextraction (SPME), gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC) methods are described. The excellent properties of MOFs and COFs have resulted in intense interest in exploring their performance and mechanisms for sample preparation and chromatographic separation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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....

  12. 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...

  13. High performance hydrogen storage from Be-BTB metal-organic framework at room temperature.

    Science.gov (United States)

    Lim, Wei-Xian; Thornton, Aaron W; Hill, Anita J; Cox, Barry J; Hill, James M; Hill, Matthew R

    2013-07-09

    The metal-organic framework beryllium benzene tribenzoate (Be-BTB) has recently been reported to have one of the highest gravimetric hydrogen uptakes at room temperature. Storage at room temperature is one of the key requirements for the practical viability of hydrogen-powered vehicles. Be-BTB has an exceptional 298 K storage capacity of 2.3 wt % hydrogen. This result is surprising given that the low adsorption enthalpy of 5.5 kJ mol(-1). In this work, a combination of atomistic simulation and continuum modeling reveals that the beryllium rings contribute strongly to the hydrogen interaction with the framework. These simulations are extended with a thermodynamic energy optimization (TEO) model to compare the performance of Be-BTB to a compressed H2 tank and benchmark materials MOF-5 and MOF-177 in a MOF-based fuel cell. Our investigation shows that none of the MOF-filled tanks satisfy the United States Department of Energy (DOE) storage targets within the required operating temperatures and pressures. However, the Be-BTB tank delivers the most energy per volume and mass compared to the other material-based storage tanks. The pore size and the framework mass are shown to be contributing factors responsible for the superior room temperature hydrogen adsorption of Be-BTB.

  14. Research Update: Mechanical properties of metal-organic frameworks – Influence of structure and chemical bonding

    Directory of Open Access Journals (Sweden)

    Wei Li

    2014-12-01

    Full Text Available Metal-organic frameworks (MOFs, a young family of functional materials, have been attracting considerable attention from the chemistry, materials science, and physics communities. In the light of their potential applications in industry and technology, the fundamental mechanical properties of MOFs, which are of critical importance for manufacturing, processing, and performance, need to be addressed and understood. It has been widely accepted that the framework topology, which describes the overall connectivity pattern of the MOF building units, is of vital importance for the mechanical properties. However, recent advances in the area of MOF mechanics reveal that chemistry plays a major role as well. From the viewpoint of materials science, a deep understanding of the influence of chemical effects on MOF mechanics is not only highly desirable for the development of novel functional materials with targeted mechanical response, but also for a better understanding of important properties such as structural flexibility and framework breathing. The present work discusses the intrinsic connection between chemical effects and the mechanical behavior of MOFs through a number of prototypical examples.

  15. Research Update: Mechanical properties of metal-organic frameworks - Influence of structure and chemical bonding

    Science.gov (United States)

    Li, Wei; Henke, Sebastian; Cheetham, Anthony K.

    2014-12-01

    Metal-organic frameworks (MOFs), a young family of functional materials, have been attracting considerable attention from the chemistry, materials science, and physics communities. In the light of their potential applications in industry and technology, the fundamental mechanical properties of MOFs, which are of critical importance for manufacturing, processing, and performance, need to be addressed and understood. It has been widely accepted that the framework topology, which describes the overall connectivity pattern of the MOF building units, is of vital importance for the mechanical properties. However, recent advances in the area of MOF mechanics reveal that chemistry plays a major role as well. From the viewpoint of materials science, a deep understanding of the influence of chemical effects on MOF mechanics is not only highly desirable for the development of novel functional materials with targeted mechanical response, but also for a better understanding of important properties such as structural flexibility and framework breathing. The present work discusses the intrinsic connection between chemical effects and the mechanical behavior of MOFs through a number of prototypical examples.

  16. Superior removal of arsenic from water with zirconium metal-organic framework UiO-66

    Science.gov (United States)

    Wang, Chenghong; Liu, Xinlei; Chen, J. Paul; Li, Kang

    2015-01-01

    In this study, water stable zirconium metal-organic framework (UiO-66) has been synthesized and for the first time applied as an adsorbent to remove aquatic arsenic contamination. The as-synthesized UiO-66 adsorbent functions excellently across a broad pH range of 1 to 10, and achieves a remarkable arsenate uptake capacity of 303 mg/g at the optimal pH, i.e., pH = 2. To the best of our knowledge, this is the highest arsenate As(V) adsorption capacity ever reported, much higher than that of currently available adsorbents (5–280 mg/g, generally less than 100 mg/g). The superior arsenic uptake performance of UiO-66 adsorbent could be attributed to the highly porous crystalline structure containing zirconium oxide clusters, which provides a large contact area and plenty of active sites in unit space. Two binding sites within the adsorbent framework are proposed for arsenic species, i.e., hydroxyl group and benzenedicarboxylate ligand. At equilibrium, seven equivalent arsenic species can be captured by one Zr6 cluster through the formation of Zr-O-As coordination bonds. PMID:26559001

  17. Three-Dimensional Networked Metal-Organic Frameworks with Conductive Polypyrrole Tubes for Flexible Supercapacitors.

    Science.gov (United States)

    Xu, Xingtao; Tang, Jing; Qian, Huayu; Hou, Shujin; Bando, Yoshio; Hossain, Md Shahriar A; Pan, Likun; Yamauchi, Yusuke

    2017-11-08

    Metal-organic frameworks (MOFs) with high porosity and a regular porous structure have emerged as a promising electrode material for supercapacitors, but their poor electrical conductivity limits their utilization efficiency and capacitive performance. To increase the overall electrical conductivity as well as the efficiency of MOF particles, three-dimensional networked MOFs are developed via using preprepared conductive polypyrrole (PPy) tubes as the support for in situ growth of MOF particles. As a result, the highly conductive PPy tubes that run through the MOF particles not only increase the electron transfer between MOF particles and maintain the high effective porosity of the MOFs but also endow the MOFs with flexibility. Promoted by such elaborately designed MOF-PPy networks, the specific capacitance of MOF particles has been increased from 99.2 F g -1 for pristine zeolitic imidazolate framework (ZIF)-67 to 597.6 F g -1 for ZIF-PPy networks, indicating the importance of the design of the ZIF-PPy continuous microstructure. Furthermore, a flexible supercapacitor device based on ZIF-PPy networks shows an outstanding areal capacitance of 225.8 mF cm -2 , which is far above other MOFs-based supercapacitors reported up to date, confirming the significance of in situ synthetic chemistry as well as the importance of hybrid materials on the nanoscale.

  18. A 3D Ag(I) metal-organic framework for sensing luminescence and photocatalytic activities

    Science.gov (United States)

    Chang, Hai-Ning; Liu, Li-Wei; Hao, Zeng Chuan; Cui, Guang-Hua

    2018-03-01

    A fluorescent metal-organic framework (MOF), [Ag(btx)0.5(DCTP)0.5]n (1) (H2DCTP = 2,5-dichloroterephthalic acid and btx = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) has been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, powder X-ray diffractions and thermogravimetry. The framework of 1 can be classified as a binodal (4,4)-connected PtS topological network. The fluorescence explorations demonstrated that 1 shows selective and sensitive detection towards Cr2O72- with high quenching efficiency of 1.92 × 104 M-1. The rapid and efficient response of 1 to Cr2O72- ion suggests that this material could be used as a luminescent sensor for Cr2O72- ion. Meanwhile the photocatalytic properties of 1 for the degradation of RhB have also been investigated under UV radiation. The possible photocatalytic mechanisms were also speculated. Hence, 1 can become multi-functional material in sensitive detection and effective removal of some environment pollutants in industrial waste water solutions.

  19. Structure-directing effects of ionic liquids in the ionothermal synthesis of metal-organic frameworks.

    Science.gov (United States)

    Vaid, Thomas P; Kelley, Steven P; Rogers, Robin D

    2017-07-01

    Traditional synthesis of metal-organic frameworks (MOFs) involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a 'solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs), rather than an organic solvent, in 'ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

  20. Direct Electrical Detection of Iodine Gas by a Novel Metal-Organic-Framework-Based Sensor.

    Science.gov (United States)

    Small, Leo J; Nenoff, Tina M

    2017-12-27

    High-fidelity detection of iodine species is of utmost importance to the safety of the population in cases of nuclear accidents or advanced nuclear fuel reprocessing. Herein, we describe the success at using impedance spectroscopy to directly detect the real-time adsorption of I 2 by a metal-organic framework zeolitic imidazolate framework (ZIF)-8-based sensor. Methanolic suspensions of ZIF-8 were dropcast onto platinum interdigitated electrodes, dried, and exposed to gaseous I 2 at 25, 40, or 70 °C. Using an unoptimized sensor geometry, I 2 was readily detected at 25 °C in air within 720 s of exposure. The specific response is attributed to the chemical selectivity of the ZIF-8 toward I 2 . Furthermore, equivalent circuit modeling of the impedance data indicates a >10 5 × decrease in ZIF-8 resistance when 116 wt % I 2 is adsorbed by ZIF-8 at 70 °C in air. This irreversible decrease in resistance is accompanied by an irreversible loss in the long-range crystallinity, as evidenced by X-ray diffraction and infrared spectroscopy. Air, argon, methanol, and water were found to produce minimal changes in ZIF-8 impedance. This report demonstrates how selective I 2 adsorption by ZIF-8 can be leveraged to create a highly selective sensor using >10 5 × changes in impedance response to enable the direct electrical detection of environmentally relevant gaseous toxins.

  1. Sulfation of metal-organic framework: Opportunities for acid catalysis and proton conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Goesten, M.G.; Stavitski, E.; Juan-Alcaniz, J.; Ramos-Fernandez, E.V.; Sai Sankar Gupta, K.B.; van Bekkum, H.; Gascon, J. and Kapteijn, F.

    2011-05-24

    A new post-functionalization method for metal-organic frameworks (MOFs) has been developed to introduce acidity for catalysis. Upon treatment with a mixture of triflic anhydride and sulfuric acid, chemically stable MOF structures MIL-101(Cr) and MIL-53(Al) can be sulfated, resulting in a Broensted sulfoxy acid group attached to up to 50% of the aromatic terephthalate linkers of the structure. The sulfated samples have been extensively characterized by solid-state NMR, XANES, and FTIR spectroscopy. The functionalized acidic frameworks show catalytic activity similar to that of acidic polymers like Nafion{reg_sign} display in the esterification of n-butanol with acetic acid (TOF {approx} 1 min{sup -1} {at} 343 K). Water adsorbs strongly up to 4 molecules per sulfoxy acid group, and an additional 2 molecules are taken up at lower temperatures in the 1-D pore channels of S-MIL-53(Al). The high water content and Broensted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.

  2. Superior removal of arsenic from water with zirconium metal-organic framework UiO-66.

    Science.gov (United States)

    Wang, Chenghong; Liu, Xinlei; Chen, J Paul; Li, Kang

    2015-11-12

    In this study, water stable zirconium metal-organic framework (UiO-66) has been synthesized and for the first time applied as an adsorbent to remove aquatic arsenic contamination. The as-synthesized UiO-66 adsorbent functions excellently across a broad pH range of 1 to 10, and achieves a remarkable arsenate uptake capacity of 303 mg/g at the optimal pH, i.e., pH = 2. To the best of our knowledge, this is the highest arsenate As(V) adsorption capacity ever reported, much higher than that of currently available adsorbents (5-280 mg/g, generally less than 100 mg/g). The superior arsenic uptake performance of UiO-66 adsorbent could be attributed to the highly porous crystalline structure containing zirconium oxide clusters, which provides a large contact area and plenty of active sites in unit space. Two binding sites within the adsorbent framework are proposed for arsenic species, i.e., hydroxyl group and benzenedicarboxylate ligand. At equilibrium, seven equivalent arsenic species can be captured by one Zr6 cluster through the formation of Zr-O-As coordination bonds.

  3. CFA-4 - a fluorinated metal-organic framework with exchangeable interchannel cations.

    Science.gov (United States)

    Fritzsche, J; Grzywa, M; Denysenko, D; Bon, V; Senkovska, I; Kaskel, S; Volkmer, D

    2017-05-23

    The syntheses and crystal structures of the fluorinated linker 1,4-bis(3,5-bis(trifluoromethyl)-1H-pyrazole-4-yl)benzene (H 2 -tfpb; 1) and the novel metal-organic framework family M[CFA-4] (Coordination Framework Augsburg University-4), M[Cu 5 (tfpb) 3 ] (M = Cu(i), K, Cs, Ca(0.5)), are described. The ligand 1 is fully characterized by single crystal X-ray diffraction, photoluminescence-, NMR-, IR spectroscopy, and mass spectrometry. The copper(i)-containing MOF crystallizes in the hexagonal crystal system within the chiral space group P6 3 22 (no. 182) and the unit cell parameters are as follows: a = 23.630(5) Å, c = 41.390(5) Å, V = 20 015(6) Å 3 . M[CFA-4] features a porous 3-D structure constructed from pentanuclear copper(i) secondary building units {Cu(pz) 6 } - (pz = pyrazolate). Cu(I)[CFA-4] is fully characterized by synchrotron single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence and gas sorption measurements. Moreover, thermal stability and gas sorption properties of K[CFA-4] and Cu(I)[CFA-4] are compared.

  4. A polyoxometalate-encapsulating cationic metal-organic framework as a heterogeneous catalyst for desulfurization.

    Science.gov (United States)

    Hao, Xiu-Li; Ma, Yuan-Yuan; Zang, Hong-Ying; Wang, Yong-Hui; Li, Yang-Guang; Wang, En-Bo

    2015-02-23

    A new cationic triazole-based metal-organic framework encapsulating Keggin-type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of compound 1 contains a non-interpenetrated 3D CdSO4 (cds)-type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin-type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size-selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Metal organic framework Cu9Cl2(cpa)6 as tunable molecular magnet

    Science.gov (United States)

    Hamilton, Heather S. C.; Farmer, William M.; Skinner, Samuel F.; ter Haar, Leonard W.

    2018-05-01

    Chemical modifications of the magnetic metal organic framework (MOF) Cu9X2(cpa)6.42H2O (X = F, Cl, Br; cpa = anion of 2-carboxypentonicacid) have been investigated as a means of modifying, in a tunable manner, the magnetism of this 2-D material best described as a triangles-in-triangles (TIT) or triangulated-Kagomé-latttice (TKL). Since numerous theoretical studies have already attempted to describe the enigmatic ground state of this Heisenberg lattice, tunable chemical modifications should provide an excellent opportunity to expand this class of materials for studies concerning fundamental physics of frustrated spins, and applications such as adiabatic demagnetization refrigeration (ADR) that depend on the magnetocaloric effect (MCE). The chemical modification investigated is the intercalation of d- and f-orbital ions into the voids of the framework (channels of nearly 20 Å diameter). Magnetic measurements in the temperature range 1.8 - 300 K confirm signature features of TKL magnetism in intercalated samples persist, specifically: i) large negative Weiss constant (θCW); ii) absence of a phase transition down to 1.8 K; iii) minimum in χMT; iv) low temperature χMT values increasingly divergent at low fields indicating net ferromagnetic correlations; and, v) increasing field dependence of magnetization at low temperatures suggestive of intermediate plateaus, or ferrimagnetism, not saturation.

  6. Unravelling surface and interfacial structures of a metal-organic framework by transmission electron microscopy.

    Science.gov (United States)

    Zhu, Yihan; Ciston, Jim; Zheng, Bin; Miao, Xiaohe; Czarnik, Cory; Pan, Yichang; Sougrat, Rachid; Lai, Zhiping; Hsiung, Chia-En; Yao, Kexin; Pinnau, Ingo; Pan, Ming; Han, Yu

    2017-05-01

    Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

  7. Biomolecule-embedded metal-organic frameworks as an innovative sensing platform.

    Science.gov (United States)

    Kempahanumakkagari, Sureshkumar; Kumar, Vanish; Samaddar, Pallabi; Kumar, Pawan; Ramakrishnappa, Thippeswamy; Kim, Ki-Hyun

    Technological advancements combined with materials research have led to the generation of enormous types of novel substrates and materials for use in various biological/medical, energy, and environmental applications. Lately, the embedding of biomolecules in novel and/or advanced materials (e.g., metal-organic frameworks (MOFs), nanoparticles, hydrogels, graphene, and their hybrid composites) has become a vital research area in the construction of an innovative platform for various applications including sensors (or biosensors), biofuel cells, and bioelectronic devices. Due to the intriguing properties of MOFs (e.g., framework architecture, topology, and optical properties), they have contributed considerably to recent progresses in enzymatic catalysis, antibody-antigen interactions, or many other related approaches. Here, we aim to describe the different strategies for the design and synthesis of diverse biomolecule-embedded MOFs for various sensing (e.g., optical, electrochemical, biological, and miscellaneous) techniques. Additionally, the benefits and future prospective of MOFs-based biomolecular immobilization as an innovative sensing platform are discussed along with the evaluation on their performance to seek for further development in this emerging research area. Copyright © 2018. Published by Elsevier Inc.

  8. Controlling Cooperative CO2 Adsorption in Diamine-Appended Mg2(dobpdc) Metal-Organic Frameworks.

    Science.gov (United States)

    Siegelman, Rebecca L; McDonald, Thomas M; Gonzalez, Miguel I; Martell, Jeffrey D; Milner, Phillip J; Mason, Jarad A; Berger, Adam H; Bhown, Abhoyjit S; Long, Jeffrey R

    2017-08-02

    In the transition to a clean-energy future, CO 2 separations will play a critical role in mitigating current greenhouse gas emissions and facilitating conversion to cleaner-burning and renewable fuels. New materials with high selectivities for CO 2 adsorption, large CO 2 removal capacities, and low regeneration energies are needed to achieve these separations efficiently at scale. Here, we present a detailed investigation of nine diamine-appended variants of the metal-organic framework Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) that feature step-shaped CO 2 adsorption isotherms resulting from cooperative and reversible insertion of CO 2 into metal-amine bonds to form ammonium carbamate chains. Small modifications to the diamine structure are found to shift the threshold pressure for cooperative CO 2 adsorption by over 4 orders of magnitude at a given temperature, and the observed trends are rationalized on the basis of crystal structures of the isostructural zinc frameworks obtained from in situ single-crystal X-ray diffraction experiments. The structure-activity relationships derived from these results can be leveraged to tailor adsorbents to the conditions of a given CO 2 separation process. The unparalleled versatility of these materials, coupled with their high CO 2 capacities and low projected energy costs, highlights their potential as next-generation adsorbents for a wide array of CO 2 separations.

  9. 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.

  10. Reticular Chemistry and Metal-Organic Frameworks: Design and Synthesis of Functional Materials for Clean Energy Applications

    KAUST Repository

    Alezi, Dalal A.

    2017-06-01

    Gaining control over the assembly of crystalline solid-state materials has been significantly advanced through the field of reticular chemistry and metal organic frameworks (MOFs). MOFs have emerged as a unique modular class of porous materials amenable to a rational design with targeted properties for given applications. Several design approaches have been deployed to construct targeted functional MOFs, where desired structural and geometrical attributes are incorporated in preselected building units prior to the assembly process. This dissertation illustrates the merit of the molecular building block approach (MBB) for the rational construction and discovery of stable and highly porous MOFs, and their exploration as potential gas storage medium for sustainable and clean energy applications. Specifically, emphasis was placed on gaining insights into the structure-property relationships that impact the methane (CH4) storage in MOFs and its subsequent delivery. The foreseen gained understanding is essential for the design of new adsorbent materials or adjusting existing MOF platforms to encompass the desired features that subsequently afford meeting the challenging targets for methane storage in mobile and stationary applications.In this context, we report the successful use of the MBB approach for the design and deliberate construction of a series of novel isoreticular, highly porous and stable, aluminum based MOFs with the square-octahedral (soc) underlying net topology. From this platform, Al-soc-MOF-1, with more than 6000 m2/g apparent Langmuir specific surface area, exhibits outstanding gravimetric CH4 uptake (total and working capacities). It is shown experimentally, for the first time, that the Al-soc-MOF platform can address the U.S. Department of Energy (DOE) challenging gravimetric and volumetric targets for the CH4 working capacity for on-board CH4 storage. Furthermore, Al-soc-MOF-1 exhibits the highest total gravimetric and volumetric uptake for carbon

  11. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Tanuwijaya, V. V., E-mail: viny.veronika@gmail.com [Engineering Physics, Faculty of Industrial Technology, Institut Teknologi Bandung Jalan Ganeca 10 Gd. T.P. Rachmat, Bandung 40132 (Indonesia); Hidayat, N. N., E-mail: avantgarde.vee@gmail.com; Agusta, M. K., E-mail: kemal@fti.itb.ac.id; Dipojono, H. K., E-mail: dipojono@tf.itb.ac.id

    2015-09-30

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  12. Flexible metal-organic framework compounds: In situ studies for selective CO{sub 2} capture

    Energy Technology Data Exchange (ETDEWEB)

    Allen, A.J., E-mail: andrew.allen@nist.gov [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Espinal, L.; Wong-Ng, W. [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Queen, W.L. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); The Molecular Foundry, Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA 94720 (United States); Brown, C.M. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716 (United States); Kline, S.R. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Kauffman, K.L. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); Culp, J.T. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); URS Corporation, South Park, PA 15219 (United States); Matranga, C. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States)

    2015-10-25

    Results are presented that explore the dynamic structural changes occurring in two highly flexible nanocrystalline metal-organic framework (MOF) compounds during the adsorption and desorption of pure gases and binary mixtures. The Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN){sub 4}] and catena-bis(dibenzoylmethanato)-(4,4′-bipyridyl)nickel(II) chosen for this study are 3-D and 1-D porous coordination polymers (PCP) with a similar gate opening pressure response for CO{sub 2} isotherms at 303 K, but with differing degrees of flexibility for structural change to accommodate guest molecules. As such, they serve as a potential model system for evaluating the complex kinetics associated with dynamic structure changes occurring in response to gas adsorption in flexible MOF systems. Insights into the crystallographic changes occurring as the MOF pore structure expands and contracts in response to interactions with CO{sub 2}, N{sub 2}, and CO{sub 2}/N{sub 2} mixtures have been obtained from in situ small-angle neutron scattering and neutron diffraction, combined with ex situ X-ray diffraction structure measurements. The role of structure in carbon capture functionality is discussed with reference to the ongoing characterization challenges and a possible materials-by-design approach. - Graphical abstract: We present in situ small-angle neutron scattering results for two flexible metal-organic frameworks (MOFs). The figure shows that for one (NiBpene, high CO{sub 2} adsorption) the intensity of the Bragg peak for the expandable d-spacing most associated with CO{sub 2} adsorption varies approximately with the isotherm, while for the other (NiDBM-Bpy, high CO{sub 2} selectivity) the d-spacing, itself, varies with the isotherm. The cartoons show the proposed modes of structural change. - Highlights: • Dynamic structures of two flexible MOF CO{sub 2} sorbent compounds are compared in situ. • These porous solid sorbents serve as models for pure & dual gas adsorption. • Different

  13. Metal organic framework absorbent platforms for removal of co2 and h2s from natural gas

    KAUST Repository

    Belmabkhout, Youssef; Eddaoudi, Mohamed; Adil, Karim; Cadiau, Amandine; Bhatt, Prashant M.

    2016-01-01

    Provided herein are metal organic frameworks comprising metal nodes and N-donor organic ligands which have high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Methods include capturing one or more of H2S, H2O, and CO2 from fluid compositions, such as natural gas.

  14. Metal organic framework absorbent platforms for removal of co2 and h2s from natural gas

    KAUST Repository

    Belmabkhout, Youssef

    2016-10-13

    Provided herein are metal organic frameworks comprising metal nodes and N-donor organic ligands which have high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Methods include capturing one or more of H2S, H2O, and CO2 from fluid compositions, such as natural gas.

  15. Screening metal-organic frameworks by analysis of transient breakthrough of gas mixtures in a fixed bed adsorber

    NARCIS (Netherlands)

    Krishna, R.; Long, J.R.

    2011-01-01

    Metal-organic frameworks (MOFs) offer considerable potential for separating a variety of mixtures that are important in applications such as CO2 capture and H2 purification. In view of the vast number of MOFs that have been synthesized, there is a need for a reliable procedure for comparing

  16. 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.

  17. A systematic study on the use of ultrasound energy for the synthesis of nickel-metal organic framework compounds

    NARCIS (Netherlands)

    Sargazi, G.; Afzali, D.; Daldosso, N.; Kazemian, H.; Chauhan, N.P.S.; Sadeghian, Z.; Tajerian, T.; Ghafarinazari, A.; Mozafari, M.

    2015-01-01

    A nickel metal-organic framework (Ni-MOF) was successfully synthesized using ultrasound irradiation. Further to this, X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Thermo-Gravimetric Analysis (TGA), Differential Scanning Calorimetry

  18. A charge-polarized porous metal-organic framework for gas chromatographic separation of alcohols from water.

    Science.gov (United States)

    Sun, Jian-Ke; Ji, Min; Chen, Cheng; Wang, Wu-Gen; Wang, Peng; Chen, Rui-Ping; Zhang, Jie

    2013-02-25

    A bipyridinium ligand with a charge separated skeleton has been introduced into a metal-organic framework to yield a porous material with charge-polarized pore space, which exhibits selective adsorption for polar guest molecules and can be further used in gas chromatography for the separation of alcohol-water mixtures.

  19. Metal-directed topological diversity of three fluorescent metal-organic frameworks based on a new tetracarboxylate strut

    KAUST Repository

    Lou, Xinhua

    2013-01-01

    Three d- or p-block metal ions based metal-organic frameworks (MOFs) were isolated by employing a new tetracarboxylate linker, featuring unusual flu, self-interpenetrated lvt and new (3,5)-c topological nets, respectively. Interesting photoluminescent properties of these solid-state materials were also observed. © 2013 The Royal Society of Chemistry.

  20. Gas transport in metal organic framework-polyetherimide mixed matrix membranes: The role of the polyetherimide backbone structure

    NARCIS (Netherlands)

    Hegde, Maruti; Shahid, Salman; Norder, Ben; Dingemans, T.J.; Nijmeijer, Kitty

    2015-01-01

    We report on how the morphology of the polymer matrix, i.e. amorphous vs. semi-crystalline, affects the gas transport properties in a series of mixed matrix membranes (MMMs) using Cu3(BTC)2 as the metal organic framework (MOF) filler. The aim of our work is to demonstrate how incorporation of

  1. CO 2 adsorption in mono-, di- and trivalent cation-exchanged metal-organic frameworks: A molecular simulation study

    KAUST Repository

    Chen, Yifei; Nalaparaju, Anjaiah; Eddaoudi, Mohamed; JIANG, Jianwen

    2012-01-01

    A molecular simulation study is reported for CO 2 adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, and Al 3+). The isosteric heat and Henry's constant

  2. Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity.

    Science.gov (United States)

    Lammert, Martin; Wharmby, Michael T; Smolders, Simon; Bueken, Bart; Lieb, Alexandra; Lomachenko, Kirill A; Vos, Dirk De; Stock, Norbert

    2015-08-14

    A series of nine Ce(iv)-based metal organic frameworks with the UiO-66 structure containing linker molecules of different sizes and functionalities were obtained under mild synthesis conditions and short reaction times. Thermal and chemical stabilities were determined and a Ce-UiO-66-BDC/TEMPO system was successfully employed for the aerobic oxidation of benzyl alcohol.

  3. A tetrapyridine ligand with a rigid tetrahedral core forms metal-organic frameworks with PtS type architecture.

    Science.gov (United States)

    Caputo, Christopher B; Vukotic, V Nicholas; Sirizzotti, Natalie M; Loeb, Stephen J

    2011-08-14

    A new tetradentate, pyridine ligand with a rigid tetrahedral core can be prepared in good yield by a cross-coupling methodology. Two metal organic framework structures of Cu(II) with PtS-type topology having a carbon atom as the tetrahedral node have been characterized utilising this ligand. This journal is © The Royal Society of Chemistry 2011

  4. Mechanistic Insights into Growth of Surface-Mounted Metal-Organic Framework Films Resolved by Infrared (Nano-) Spectroscopy

    NARCIS (Netherlands)

    Delen, Guusje; Ristanovic, Zoran; Mandemaker, Laurens D. B.; Weckhuysen, Bert M.

    2018-01-01

    Control over assembly, orientation, and defect-free growth of metal-organic framework (MOF) films is crucial for their future applications. A layer-by-layer approach is considered a suitable method to synthesize highly oriented films of numerous MOF topologies, but the initial stages of the film

  5. 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.

  6. CO2 Capture Using the SIFSIX-2-Cu-i Metal-Organic Framework: A Computational Approach

    KAUST Repository

    Skarmoutsos, Ioannis; Belmabkhout, Youssef; Adil, Karim; Eddaoudi, Mohamed; Maurin, Guillaume

    2017-01-01

    The adsorption of carbon dioxide and its separation from mixtures with methane using the recently synthetized SIFSIX-2-Cu-i metal-organic framework (Nature, 2014, 495, 80-84) has been systematically studied by employing a variety of molecular

  7. The concept of mixed organic ligands in metal-organic frameworks: design, tuning and functions.

    Science.gov (United States)

    Yin, Zheng; Zhou, Yan-Ling; Zeng, Ming-Hua; Kurmoo, Mohamedally

    2015-03-28

    The research on metal-organic frameworks (MOFs) has been developing at an extraordinary pace in its two decades of existence, as judged by the exponential growth of novel structures and the constant expansion of its applicability and research scope. A major part of the research and its success are due to the vital role of the concept of mixed organic ligands in the design, tuning and functions. This perspective, therefore, reviews the recent advances in MOFs based on this concept, which is generally based on employing a small polydentate ligand (here labelled as "nodal ligand") to form either clusters, rods or layers, which are then connected by a second ditopic linker ligand to form the framework. The structures of the materials can be grouped into the following three categories: layer-spacer (usually known as pillared-layer), rod-spacer, and cluster-spacer based MOFs. Depending on the size and geometry of the spacer ligands, interpenetrations of frameworks are occasionally found. These MOFs show a wide range of properties such as (a) crystal-to-crystal transformations upon solvent modifications, post-synthetic metal exchange or ligand reactions, (b) gas sorption, solvent selectivity and purification, (c) specific catalysis, (d) optical properties including colour change, luminescence, non-linear optic, (e) short- and long range magnetic ordering, metamagnetism and reversible ground-state modifications and (f) drug and iodine carriers with controlled release. In the following, we will highlight the importance of the above concept in the design, tuning, and functions of a selection of existing MOFs having mixed organic ligands and their associated structures and properties. The results obtained so far using this concept look very promising for fine-tuning the pore size and shape for selective adsorption and specificity in catalytic reactions, which appears to be one way to propel the advances in the application and commercialization of MOFs.

  8. Stress-induced chemical detection using flexible metal-organic frameworks.

    Science.gov (United States)

    Allendorf, Mark D; Houk, Ronald J T; Andruszkiewicz, Leanne; Talin, A Alec; Pikarsky, Joel; Choudhury, Arnab; Gall, Kenneth A; Hesketh, Peter J

    2008-11-05

    In this work we demonstrate the concept of stress-induced chemical detection using metal-organic frameworks (MOFs) by integrating a thin film of the MOF HKUST-1 with a microcantilever surface. The results show that the energy of molecular adsorption, which causes slight distortions in the MOF crystal structure, can be converted to mechanical energy to create a highly responsive, reversible, and selective sensor. This sensor responds to water, methanol, and ethanol vapors, but yields no response to either N2 or O2. The magnitude of the signal, which is measured by a built-in piezoresistor, is correlated with the concentration and can be fitted to a Langmuir isotherm. Furthermore, we show that the hydration state of the MOF layer can be used to impart selectivity to CO2. Finally, we report the first use of surface-enhanced Raman spectroscopy to characterize the structure of a MOF film. We conclude that the synthetic versatility of these nanoporous materials holds great promise for creating recognition chemistries to enable selective detection of a wide range of analytes.

  9. Nanoscale Metal-Organic Frameworks Decorated with Graphene Oxide for Magnetic Resonance Imaging Guided Photothermal Therapy.

    Science.gov (United States)

    Meng, Jing; Chen, Xiujin; Tian, Yang; Li, Zhongfeng; Zheng, Qingfeng

    2017-12-11

    Imaging-guided photothermal therapy (PTT) provides an attractive way to treat cancer. A composite material of a nanoscale metal-organic framework (NMOF) and graphene oxide (GO) has been prepared for potential use in tumor-guided PTT with magnetic resonance imaging (MRI). The NMOFs containing Fe 3+ were prefabricated with an octahedral morphology through a solvothermal reaction to offer a strong T 2 -weighted contrast in MRI. Then the NMOFs were decorated with GO nanosheets, which had good photothermal properties. After decoration, zeta-potential characterization shows that the aqueous stability of the composite material is enhanced, UV/Vis and near-infrared (NIR) spectra confirm that NIR absorption is also increased, and photothermal experiments reveal that the composite materials express higher photothermal conversion effects and conversion stability. The fabricated NMOF/GO shows low cytotoxicity, effective T 2 -weighted contrast of MRI, and positive PTT behavior for a tumor model in vitro. The performance of the composite NMOF/GO for MRI and PTT was also tested upon injection into A549 tumor-bearing mice. The studies in vivo revealed that the fabricated NMOF/GO was efficient in T 2 -weighted imaging and ablation of the A549 tumor with low cytotoxicity, which implied that the prepared composite contrast agent was a potential multifunctional nanotheranostic agent. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Density functional theory for adsorption of gas mixtures in metal-organic frameworks.

    Science.gov (United States)

    Liu, Yu; Liu, Honglai; Hu, Ying; Jiang, Jianwen

    2010-03-04

    In this work, a recently developed density functional theory in three-dimensional space was extended to the adsorption of gas mixtures. Weighted density approximations to the excess free energy with different weighting functions were adopted for both repulsive and attractive contributions. An equation of state for hard-sphere mixtures and a modified Benedict-Webb-Rubin equation for Lennard-Jones mixtures were used to estimate the excess free energy of a uniform fluid. The theory was applied to the adsorption of CO(2)/CH(4) and CO(2)/N(2) mixtures in two metal-organic frameworks: ZIF-8 and Zn(2)(BDC)(2)(ted). To validate the theoretical predictions, grand canonical Monte Carlo simulations were also conducted. The predicted adsorption and selectivity from DFT were found to agree well with the simulation results. CO(2) has stronger adsorption than CH(4) and N(2), particularly in Zn(2)(BDC)(2)(ted). The selectivity of CO(2) over CH(4) or N(2) increases with increasing pressure as attributed to the cooperative interactions of adsorbed CO(2) molecules. The composition of the gas mixture exhibits a significant effect on adsorption but not on selectivity.

  11. Microstructural Engineering and Architectural Design of Metal-Organic Framework Membranes.

    Science.gov (United States)

    Liu, Yi; Ban, Yujie; Yang, Weishen

    2017-08-01

    In the past decade, a huge development in rational design, synthesis, and application of molecular sieve membranes, which typically included zeolites, metal-organic frameworks (MOFs), and graphene oxides, has been witnessed. Owing to high flexibility in both pore apertures and functionality, MOFs in the form of membranes have offered unprecedented opportunities for energy-efficient gas separations. Reports on the fabrication of well-intergrown MOF membranes first appeared in 2009. Since then there has been tremendous growth in this area along with an exponential increase of MOF-membrane-related publications. In order to compete with other separation and purification technologies, like cryogenic distillation, pressure swing adsorption, and chemical absorption, separation performance (including permeability, selectivity, and long-term stability) of molecular sieve membranes must be further improved in an attempt to reach an economically attractive region. Therefore, microstructural engineering and architectural design of MOF membranes at mesoscopic and microscopic levels become indispensable. This review summarizes some intriguing research that may potentially contribute to large-scale applications of MOF membranes in the future. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Effective Recovery of Vanadium from Oil Refinery Waste into Vanadium-Based Metal-Organic Frameworks.

    Science.gov (United States)

    Zhan, Guowu; Ng, Wei Cheng; Lin, Wenlin Yvonne; Koh, Shin Nuo; Wang, Chi-Hwa

    2018-03-06

    Carbon black waste, an oil refinery waste, contains a high concentration of vanadium(V) leftover from the processing of crude oil. For the sake of environmental sustainability, it is therefore of interest to recover the vanadium as useful products instead of disposing of it. In this work, V was recovered in the form of vanadium-based metal-organic frameworks (V-MOFs) via a novel pathway by using the leaching solution of carbon black waste instead of commercially available vanadium chemicals. Two different types of V-MOFs with high levels of crystallinity and phase purity were fabricated in very high yields (>98%) based on a coordination modulation method. The V-MOFs exhibited well-defined and controlled shapes such as nanofibers (length: > 10 μm) and nanorods (length: ∼270 nm). Furthermore, the V-MOFs showed high catalytic activities for the oxidation of benzyl alcohol to benzaldehyde, indicating the strong potential of the waste-derived V-MOFs in catalysis applications. Overall, our work offers a green synthesis pathway for the preparation of V-MOFs by using heavy metals of industrial waste as the metal source.

  13. Metal-Organic Framework-Derived Materials for Sodium Energy Storage.

    Science.gov (United States)

    Zou, Guoqiang; Hou, Hongshuai; Ge, Peng; Huang, Zhaodong; Zhao, Ganggang; Yin, Dulin; Ji, Xiaobo

    2018-01-01

    Recently, sodium-ion batteries (SIBs) are extensively explored and are regarded as one of the most promising alternatives to lithium-ion batteries for electrochemical energy conversion and storage, owing to the abundant raw material resources, low cost, and similar electrochemical behavior of elemental sodium compared to lithium. Metal-organic frameworks (MOFs) have attracted enormous attention due to their high surface areas, tunable structures, and diverse applications in drug delivery, gas storage, and catalysis. Recently, there has been an escalating interest in exploiting MOF-derived materials as anodes for sodium energy storage due to their fast mass transport resulting from their highly porous structures and relatively simple preparation methods originating from in situ thermal treatment processes. In this Review, the recent progress of the sodium-ion storage performances of MOF-derived materials, including MOF-derived porous carbons, metal oxides, metal oxide/carbon nanocomposites, and other materials (e.g., metal phosphides, metal sulfides, and metal selenides), as SIB anodes is systematically and completely presented and discussed. Moreover, the current challenges and perspectives of MOF-derived materials in electrochemical energy storage are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000.

    Science.gov (United States)

    Wang, Timothy C; Vermeulen, Nicolaas A; Kim, In Soo; Martinson, Alex B F; Stoddart, J Fraser; Hupp, Joseph T; Farha, Omar K

    2016-01-01

    The synthesis of NU-1000, a highly robust mesoporous (containing pores >2 nm) metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. Tetrabromopyrene and (4-(ethoxycarbonyl)phenyl)boronic acid can easily be coupled to prepare the requisite organic strut with four metal-binding sites in the form of four carboxylic acids, while zirconyl chloride octahydrate is used as a precursor for the well-defined metal oxide clusters. NU-1000 has been reported as an excellent candidate for the separation of gases, and it is a versatile scaffold for heterogeneous catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents, and it shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg-2.5 g of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 d.

  15. Materials and Techniques for Implantable Nutrient Sensing Using Flexible Sensors Integrated with Metal-Organic Frameworks.

    Science.gov (United States)

    Ling, Wei; Liew, Guoguang; Li, Ya; Hao, Yafeng; Pan, Huizhuo; Wang, Hanjie; Ning, Baoan; Xu, Hang; Huang, Xian

    2018-06-01

    The combination of novel materials with flexible electronic technology may yield new concepts of flexible electronic devices that effectively detect various biological chemicals to facilitate understanding of biological processes and conduct health monitoring. This paper demonstrates single- or multichannel implantable flexible sensors that are surface modified with conductive metal-organic frameworks (MOFs) such as copper-MOF and cobalt-MOF with large surface area, high porosity, and tunable catalysis capability. The sensors can monitor important nutriments such as ascorbicacid, glycine, l-tryptophan (l-Trp), and glucose with detection resolutions of 14.97, 0.71, 4.14, and 54.60 × 10 -6 m, respectively. In addition, they offer sensing capability even under extreme deformation and complex surrounding environment with continuous monitoring capability for 20 d due to minimized use of biological active chemicals. Experiments using live cells and animals indicate that the MOF-modified sensors are biologically safe to cells, and can detect l-Trp in blood and interstitial fluid. This work represents the first effort in integrating MOFs with flexible sensors to achieve highly specific and sensitive implantable electrochemical detection and may inspire appearance of more flexible electronic devices with enhanced capability in sensing, energy storage, and catalysis using various properties of MOFs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 2D Metal-Organic Frameworks Derived Nanocarbon Arrays for Substrate Enhancement in Flexible Supercapacitors.

    Science.gov (United States)

    Liu, Ximeng; Guan, Cao; Hu, Yating; Zhang, Lei; Elshahawy, Abdelnaby M; Wang, John

    2017-10-27

    Direct assembling of active materials on carbon cloth (CC) is a promising way to achieve flexible electrodes for energy storage. However, the overall surface area and electrical conductivity of such electrodes are usually limited. Herein, 2D metal-organic framework derived nanocarbon nanowall (MOFC) arrays are successfully developed on carbon cloth by a facile solution + carbonization process. Upon growth of the MOFC arrays, the sites for growth of the active materials are greatly increased, and the equivalent series resistance is decreased, which contribute to the enhancement of the bare CC substrate. After decorating ultrathin flakes of MnO 2 and Bi 2 O 3 on the flexible CC/MOFC substrate, the hierarchical electrode materials show an abrupt improvement of areal capacitances by around 50% and 100%, respectively, compared to those of the active materials on pristine carbon cloth. A flexible supercapacitor can be further assembled using two hierarchical electrodes, which demonstrates an energy density of 124.8 µWh cm -2 at the power density of 2.55 mW cm -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Statistical mechanics of binary mixture adsorption in metal-organic frameworks in the osmotic ensemble

    Science.gov (United States)

    Dunne, Lawrence J.; Manos, George

    2018-03-01

    Although crucial for designing separation processes little is known experimentally about multi-component adsorption isotherms in comparison with pure single components. Very few binary mixture adsorption isotherms are to be found in the literature and information about isotherms over a wide range of gas-phase composition and mechanical pressures and temperature is lacking. Here, we present a quasi-one-dimensional statistical mechanical model of binary mixture adsorption in metal-organic frameworks (MOFs) treated exactly by a transfer matrix method in the osmotic ensemble. The experimental parameter space may be very complex and investigations into multi-component mixture adsorption may be guided by theoretical insights. The approach successfully models breathing structural transitions induced by adsorption giving a good account of the shape of adsorption isotherms of CO2 and CH4 adsorption in MIL-53(Al). Binary mixture isotherms and co-adsorption-phase diagrams are also calculated and found to give a good description of the experimental trends in these properties and because of the wide model parameter range which reproduces this behaviour suggests that this is generic to MOFs. Finally, a study is made of the influence of mechanical pressure on the shape of CO2 and CH4 adsorption isotherms in MIL-53(Al). Quite modest mechanical pressures can induce significant changes to isotherm shapes in MOFs with implications for binary mixture separation processes. This article is part of the theme issue `Modern theoretical chemistry'.

  18. Kinetic Analysis of the Uptake and Release of Fluorescein by Metal-Organic Framework Nanoparticles

    Directory of Open Access Journals (Sweden)

    Tobias Preiß

    2017-02-01

    Full Text Available Metal-organic framework nanoparticles (MOF NPs are promising guest-host materials with applications in separation, storage, catalysis, and drug delivery. However, on- and off-loading of guest molecules by porous MOF nanostructures are still poorly understood. Here we study uptake and release of fluorescein by two representative MOF NPs, MIL-100(Fe and MIL-101(Cr. Suspensions of these MOF NPs exhibit well-defined size distributions and crystallinity, as verified by electron microscopy, dynamic light scattering, and X-ray diffraction. Using absorbance spectroscopy the equilibrium dissociation constants and maximum numbers of adsorbed fluorescein molecules per NP were determined. Time-resolved fluorescence studies reveal that rates of release and loading are pH dependent. The kinetics observed are compared to theoretical estimates that account for bulk diffusion into NPs, and retarded internal diffusion and adsorption rates. Our study shows that, rather than being simple volumetric carriers, MOF-NPs are dominated by internal surface properties. The findings will help to optimize payload levels and develop release strategies that exploit varying pH for drug delivery.

  19. Specific oriented metal-organic framework membranes and their facet-tuned separation performance.

    Science.gov (United States)

    Mao, Yiyin; Su, Binbin; Cao, Wei; Li, Junwei; Ying, Yulong; Ying, Wen; Hou, Yajun; Sun, Luwei; Peng, Xinsheng

    2014-09-24

    Modulating the crystal morphology, or the exposed crystal facets, of metal-organic frameworks (MOFs) expands their potential applications in catalysis, adsorption, and separation. In this article, by immobilizing the citrate modulators on Au nanoparticles and subsequently being fixed on solid copper hydroxide nanostrands, a well-intergrown and oriented HKUST-1 cube crystal membrane was formed at room temperature. In contrast, in the absence of Au nanoparticles, well-intergrown and oriented cuboctahedron and octahedron membranes were formed in water/ethanol and ethanol, respectively. The gas separation performances of these HKUST-1 membranes were tuned via their exposed facets with defined pore sizes. The HKUST-1 cube membrane with exposed {001} facets demonstrated the highest permeance but lowest gas binary separation factors, while the octahedron membrane with exposed {111} facets presented the highest separation factors but lowest permeance, since the window size of {111} facets is 0.46 nm which is smaller than 0.9 nm of {001} facets. Separation of 0.38 nm CO2 from 0.55 nm SF6 was realized by the HKUST-1 octahedron membrane. As a proof of concept, this will open a new way to design MOF-related separation membranes by facet controlling.

  20. Two-Dimensional Metal-Organic Framework Nanosheets for Membrane-Based Gas Separation.

    Science.gov (United States)

    Peng, Yuan; Li, Yanshuo; Ban, Yujie; Yang, Weishen

    2017-08-07

    Metal-organic framework (MOF) nanosheets could serve as ideal building blocks of molecular sieve membranes owing to their structural diversity and minimized mass-transfer barrier. To date, discovery of appropriate MOF nanosheets and facile fabrication of high performance MOF nanosheet-based membranes remain as great challenges. A modified soft-physical exfoliation method was used to disintegrate a lamellar amphiprotic MOF into nanosheets with a high aspect ratio. Consequently sub-10 nm-thick ultrathin membranes were successfully prepared, and these demonstrated a remarkable H 2 /CO 2 separation performance, with a separation factor of up to 166 and H 2 permeance of up to 8×10 -7  mol m -2  s -1  Pa -1 at elevated testing temperatures owing to a well-defined size-exclusion effect. This nanosheet-based membrane holds great promise as the next generation of ultrapermeable gas separation membrane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Ionic Liquid/Metal-Organic Framework Composites: From Synthesis to Applications.

    Science.gov (United States)

    Kinik, Fatma Pelin; Uzun, Alper; Keskin, Seda

    2017-07-21

    Metal-organic frameworks (MOFs) have been widely studied for different applications owing to their fascinating properties such as large surface areas, high porosities, tunable pore sizes, and acceptable thermal and chemical stabilities. Ionic liquids (ILs) have been recently incorporated into the pores of MOFs as cavity occupants to change the physicochemical properties and gas affinities of MOFs. Several recent studies have shown that IL/MOF composites show superior performances compared with pristine MOFs in various fields, such as gas storage, adsorption and membrane-based gas separation, catalysis, and ionic conductivity. In this review, we address the recent advances in syntheses of IL/MOF composites and provide a comprehensive overview of their applications. Opportunities and challenges of using IL/MOF composites in many applications are reviewed and the requirements for the utilization of these composite materials in real industrial processes are discussed to define the future directions in this field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Complex Nanostructures from Materials based on Metal-Organic Frameworks for Electrochemical Energy Storage and Conversion.

    Science.gov (United States)

    Guan, Bu Yuan; Yu, Xin Yao; Wu, Hao Bin; Lou, Xiong Wen David

    2017-12-01

    Metal-organic frameworks (MOFs) have drawn tremendous attention because of their abundant diversity in structure and composition. Recently, there has been growing research interest in deriving advanced nanomaterials with complex architectures and tailored chemical compositions from MOF-based precursors for electrochemical energy storage and conversion. Here, a comprehensive overview of the synthesis and energy-related applications of complex nanostructures derived from MOF-based precursors is provided. After a brief summary of synthetic methods of MOF-based templates and their conversion to desirable nanostructures, delicate designs and preparation of complex architectures from MOFs or their composites are described in detail, including porous structures, single-shelled hollow structures, and multishelled hollow structures, as well as other unusual complex structures. Afterward, their applications are discussed as electrode materials or catalysts for lithium-ion batteries, hybrid supercapacitors, water-splitting devices, and fuel cells. Lastly, the research challenges and possible development directions of complex nanostructures derived from MOF-based-templates for electrochemical energy storage and conversion applications are outlined. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Elucidating the mechanism responsible for anomalous thermal expansion in a metal-organic framework.

    Science.gov (United States)

    van Heerden, Dewald P; Esterhuysen, Catharine; Barbour, Leonard J

    2016-03-14

    The previously reported anisotropic thermal expansion of a three-dimensional metal-organic framework (MOF) is examined by means of theoretical calculations. Inspection of the 100, 190, 280 and 370 K single crystal X-ray diffraction (SCD) structures indicated a concerted change in the coordination sphere of the zinc centre leading to elongation of the coordination helix in the crystallographic c direction (the Zn-O(H)-Zn angle expands), while the largely unaltered ligands (the ZnLZn distance remains constant) are pulled closer together in the ab plane. This study develops and evaluates a mechanistic model at the DFT level of theory that reproduces the convergent expansion of the coordination helix of the material. The linear increase in energy calculated for extension of a model consisting of six zinc centres and truncated ligands compares favourably with results obtained from a periodic DFT evaluation of the SCD structures. It was also found that the anisotropic thermal expansion trend could be reproduced qualitatively by Molecular Dynamics (MD) simulations in the NPT ensemble.

  4. Synthesis of nanoporous carbohydrate metal-organic framework and encapsulation of acetaldehyde

    Science.gov (United States)

    Al-Ghamdi, Saleh; Kathuria, Ajay; Abiad, Mohamad; Auras, Rafael

    2016-10-01

    Gamma cyclodextrin (γ-CD) metal organic frameworks (CDMOFs) were synthesized by coordinating γ-CDs with potassium hydroxide (KOH), referred hereafter as CDMOF-a, and potassium benzoate (C7H5KO2), denoted as CDMOF-b. The obtained CDMOF structures were characterized using nitrogen sorption isotherm, thermo-gravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). High surface areas were achieved by the γ-CD based MOF structures where the Langmuir specific surface areas (SSA) of CDMOF-a and CDMOF-b were determined as 1376 m2 g-1 and 607 m2 g-1; respectively. The dehydrated CDMOF structures demonstrated good thermal stability up to 250 °C as observed by the TGA studies. XRD results for CDMOF-a and CDMOF-b reveal a body centered-cubic (BCC) and trigonal crystal system; respectively. Due to its accessible porous structure and high surface area, acetaldehyde was successfully encapsulated in CDMOF-b. During the release kinetic studies, we observed peak release of 53 μg of acetaldehyde per g of CDMOF-b, which was 100 times greater than previously reported encapsulation in β-CD. However, aldol condensation reaction occurred during encapsulation of acetaldehyde into CDMOF-a. This research work demonstrates the potential to encapsulate volatile organic compounds in CDMOF-b, and their associated release for applications including food, pharmaceuticals and packaging.

  5. Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

    International Nuclear Information System (INIS)

    Metere, Alfredo; Oleynikov, Peter; Dzugutov, Mikhail; O’Keeffe, Michael

    2014-01-01

    We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction

  6. First-principles Hubbard U approach for small molecule binding in metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Mann, Gregory W., E-mail: gmann@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Mesosphere, Inc., San Francisco, California 94105 (United States); Lee, Kyuho, E-mail: kyuholee@lbl.gov [Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Synopsys, Inc., Mountain View, California 94043 (United States); Cococcioni, Matteo, E-mail: matteo.cococcioni@epfl.ch [Theory and Simulation of Materials (THEOS), École Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Smit, Berend, E-mail: Berend-Smit@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Laboratory of Molecular Simulation, Institut des Sciences et Ingénierie Chimiques, Valais Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l’Industrie 17, CH-1951 Sion (Switzerland); Neaton, Jeffrey B., E-mail: jbneaton@lbl.gov [Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720 (United States)

    2016-05-07

    We apply first-principles approaches with Hubbard U corrections for calculation of small molecule binding energetics to open-shell transition metal atoms in metal-organic frameworks (MOFs). Using density functional theory with van der Waals dispersion-corrected functionals, we determine Hubbard U values ab initio through an established linear response procedure for M-MOF-74, for a number of different metal centers (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu). While our ab initio U values differ from those used in previous work, we show that they result in lattice parameters and electronic contributions to CO{sub 2}-MOF binding energies that lead to excellent agreement with experiments and previous results, yielding lattice parameters within 3%. In addition, U-dependent calculations for an example system, Co-MOF-74, suggest that the CO{sub 2} binding energy grows monotonically with the value of Hubbard U, with the binding energy shifting 4 kJ/mol (or 0.041 eV) over the range of U = 0-5.4 eV. These results provide insight into an approximate but computationally efficient means for calculation of small molecule binding energies to open-shell transition metal atoms in MOFs and suggest that the approach can be predictive with good accuracy, independent of the cations used and the availability of experimental data.

  7. High-Throughput Molecular Simulations of Metal Organic Frameworks for CO2 Separation: Opportunities and Challenges

    Directory of Open Access Journals (Sweden)

    Ilknur Erucar

    2018-02-01

    Full Text Available 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.

  8. Smart Resonant Gas Sensor and Switch Operating in Air With Metal-Organic Frameworks Coating

    KAUST Repository

    Jaber, Nizar; Ilyas, Saad; Shekhah, Osama; Eddaoudi, Mohamed; Younis, Mohammad I.

    2017-01-01

    We report a resonant gas sensor, uniformly coated with a metal-organic framework (MOF), and excited it near the higher order modes for a higher attained sensitivity. Also, switching upon exceeding a threshold value is demonstrated by operating the resonator near the bifurcation point and the dynamic pull-in instabilities. The resonator is based on an electrostatically excited clamped-clamped microbeam. The microbeam is fabricated from a polyimide layer coated from the top with Cr/Au and from the bottom with Cr/Au/Cr layer. The geometry of the resonator is optimized to reduce the effect of squeeze film damping, thereby allowing operation under atmospheric pressure. The electrostatic electrode is designed to enhance the excitation of the second mode of vibration with the minimum power required. Significant frequency shift (kHz) is demonstrated for the first time upon water vapor, acetone, and ethanol exposure due to the MOF functionalization and the higher order modes excitation. Also, the adsorption dynamics and MOF selectivity is investigated by studying the decaying time constants of the response upon gas exposure.

  9. Photoreactivity of Metal-Organic Frameworks in Aqueous Solutions: Metal Dependence of Reactive Oxygen Species Production.

    Science.gov (United States)

    Liu, Kai; Gao, Yanxin; Liu, Jing; Wen, Yifan; Zhao, Yingcan; Zhang, Kunyang; Yu, Gang

    2016-04-05

    Promising applications of metal-organic frameworks (MOFs) in various fields have raised concern over their environmental fate and safety upon inevitable discharge into aqueous environments. Currently, no information regarding the transformation processes of MOFs is available. Due to the presence of repetitive π-bond structure and semiconductive property, photochemical transformations are an important fate process that affects the performance of MOFs in practical applications. In the current study, the generation of reactive oxygen species (ROS) in isoreticular MIL-53s was studied. Scavengers were employed to probe the production of (1)O2, O2(•-), and •OH, respectively. In general, MIL-53(Cr) and MIL-53(Fe) are dominated by type I and II photosensitization reactions, respectively, and MIL-53(Al) appears to be less photoreactive. The generation of ROS in MIL-53(Fe) may be underestimated due to dismutation. Further investigation of MIL-53(Fe) encapsulated diclofenac transformation revealed that diclofenac can be easily transformed by MIL-53(Fe) generated ROS. However, the cytotoxicity results implied that the ROS generated from MIL-53s have little effect on the viability of the human hepatocyte (HepG2) cell line. These results suggest that the photogeneration of ROS by MOFs may be metal-node dependent, and the application of MIL-53s as drug carriers needs to be carefully considered due to their high photoreactivity.

  10. Insulator-to-Proton-Conductor Transition in a Dense Metal-Organic Framework.

    Science.gov (United States)

    Tominaka, Satoshi; Coudert, François-Xavier; Dao, Thang D; Nagao, Tadaaki; Cheetham, Anthony K

    2015-05-27

    Metal-organic frameworks (MOFs) are prone to exhibit phase transitions under stimuli such as changes in pressure, temperature, or gas sorption because of their flexible and responsive structures. Here we report that a dense MOF, ((CH3)2NH2)2[Li2Zr(C2O4)4], exhibits an abrupt increase in proton conductivity from topotactic hydration (H2O/Zr = 0.5), wherein one-fourth of the Li ions are irreversibly rearranged and coordinated by water molecules. This structure further transforms into a third crystalline structure by water uptake (H2O/Zr = 4.0). The abrupt increase in conductivity is reversible and is associated with the latter reversible structure transformation. The H2O molecules coordinated to Li ions, which are formed in the first step of the transformation, are considered to be the proton source, and the absorbed water molecules, which are formed in the second step, are considered to be proton carriers.

  11. 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:

  12. A flexible ligand-based wavy layered metal-organic framework for lithium-ion storage.

    Science.gov (United States)

    An, Tiance; Wang, Yuhang; Tang, Jing; Wang, Yang; Zhang, Lijuan; Zheng, Gengfeng

    2015-05-01

    A substantial challenge for direct utilization of metal-organic frameworks (MOFs) as lithium-ion battery anodes is to maintain the rigid MOF structure during lithiation/delithiation cycles. In this work, we developed a flexible, wavy layered nickel-based MOF (C20H24Cl2N8Ni, designated as Ni-Me4bpz) by a solvothermal approach of 3,3',5,5'-tetramethyl-4,4'-bipyrazole (H2Me4bpz) with nickel(II) chloride hexahydrate. The obtained MOF materials (Ni-Me4bpz) with metal azolate coordination mode provide 2-dimensional layered structure for Li(+) intercalation/extraction, and the H2Me4bpz ligands allow for flexible rotation feature and structural stability. Lithium-ion battery anodes made of the Ni-Me4bpz material demonstrate excellent specific capacity and cycling performance, and the crystal structure is well preserved after the electrochemical tests, suggesting the potential of developing flexible layered MOFs for efficient and stable electrochemical storage. Copyright © 2015 Elsevier Inc. All rights reserved.

  13. Characterization of compositional modifications in metal-organic frameworks using carbon and alpha particle microbeams

    Science.gov (United States)

    Paneta, V.; Fluch, U.; Petersson, P.; Ott, S.; Primetzhofer, D.

    2017-08-01

    Zirconium-oxide based metal-organic frameworks (MOFs) were grown on p-type Si wafers. A modified linker molecule containing iodine was introduced by post synthetic exchange (PSE). Samples have been studied using Rutherford Backscattering Spectrometry (RBS) and Particle Induced X-ray Emission (PIXE) techniques, employing the 5 MV 15SDH-2 Pelletron Tandem accelerator at the Ångström laboratory. The degree of post synthetic uptake of the iodine-containing linker has been investigated with both a broad beam and a focused beam of carbon and alpha particles targeting different kind of MOF crystals which were of ∼1-10 μm in size, depending on the linker used. Iodine concentrations in MOF crystallites were also measured by Nuclear Magnetic Resonance Spectroscopy (NMR) and are compared to the RBS results. In parallel to the ion beam studies, samples were investigated by Scanning Electron Microscopy (SEM) to quantify possible crystallite clustering, develop optimum sample preparation routines and to characterize the potential ion beam induced sample damage and its dependence on different parameters. Based on these results the reliability and accuracy of ion beam data is assessed.

  14. Nanoscale zinc-based metal-organic framework with high capacity for lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Changdong [Changzhou University, School of Petrochemical Engineering, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, and Advanced Catalysis and Green Manufacturing Collaborative Innovation Center (China); Gao, Yuanrui; Liu, Lili [Shanghai University, Department of Chemistry, College of Science (China); Song, Yidan; Wang, Xianmei [Changzhou University, School of Petrochemical Engineering, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, and Advanced Catalysis and Green Manufacturing Collaborative Innovation Center (China); Liu, Hong-Jiang, E-mail: liuhj@shu.edu.cn [Shanghai University, Department of Chemistry, College of Science (China); Liu, Qi, E-mail: liuqi62@163.com [Changzhou University, School of Petrochemical Engineering, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, and Advanced Catalysis and Green Manufacturing Collaborative Innovation Center (China)

    2016-12-15

    Layered zinc-based metal-organic framework ([Zn(4,4′-bpy)(tfbdc)(H{sub 2}O){sub 2}], Zn-LMOF) nanosheets were synthesized by a facile hydrothermal method (4,4′-bpy = 4,4′-bipyridine, H{sub 2}tfbdc = tetrafluoroterephthalic acid). The materials were characterized by IR spectrum, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, transmission electron microscope (TEM), scanning electron microscope (SEM), and the Brunauer–Emmett–Teller (BET) surface. When the Zn-LMOF nanosheets with the thickness of about 24 ± 8 nm were used as an anode material of lithium-ion batteries, not only the Zn-LMOF electrode shows a high reversible capacity, retaining 623 mAh g{sup −1} after 100 cycles at a current density of 50 mA g{sup −1} but also exhibits an excellent cyclic stability and a higher rate performance.

  15. Hybrid glasses from strong and fragile metal-organic framework liquids.

    Science.gov (United States)

    Bennett, Thomas D; Tan, Jin-Chong; Yue, Yuanzheng; Baxter, Emma; Ducati, Caterina; Terrill, Nick J; Yeung, Hamish H-M; Zhou, Zhongfu; Chen, Wenlin; Henke, Sebastian; Cheetham, Anthony K; Greaves, G Neville

    2015-08-28

    Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship between amorphization and melting has so far not been investigated. Here we show how heating MOFs of zeolitic topology first results in a low density 'perfect' glass, similar to those formed in ice, silicon and disaccharides. This order-order transition leads to a super-strong liquid of low fragility that dynamically controls collapse, before a subsequent order-disorder transition, which creates a more fragile high-density liquid. After crystallization to a dense phase, which can be remelted, subsequent quenching results in a bulk glass, virtually identical to the high-density phase. We provide evidence that the wide-ranging melting temperatures of zeolitic MOFs are related to their network topologies and opens up the possibility of 'melt-casting' MOF glasses.

  16. Valuing Metal-Organic Frameworks for Postcombustion Carbon Capture: A Benchmark Study for Evaluating Physical Adsorbents

    KAUST Repository

    Adil, Karim

    2017-08-22

    The development of practical solutions for the energy-efficient capture of carbon dioxide is of prime importance and continues to attract intensive research interest. Conceivably, the implementation of adsorption-based processes using different cycling modes, e.g., pressure-swing adsorption or temperature-swing adsorption, offers great prospects to address this challenge. Practically, the successful deployment of practical adsorption-based technologies depends on the development of made-to-order adsorbents expressing mutually two compulsory requisites: i) high selectivity/affinity for CO2 and ii) excellent chemical stability in the presence of impurities. This study presents a new comprehensive experimental protocol apposite for assessing the prospects of a given physical adsorbent for carbon capture under flue gas stream conditions. The protocol permits: i) the baseline performance of commercial adsorbents such as zeolite 13X, activated carbon versus liquid amine scrubbing to be ascertained, and ii) a standardized evaluation of the best reported metal-organic framework (MOF) materials for carbon dioxide capture from flue gas to be undertaken. This extensive study corroborates the exceptional CO2 capture performance of the recently isolated second-generation fluorinated MOF material, NbOFFIVE-1-Ni, concomitant with an impressive chemical stability and a low energy for regeneration. Essentially, the NbOFFIVE-1-Ni adsorbent presents the best compromise by satisfying all the required metrics for efficient CO2 scrubbing.

  17. Metal-Organic Frameworks for Sensing Applications in the Gas Phase

    Directory of Open Access Journals (Sweden)

    Sabine Achmann

    2009-03-01

    Full Text Available Several metal-organic framework (MOF materials were under investigated to test their applicability as sensor materials for impedimetric gas sensors. The materials were tested in a temperature range of 120 °C - 240 °C with varying concentrations of O2, CO2, C3H8, NO, H2, ethanol and methanol in the gas atmosphere and under different test gas humidity conditions. Different sensor configurations were studied in a frequency range of 1 Hz -1 MHz and time-continuous measurements were performed at 1 Hz. The materials did not show any impedance response to O2, CO2, C3H8, NO, or H2 in the gas atmospheres, although for some materials a significant impedance decrease was induced by a change of the ethanol or methanol concentration in the gas phase. Moreover, pronounced promising and reversible changes in the electric properties of a special MOF material were monitored under varying humidity, with a linear response curve at 120 °C. Further investigations were carried out with differently doped MOF materials of this class, to evaluate the influence of special dopants on the sensor effect.

  18. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

    Science.gov (United States)

    Kim, In Soo; Li, Zhanyong; Zheng, Jian; Platero-Prats, Ana E; Mavrandonakis, Andreas; Pellizzeri, Steven; Ferrandon, Magali; Vjunov, Aleksei; Gallington, Leighanne C; Webber, Thomas E; Vermeulen, Nicolaas A; Penn, R Lee; Getman, Rachel B; Cramer, Christopher J; Chapman, Karena W; Camaioni, Donald M; Fulton, John L; Lercher, Johannes A; Farha, Omar K; Hupp, Joseph T; Martinson, Alex B F

    2018-01-22

    Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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.

  20. Mesoporous stilbene-based lanthanide metal organic frameworks: synthesis, photoluminescence and radioluminescence characteristics.

    Science.gov (United States)

    Mathis Ii, Stephan R; Golafale, Saki T; Bacsa, John; Steiner, Alexander; Ingram, Conrad W; Doty, F Patrick; Auden, Elizabeth; Hattar, Khalid

    2017-01-03

    Ultra large pore isostructural metal organic frameworks (MOFs) which exhibit both photoluminescence and scintillation properties, were synthesized from trans-4,4'-stilbenedicarboxylic acid (H 2 L) and trivalent lanthanide (Ln) metal salts under solvothermal conditions (Ln = Er 3+ (1) and Tm 3+ (2)). This new class of mesoporous materials is a non-interpenetrating network that features ultra-large diamond shaped pores of dimensions with approximate cross-sectional dimensions of 28 Å × 12 Å. The fully deprotonated ligand, L, is isolated and rigidified as it serves as the organic linker component of the MOF structure. Its low density unit cells possess asymmetric units with two crystallographically independent Ln 3+ ions in seven coordinate arrangements. A distinct feature of the structure is the bis-bidentate carboxylate groups. They serve as a ligand that coordinates two Ln(iii) ions while each L connects four Ln(iii) ions yielding an exceptionally large diamond-shaped rectangular network. The structure exhibits ligand-based photoluminescence with increased lifetime compared to free stilbene molecules on exposure to UV radiation, and also exhibits strong scintillation characteristics, comprising of both prompt and delayed radioluminescence features, on exposure to ionizing radiation.

  1. Adsorption and Detection of Hazardous Trace Gases by Metal-Organic Frameworks.

    Science.gov (United States)

    Woellner, Michelle; Hausdorf, Steffen; Klein, Nicole; Mueller, Philipp; Smith, Martin W; Kaskel, Stefan

    2018-06-19

    The quest for advanced designer adsorbents for air filtration and monitoring hazardous trace gases has recently been more and more driven by the need to ensure clean air in indoor, outdoor, and industrial environments. How to increase safety with regard to personal protection in the event of hazardous gas exposure is a critical question for an ever-growing population spending most of their lifetime indoors, but is also crucial for the chemical industry in order to protect future generations of employees from potential hazards. Metal-organic frameworks (MOFs) are already quite advanced and promising in terms of capacity and specific affinity to overcome limitations of current adsorbent materials for trace and toxic gas adsorption. Due to their advantageous features (e.g., high specific surface area, catalytic activity, tailorable pore sizes, structural diversity, and range of chemical and physical properties), MOFs offer a high potential as adsorbents for air filtration and monitoring of hazardous trace gases. Three advanced topics are considered here, in applying MOFs for selective adsorption: (i) toxic gas adsorption toward filtration for respiratory protection as well as indoor and cabin air, (ii) enrichment of hazardous gases using MOFs, and (iii) MOFs as sensors for toxic trace gases and explosives. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Graphene-Templated Synthesis of Magnetic Metal Organic Framework Nanocomposites for Selective Enrichment of Biomolecules.

    Science.gov (United States)

    Cheng, Gong; Wang, Zhi-Gang; Denagamage, Sachira; Zheng, Si-Yang

    2016-04-27

    Successful control of homogeneous and complete coating of graphene or graphene-based composites with well-defined metal organic framework (MOF) layers is a great challenge. Herein, novel magnetic graphene MOF composites were constructed via a simple strategy for self-assembly of well-distributed, dense, and highly porous MOFs on both sides of graphene nanosheets. Graphene functionalized with magnetic nanoparticles and carboxylic groups on both sides was explored as the backbone and template to direct the controllable self-assembly of MOFs. The prepared composite materials have a relatively high specific surface area (345.4 m(2) g(-1)), and their average pore size is measured to be 3.2 nm. Their relatively high saturation magnetization (23.8 emu g(-1)) indicates their strong magnetism at room temperature. Moreover, the multifunctional composite was demonstrated to be a highly effective affinity material in selective extraction and separation of low-concentration biomolecules from biological samples, in virtue of the size-selection property of the unique porous structure and the excellent affinity of the composite materials. Besides providing a solution for the construction of well-defined functional graphene-based MOFs, this work could also contribute to selective extraction of biomolecules, in virtue of the universal affinity between immobilized metal ions and biomolecules.

  3. Block Copolymer-Templated Approach to Nanopatterned Metal-Organic Framework Films.

    Science.gov (United States)

    Zhou, Meimei; Wu, Yi-Nan; Wu, Baozhen; Yin, Xianpeng; Gao, Ning; Li, Fengting; Li, Guangtao

    2017-08-17

    The fabrication of patterned metal-organic framework (MOF) films with precisely controlled nanoscale resolution has been a fundamental challenge in nanoscience and nanotechnology. In this study, nanopatterned MOF films were fabricated using a layer-by-layer (LBL) growth method on functional templates (such as a bicontinuous nanoporous membrane or a structure with highly long-range-ordered nanoscopic channels parallel to the underlying substrate) generated by the microphase separation of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymers. HKUST-1 can be directly deposited on the templates without any chemical modification because the pyridine groups in P2VP interact with metal ions via metal-BCP complexes. As a result, nanopatterned HKUST-1 films with feature sizes below 50 nm and controllable thicknesses can be fabricated by controlling the number of LBL growth cycles. The proposed fabrication method further extends the applications of MOFs in various fields. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Supramolecular architecture of metal-organic frameworks involving dinuclear copper paddle-wheel complexes.

    Science.gov (United States)

    Gomathi, Sundaramoorthy; Muthiah, Packianathan Thomas

    2013-12-15

    The two centrosymmetric dinuclear copper paddle-wheel complexes tetrakis(μ-4-hydroxybenzoato-κ(2)O:O')bis[aquacopper(II)] dimethylformamide disolvate dihydrate, [Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O, (I), and tetrakis(μ-4-methoxybenzoato-κ(2)O:O')bis[(dimethylformamide-κO)copper(II)], [Cu2(C8H7O3)4(C3H7NO)2], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one dimethylformamide (DMF) and one water solvent molecule in the asymmetric unit. In both (I) and (II), two Cu(II) ions are bridged by four syn,syn-η(1):η(1):μ carboxylate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxylate groups of 4-hydroxy- and 4-methoxybenzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supramolecular metal-organic framework of (I) consists of three different R2(2)(20) and an R4(4)(36) ring motif formed via O-H···O and OW-HW···O hydrogen bonds. Complex (II) simply packs as molecular species.

  5. Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

    Science.gov (United States)

    Best, James P.; Michler, Johann; Liu, Jianxi; Wang, Zhengbang; Tsotsalas, Manuel; Maeder, Xavier; Röse, Silvana; Oberst, Vanessa; Liu, Jinxuan; Walheim, Stefan; Gliemann, Hartmut; Weidler, Peter G.; Redel, Engelbert; Wöll, Christof

    2015-09-01

    Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (EITO ≈ 96.7 GPa, EHKUST-1 ≈ 22.0 GPa). For indentation of multilayer stacks, it was found that as the layer thicknesses were increased, while holding the relative thickness of ITO and HKUST-1 constant, the resistance to deformation was significantly altered. Such an observation is likely due to small, albeit significant, changes in film texture, interfacial roughness, size effects, and controlling deformation mechanism as a result of increasing material deposition during processing. Such effects may have consequences regarding the rational mechanical design and utilization of MOF-based hybrid thin-film devices.

  6. Copper Metal-Organic Framework Nanoparticles Stabilized with Folic Acid Improve Wound Healing in Diabetes.

    Science.gov (United States)

    Xiao, Jisheng; Zhu, Yunxiao; Huddleston, Samantha; Li, Peng; Xiao, Baixue; Farha, Omar K; Ameer, Guillermo A

    2018-02-27

    The successful treatment of chronic nonhealing wounds requires strategies that promote angiogenesis, collagen deposition, and re-epithelialization of the wound. Copper ions have been reported to stimulate angiogenesis; however, several applications of copper salts or oxides to the wound bed are required, leading to variable outcomes and raising toxicity concerns. We hypothesized that copper-based metal-organic framework nanoparticles (Cu-MOF NPs), referred to as HKUST-1, which are rapidly degraded in protein solutions, can be modified to slowly release Cu 2+ , resulting in reduced toxicity and improved wound healing rates. Folic acid was added during HKUST-1 synthesis to generate folic-acid-modified HKUST-1 (F-HKUST-1). The effect of folic acid incorporation on NP stability, size, hydrophobicity, surface area, and copper ion release profile was measured. In addition, cytotoxicity and in vitro cell migration processes due to F-HKUST-1 and HKUST-1 were evaluated. Wound closure rates were assessed using the splinted excisional dermal wound model in diabetic mice. The incorporation of folic acid into HKUST-1 enabled the slow release of copper ions, which reduced cytotoxicity and enhanced cell migration in vitro. In vivo, F-HKUST-1 induced angiogenesis, promoted collagen deposition and re-epithelialization, and increased wound closure rates. These results demonstrate that folic acid incorporation into HKUST-1 NPs is a simple, safe, and promising approach to control Cu 2+ release, thus enabling the direct application of Cu-MOF NPs to wounds.

  7. Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Best, James P., E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu; Michler, Johann; Maeder, Xavier [Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Mechanics of Materials and Nanostructures, Feuerwerkerstrasse 39, CH-3602 Thun (Switzerland); Liu, Jianxi; Wang, Zhengbang; Tsotsalas, Manuel; Liu, Jinxuan; Gliemann, Hartmut; Weidler, Peter G.; Redel, Engelbert, E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu; Wöll, Christof, E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu [Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Röse, Silvana [Preparative Macromolecular Chemistry, Institute for Chemical Technology and Polymer Chemistry (ICTP), Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76128 Karlsruhe (Germany); Institute for Biological Interfaces (IBG), Karlsruhe Institute of Technology (KIT), Herrmann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Oberst, Vanessa [Institute of Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Walheim, Stefan [Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

    2015-09-07

    Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (E{sub ITO} ≈ 96.7 GPa, E{sub HKUST−1} ≈ 22.0 GPa). For indentation of multilayer stacks, it was found that as the layer thicknesses were increased, while holding the relative thickness of ITO and HKUST-1 constant, the resistance to deformation was significantly altered. Such an observation is likely due to small, albeit significant, changes in film texture, interfacial roughness, size effects, and controlling deformation mechanism as a result of increasing material deposition during processing. Such effects may have consequences regarding the rational mechanical design and utilization of MOF-based hybrid thin-film devices.

  8. Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

    International Nuclear Information System (INIS)

    Best, James P.; Michler, Johann; Maeder, Xavier; Liu, Jianxi; Wang, Zhengbang; Tsotsalas, Manuel; Liu, Jinxuan; Gliemann, Hartmut; Weidler, Peter G.; Redel, Engelbert; Wöll, Christof; Röse, Silvana; Oberst, Vanessa; Walheim, Stefan

    2015-01-01

    Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (E ITO  ≈ 96.7 GPa, E HKUST−1  ≈ 22.0 GPa). For indentation of multilayer stacks, it was found that as the layer thicknesses were increased, while holding the relative thickness of ITO and HKUST-1 constant, the resistance to deformation was significantly altered. Such an observation is likely due to small, albeit significant, changes in film texture, interfacial roughness, size effects, and controlling deformation mechanism as a result of increasing material deposition during processing. Such effects may have consequences regarding the rational mechanical design and utilization of MOF-based hybrid thin-film devices

  9. Synthesis of metal-organic framework films by pore diffusion method

    Science.gov (United States)

    Murayama, Naohiro; Nishimura, Yuki; Kajiro, Hiroshi; Kishida, Satoru; Kinoshita, Kentaro; Tottori Univ Team; Nippon Steel; Sumitomo Metal Co. Collaboration; Tottori Integrated Frontier Resaerch Center (Tifrec) Collaboration; Tottori University Electronic Display Resaerch Center (Tedrec) Collaboration

    Metal-organic frameworks (MOFs) presents high controllability in designing the nano-scale pore, and this enable molecular storages, catalysts, gas sensors, gas separation membranes, and electronic devices for next-generation. Therefore, a simple method for film synthesis of MOFs compared with conventional methods [1] is strongly required. In this paper, we provide pore diffusion method, in which a substrate containing constituent metals of MOF is inserted in solution that includes only linker molecules of MOF. As a result, 2D growth of MOF was effectively enhanced, and the formation of flat and dense MOF films was attained. The growth time, t, dependence of film thickness, d, can be expressed by the relation of d = Aln(t + 1) + B, where A and B are constants. It means that ionized coppers diffuse through the pores of MOFs and the synthesis reaction proceeds at the MOF/solvent interface. We demonstrated the fabrication of a HKUST-1/Cu-TPA hetero structure by synthesizing a Cu-TPA film continuously after the growth of a HKUST-1 film on the CuOx substrate.

  10. Double-Sided Electrochromic Device Based on Metal-Organic Frameworks.

    Science.gov (United States)

    Mjejri, Issam; Doherty, Cara M; Rubio-Martinez, Marta; Drisko, Glenna L; Rougier, Aline

    2017-11-22

    Devices displaying controllably tunable optical properties through an applied voltage are attractive for smart glass, mirrors, and displays. Electrochromic material development aims to decrease power consumption while increasing the variety of attainable colors, their brilliance, and their longevity. We report the first electrochromic device constructed from metal organic frameworks (MOFs). Two MOF films, HKUST-1 and ZnMOF-74, are assembled so that the oxidation of one corresponds to the reduction of the other, allowing the two sides of the device to simultaneously change color. These MOF films exhibit cycling stability unrivaled by other MOFs and a significant optical contrast in a lithium-based electrolyte. HKUST-1 reversibly changed from bright blue to light blue and ZnMOF-74 from yellow to brown. The electrochromic device associates the two MOF films via a PMMA-lithium based electrolyte membrane. The color-switching of these MOFs does not arise from an organic-linker redox reaction, signaling unexplored possibilities for electrochromic MOF-based materials.

  11. Rapid, Selective Heavy Metal Removal from Water by a Metal-Organic Framework/Polydopamine Composite.

    Science.gov (United States)

    Sun, Daniel T; Peng, Li; Reeder, Washington S; Moosavi, Seyed Mohamad; Tiana, Davide; Britt, David K; Oveisi, Emad; Queen, Wendy L

    2018-03-28

    Drinking water contamination with heavy metals, particularly lead, is a persistent problem worldwide with grave public health consequences. Existing purification methods often cannot address this problem quickly and economically. Here we report a cheap, water stable metal-organic framework/polymer composite, Fe-BTC/PDA, that exhibits rapid, selective removal of large quantities of heavy metals, such as Pb 2+ and Hg 2+ , from real world water samples. In this work, Fe-BTC is treated with dopamine, which undergoes a spontaneous polymerization to polydopamine (PDA) within its pores via the Fe 3+ open metal sites. The PDA, pinned on the internal MOF surface, gains extrinsic porosity, resulting in a composite that binds up to 1634 mg of Hg 2+ and 394 mg of Pb 2+ per gram of composite and removes more than 99.8% of these ions from a 1 ppm solution, yielding drinkable levels in seconds. Further, the composite properties are well-maintained in river and seawater samples spiked with only trace amounts of lead, illustrating unprecedented selectivity. Remarkably, no significant uptake of competing metal ions is observed even when interferents, such as Na + , are present at concentrations up to 14 000 times that of Pb 2+ . The material is further shown to be resistant to fouling when tested in high concentrations of common organic interferents, like humic acid, and is fully regenerable over many cycles.

  12. Mimic Carbonic Anhydrase Using Metal-Organic Frameworks for CO2 Capture and Conversion.

    Science.gov (United States)

    Jin, Chaonan; Zhang, Sainan; Zhang, Zhenjie; Chen, Yao

    2018-02-19

    Carbonic anhydrase (CA) is a zinc-containing metalloprotein, in which the Zn active center plays the key role to transform CO 2 into carbonate. Inspired by nature, herein we used metal-organic frameworks (MOFs) to mimic CA for CO 2 conversion, on the basis of the structural similarity between the Zn coordination in MOFs and CA active center. The biomimetic activity of MOFs was investigated by detecting the hydrolysis of para-nitrophenyl acetate, which is a model reaction used to evaluate CA activity. The biomimetic materials (e.g., CFA-1) showed good catalytic activity, and excellent reusability, and solvent and thermal stability, which is very important for practical applications. In addition, ZIF-100 and CFA-1 were used to mimic CA to convert CO 2 gas, and exhibited good efficiency on CO 2 conversion compared with those of other porous materials (e.g., MCM-41, active carbon). This biomimetic study revealed a novel CO 2 treatment method. Instead of simply using MOFs to absorb CO 2 , ZIF-100 and CFA-1 were used to mimic CA for in situ CO 2 conversion, which provides a new prospect in the biological and industrial applications of MOFs.

  13. Proton Conductivity of Proton Exchange Membrane Synergistically Promoted by Different Functionalized Metal-Organic Frameworks.

    Science.gov (United States)

    Rao, Zhuang; Tang, Beibei; Wu, Peiyi

    2017-07-12

    In this study, two functionalized metal-organic frameworks (MOFs), UiO-66-SO 3 H and UiO-66-NH 2 , were synthesized. Then, different composite proton exchange membranes (PEMs) were prepared by single doping and codoping of these two MOFs, respectively. It was found that codoping of these two MOFs with suitable sizes was more conducive to the proton conductivity enhancement of the composite PEM. A synergistic effect between these two MOFs led to the the formation of more consecutive hydration channels in the composite PEM. It further greatly promoted the proton conductivity of the composite PEM. The proton conductivity of the codoped PEM reached up to 0.256 S/cm under 90 °C, 95% RH, which was ∼1.17 times higher than that of the recast Nafion (0.118 S/cm). Besides, the methanol permeability of the codoped PEM was prominently decreased owing to the methanol trapping effect of the pores of these two MOFs. Meanwhile, the high water and thermal stabilities of these two MOFs were beneficial to the high proton conductivity stability of the codoped PEM under high humidity and high temperature. The proton conductivity of the codoped PEM was almost unchanged throughout 3000 min of testing under 90 °C, 95% RH. This work provides a valuable reference for designing different functionalized MOFs to synergistically promote the proton conductivities of PEMs.

  14. First-principles Hubbard U approach for small molecule binding in metal-organic frameworks

    International Nuclear Information System (INIS)

    Mann, Gregory W.; Lee, Kyuho; Cococcioni, Matteo; Smit, Berend; Neaton, Jeffrey B.

    2016-01-01

    We apply first-principles approaches with Hubbard U corrections for calculation of small molecule binding energetics to open-shell transition metal atoms in metal-organic frameworks (MOFs). Using density functional theory with van der Waals dispersion-corrected functionals, we determine Hubbard U values ab initio through an established linear response procedure for M-MOF-74, for a number of different metal centers (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu). While our ab initio U values differ from those used in previous work, we show that they result in lattice parameters and electronic contributions to CO 2 -MOF binding energies that lead to excellent agreement with experiments and previous results, yielding lattice parameters within 3%. In addition, U-dependent calculations for an example system, Co-MOF-74, suggest that the CO 2 binding energy grows monotonically with the value of Hubbard U, with the binding energy shifting 4 kJ/mol (or 0.041 eV) over the range of U = 0-5.4 eV. These results provide insight into an approximate but computationally efficient means for calculation of small molecule binding energies to open-shell transition metal atoms in MOFs and suggest that the approach can be predictive with good accuracy, independent of the cations used and the availability of experimental data.

  15. Synthesis, characterization and application of metal organic frameworks in the adsorption of dimethylamine

    International Nuclear Information System (INIS)

    Sun-Kou, Maria del Rosario; Bravo Hualpa, Fabiola; Beltran Suito, Rodrigo; Samanamu, Christian; Picasso Escobar, Gino

    2014-01-01

    This study investigated the removal of dimethylamine (DMA) by an adsorption mechanism using metal-organic frameworks (MOFs). The synthesis of the MOFs was performed by solvothermal methods. The characterization of the MOF obtained was made by attenuated total reflectance spectroscopy (ATR), proton nuclear magnetic resonance spectroscopy ("1H-NMR), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and scanning electron microscopy (SEM). The XRD diffractograms allowed to identify the structure of MOF as Dashkovaite, which has the molecular formula Mg(HCOO)_2.2H_2O; while the ATR studies revealed the presence of carbonyl group as most important functional group in the MOF structure. The morphological analysis showed that the MOF crystalline particles had a hexagonal shape, formed from filaments of around 7,5-8 microns in length. Adsorption experiments showed that the MOF had a high adsorption capacity of DMA (q_e= 307,96 mg.g"-"1). The kinetic data were fitted to the pseudo second order equation and the Elovich equation, while the adsorption isotherm was fitted to the Temkin equation and the Dubinin - Radushkevich equation, processes related to chemisorptions preferably on a heterogeneous surface. (author)

  16. Smart Resonant Gas Sensor and Switch Operating in Air With Metal-Organic Frameworks Coating

    KAUST Repository

    Jaber, Nizar

    2017-11-03

    We report a resonant gas sensor, uniformly coated with a metal-organic framework (MOF), and excited it near the higher order modes for a higher attained sensitivity. Also, switching upon exceeding a threshold value is demonstrated by operating the resonator near the bifurcation point and the dynamic pull-in instabilities. The resonator is based on an electrostatically excited clamped-clamped microbeam. The microbeam is fabricated from a polyimide layer coated from the top with Cr/Au and from the bottom with Cr/Au/Cr layer. The geometry of the resonator is optimized to reduce the effect of squeeze film damping, thereby allowing operation under atmospheric pressure. The electrostatic electrode is designed to enhance the excitation of the second mode of vibration with the minimum power required. Significant frequency shift (kHz) is demonstrated for the first time upon water vapor, acetone, and ethanol exposure due to the MOF functionalization and the higher order modes excitation. Also, the adsorption dynamics and MOF selectivity is investigated by studying the decaying time constants of the response upon gas exposure.

  17. Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties

    Directory of Open Access Journals (Sweden)

    Stephan R. Mathis

    2018-01-01

    Full Text Available Four anthracene-based lanthanide metal-organic framework structures (MOFs were synthesized from the combination of the lanthanide ions, Eu3+, Tb3+, Er3+, and Tm3+, with 9,10-anthracenedicarboxylic acid (H2ADC in dimethylformamide (DMF under hydrothermal conditions. The 3-D networks crystalize in the triclinic system with P-1 space group with the following compositions: (i {{[Ln2(ADC3(DMF4·DMF]}n, Ln = Eu (1 and Tb (2} and (ii {{[Ln2(ADC3(DMF2(OH22·2DMF·H2O]}n, Ln = Er (3 and Tm (4}. The metal centers exist in various coordination environments; nine coordinate in (i, while seven and eight coordinate in (ii. The deprotonated ligand, ADC, assumes multiple coordination modes, with its carboxylate functional groups severely twisted away from the plane of the anthracene moiety. The structures show ligand-based photoluminescence, which appears to be significantly quenched when compared with that of the parent H2ADC solid powder. Structure 2 is the least quenched and showed an average photoluminescence lifetime from bi-exponential decay of 0.3 ns. On exposure to ionizing radiation, the structures show radioluminescence spectral features that are consistent with the isolation of the ligand units in its 3-D network. The spectral features vary among the 3-D networks and appear to suggest that the latter undergo significant changes in their molecular and/or electronic structure in the presence of the ionizing radiation.

  18. Chemical Reactions Catalyzed by Metalloporphyrin-Based Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Kelly Aparecida Dias de Freitas Castro

    2013-06-01

    Full Text Available The synthetic versatility and the potential application of metalloporphyrins (MP in different fields have aroused researchers’ interest in studying these complexes, in an attempt to mimic biological systems such as cytochrome P-450. Over the last 40 years, synthetic MPs have been mainly used as catalysts for homogeneous or heterogeneous chemical reactions. To employ them in heterogeneous catalysis, chemists have prepared new MP-based solids by immobilizing MP onto rigid inorganic supports, a strategy that affords hybrid inorganic-organic materials. More recently, materials obtained by supramolecular assembly processes and containing MPs as building blocks have been applied in a variety of areas, like gas storage, photonic devices, separation, molecular sensing, magnets, and heterogeneous catalysis, among others. These coordination polymers, known as metal-organic frameworks (MOFs, contain organic ligands or complexes connected by metal ions or clusters, which give rise to a 1-, 2- or 3-D network. These kinds of materials presents large surface areas, Brønsted or redox sites, and high porosity, all of which are desirable features in catalysts with potential use in heterogeneous phases. Building MOFs based on MP is a good way to obtain solid catalysts that offer the advantages of bioinspired systems and zeolitic materials. In this mini review, we will adopt a historical approach to present the most relevant MP-based MOFs applicable to catalytic reactions such as oxidation, reduction, insertion of functional groups, and exchange of organic functions.

  19. Mathematical modeling and experimental breakthrough curves of carbon dioxide adsorption on metal organic framework CPM-5.

    Science.gov (United States)

    Sabouni, Rana; Kazemian, Hossein; Rohani, Sohrab

    2013-08-20

    It is essential to capture carbon dioxide from flue gas because it is considered one of the main causes of global warming. Several materials and different methods have been reported for CO2 capturing including adsorption onto zeolites and porous membranes, as well as absorption in amine solutions. All such methods require high energy input and high cost. A new class of porous materials called Metal Organic Frameworks (MOFs) exhibited excellent performance in extracting carbon dioxide from a gas mixture. In this study, the breakthrough curves for the adsorption of carbon dioxide on CPM-5 (crystalline porous materials) were obtained experimentally and theoretically using a laboratory-scale fixed-bed column at different experimental conditions such as feed flow rate, adsorption temperature, and feed concentration. It was found that the CPM-5 has a dynamic CO2 adsorption capacity of 11.9 wt % (2.7 mmol/g) (corresponding to 8 mL/min, 298 K, and 25% v/v CO2). The tested CPM-5 showed an outstanding adsorption equilibrium capacity (e.g., 2.3 mmol/g (10.2 wt %) at 298 K) compared to other adsorbents, which can be considered as an attractive adsorbent for separation of CO2 from flue gas.

  20. Electrochemistry and electrochemiluminescence from a redox-active metal-organic framework.

    Science.gov (United States)

    Xu, Yang; Yin, Xue-Bo; He, Xi-Wen; Zhang, Yu-Kui

    2015-06-15

    The marriage of metal-organic frameworks (MOFs) and electrochemiluminescence (ECL) can combine their merits together. Designing ECL-active MOF with a high electron transfer capacity and high stability is critical for ECL emission. Here we reported the ECL from a redox-active MOF prepared from {Ru[4,4'-(HO2C)2-bpy]2bpy}(2+) and Zn(2+); a property of MOFs has not been reported previously. The MOF structure is independent of its charge and is therefore stable electrochemically. The redox-activity and well-ordered porous structure of the MOF were confirmed by its electrochemical properties and ECL emission. The high ECL emission indicated the ease of electron transfer between the MOF and co-reactants. Furthermore, the MOF exhibited permselectivity, charge selectivity, and catalytic selectivity along with a stable and concentration-dependent ECL emission toward co-reactants. ECL mechanism was proposed based on the results. The detection and recovery of cocaine in the serum sample was used to validate the feasibility of MOF- based ECL system. The information obtained in this study provides a better understanding of the redox properties of MOFs and their potential electrochemical applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Gas/vapour separation using ultra-microporous metal–organic frameworks: insights into the structure/separation relationship

    KAUST Repository

    Adil, Karim; Belmabkhout, Youssef; Pillai, Renjith S.; Cadiau, Amandine; Bhatt, Prashant; Assen, Ayalew Hussen Assen; Maurin, Guillaume; Eddaoudi, Mohamed

    2017-01-01

    The separation of related molecules with similar physical/chemical properties is of prime industrial importance and practically entails a substantial energy penalty, typically necessitating the operation of energy-demanding low temperature fractional distillation techniques. Certainly research efforts, in academia and industry alike, are ongoing with the main aim to develop advanced functional porous materials to be adopted as adsorbents for the effective and energy-efficient separation of various important commodities. Of special interest is the subclass of metal-organic frameworks (MOFs) with pore aperture sizes below 5-7 Å, namely ultra-microporous MOFs, which in contrast to conventional zeolites and activated carbons show great prospects for addressing key challenges in separations pertaining to energy and environmental sustainability, specifically materials for carbon capture and separation of olefin/paraffin, acetylene/ethylene, linear/branched alkanes, xenon/krypton, etc. In this tutorial review we discuss the latest developments in ultra-microporous MOF adsorbents and their use as separating agents via thermodynamics and/or kinetics and molecular sieving. Appreciably, we provide insights into the distinct microscopic mechanisms governing the resultant separation performances, and suggest a plausible correlation between the inherent structural features/topology of MOFs and the associated gas/vapour separation performance.

  2. Highly selective sieving of small gas molecules by using an ultra-microporous metal–organic framework membrane

    KAUST Repository

    Kang, Zixi; Xue, Ming; Fan, Lili; Huang, Lin; Guo, Lijia; Wei, Guoying; Chen, Banglin; Qiu, Shilun

    2014-01-01

    © 2014 The Royal Society of Chemistry. Two tailor-made microporous metal-organic framework (MOF) membranes were successfully fabricated on nickel screens by secondary growth. The effect of pore structures on gas separation was examined by means of single and binary gas permeation tests. The MOF JUC-150 membrane with its ultra-micropores showed marked preferential permeance to H2 relative to other gas molecules. The selectivity factors of this membrane were 26.3, 17.1 and 38.7 for H2/CH4, H2/N2 and H2/CO2, respectively, at room temperature. To the best of our knowledge, these values represent unprecedentedly high separation selectivity among those for all MOF membranes reported to date. The JUC-150 membrane also shows high thermal stability and outstanding separation performance at a high temperature of 200 °C. The separation performance of these membranes persists even after more than 1 year exposure to air. The superiority of the tailored pore size, high selectivity for H2 over other gases, significant stability and recyclability make these materials potential candidates for industrial H2 recycling applications.

  3. Highly selective sieving of small gas molecules by using an ultra-microporous metal–organic framework membrane

    KAUST Repository

    Kang, Zixi

    2014-09-12

    © 2014 The Royal Society of Chemistry. Two tailor-made microporous metal-organic framework (MOF) membranes were successfully fabricated on nickel screens by secondary growth. The effect of pore structures on gas separation was examined by means of single and binary gas permeation tests. The MOF JUC-150 membrane with its ultra-micropores showed marked preferential permeance to H2 relative to other gas molecules. The selectivity factors of this membrane were 26.3, 17.1 and 38.7 for H2/CH4, H2/N2 and H2/CO2, respectively, at room temperature. To the best of our knowledge, these values represent unprecedentedly high separation selectivity among those for all MOF membranes reported to date. The JUC-150 membrane also shows high thermal stability and outstanding separation performance at a high temperature of 200 °C. The separation performance of these membranes persists even after more than 1 year exposure to air. The superiority of the tailored pore size, high selectivity for H2 over other gases, significant stability and recyclability make these materials potential candidates for industrial H2 recycling applications.

  4. Gas/vapour separation using ultra-microporous metal–organic frameworks: insights into the structure/separation relationship

    KAUST Repository

    Adil, Karim

    2017-05-30

    The separation of related molecules with similar physical/chemical properties is of prime industrial importance and practically entails a substantial energy penalty, typically necessitating the operation of energy-demanding low temperature fractional distillation techniques. Certainly research efforts, in academia and industry alike, are ongoing with the main aim to develop advanced functional porous materials to be adopted as adsorbents for the effective and energy-efficient separation of various important commodities. Of special interest is the subclass of metal-organic frameworks (MOFs) with pore aperture sizes below 5-7 Å, namely ultra-microporous MOFs, which in contrast to conventional zeolites and activated carbons show great prospects for addressing key challenges in separations pertaining to energy and environmental sustainability, specifically materials for carbon capture and separation of olefin/paraffin, acetylene/ethylene, linear/branched alkanes, xenon/krypton, etc. In this tutorial review we discuss the latest developments in ultra-microporous MOF adsorbents and their use as separating agents via thermodynamics and/or kinetics and molecular sieving. Appreciably, we provide insights into the distinct microscopic mechanisms governing the resultant separation performances, and suggest a plausible correlation between the inherent structural features/topology of MOFs and the associated gas/vapour separation performance.

  5. Metal Organic Framework-Metal Oxide Composites for Toxic Gas Adsorption and Sensing

    Science.gov (United States)

    2014-05-01

    Granato, T.; Testa, F.; Olivo, R. Microporous Mesoporous Mat. 2012, 153, 236. 39 (5) Stavila, V.; Volponi, J.; Katzenmeyer, A. M.; Dixon, M. C...Yoo, Y.; Lai, Z. P.; Jeong, H. K. Microporous Mesoporous Mat. 2009, 123, 100. (12) Shekhah, O.; Wang, H.; Kowarik, S.; Schreiber, F.; Paulus, M...Jiao, Z.; Wu, M. H.; Zhao, B. J. Power Sources 2010, 195, 2950. (23) Bhagiyalakshmi, M.; Lee, J. Y.; Jang, H. T. International Journal of Greenhouse

  6. Nanosizing a Metal-Organic Framework Enzyme Carrier for Accelerating Nerve Agent Hydrolysis

    Science.gov (United States)

    2016-10-05

    non-commercial purposes. hierarchical hexagonal mesoporous and triangular microporous channels, is superior to other existing channel-type MOFs for...this internal diffusion and reaction limitation can be minimized by enlarging the aperture of the cavity and/or minimizing the size of the MOF−enzyme...both PCN-128 (9 × 9 Å) and NU-1000 (8 × 10 Å). These larger micropores and windows between micro- and mesopores (one-dimensional channels) can aid with

  7. Water-Stable Metal-Organic Framework with Three Hydrogen-Bond Acceptors: Versatile Theoretical and Experimental Insights into Adsorption Ability and Thermo-Hydrolytic Stability.

    Science.gov (United States)

    Roztocki, Kornel; Lupa, Magdalena; Sławek, Andrzej; Makowski, Wacław; Senkovska, Irena; Kaskel, Stefan; Matoga, Dariusz

    2018-03-19

    A new microporous cadmium metal-organic framework was synthesized both mechanochemically and in solution by using a sulfonyl-functionalized dicarboxylate linker and an acylhydrazone colinker. The three-dimensional framework is highly stable upon heating to 300 °C as well as in aqueous solutions at elevated temperatures or acidic conditions. The thermally activated material exhibits steep water vapor uptake at low relative pressures at 298 K and excellent recyclability up to 260 °C as confirmed by both quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) method as well as adsorption isotherm measurements. Reversible isotherms and hysteretic isobars recorded for the desorption-adsorption cycles indicate the maximum uptake of 0.19 g/g (at 298 K, up to p/p 0 = 1) or 0.18 g/g (at 1 bar, within 295-375 K range), respectively. The experimental isosteric heat of adsorption (48.9 kJ/mol) indicates noncoordinative interactions of water molecules with the framework. Exchange of the solvent molecules in the as-made material with water, performed in the single-crystal to single-crystal manner, allows direct comparison of both X-ray crystal structures. The single-crystal X-ray diffraction for the water-loaded framework demonstrates the orientation of water clusters in the framework cavities and reveals their strong hydrogen bonding with sulfonyl, acyl, and carboxylate groups of the two linkers. The grand canonical Monte Carlo (GCMC) simulations of H 2 O adsorption corroborate the experimental findings and reveal preferable locations of guest molecules in the framework voids at various pressures. Additionally, both experimental and GCMC simulation insights into the adsorption of CO 2 (at 195 K) on the activated framework are presented.

  8. Highly stable ni-m f6-nh2o/onpyrazine2(solvent)x metal organic frameworks and methods of use

    KAUST Repository

    Eddaoudi, Mohamed; Adil, Karim; Belmabkhout, Youssef; Cadiau, Amandine

    2016-01-01

    Provided herein are metal organic frameworks comprising metal nodes and N-donor organic ligands. Methods for capturing chemical species from fluid compositions comprise contacting a metal organic framework characterized by the formula [MaMbF6-n(O/H2

  9. Highly stable [mambf6-n(o/h2o)n(ligand)2(solvent)x]n metal organic frameworks

    KAUST Repository

    Eddaoudi, Mohamed; Adil, Karim; Belmabkhout, Youssef; Shekhah, Osama; Bhatt, Prashant M.; Cadiau, Amandine

    2016-01-01

    Provided herein are metal organic frameworks having high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Metal organic frameworks can comprise metal nodes and N-donor organic ligands. Further provided

  10. 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

  11. 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.

  12. 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.

  13. Creating a Discovery Platform for Confined-Space Chemistry and Materials: Metal-Organic Frameworks.

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Greathouse, Jeffery A.; Simmons, Blake

    2008-09-01

    Metal organic frameworks (MOF) are a recently discovered class of nanoporous, defect-free crystalline materials that enable rational design and exploration of porous materials at the molecular level. MOFs have tunable monolithic pore sizes and cavity environments due to their crystalline nature, yielding properties exceeding those of most other porous materials. These include: the lowest known density (91% free space); highest surface area; tunable photoluminescence; selective molecular adsorption; and methane sorption rivaling gas cylinders. These properties are achieved by coupling inorganic metal complexes such as ZnO4 with tunable organic ligands that serve as struts, allowing facile manipulation of pore size and surface area through reactant selection. MOFs thus provide a discovery platform for generating both new understanding of chemistry in confined spaces and novel sensors and devices based on their unique properties. At the outset of this project in FY06, virtually nothing was known about how to couple MOFs to substrates and the science of MOF properties and how to tune them was in its infancy. An integrated approach was needed to establish the required knowledge base for nanoscale design and develop methodologies integrate MOFs with other materials. This report summarizes the key accomplishments of this project, which include creation of a new class of radiation detection materials based on MOFs, luminescent MOFs for chemical detection, use of MOFs as templates to create nanoparticles of hydrogen storage materials, MOF coatings for stress-based chemical detection using microcantilevers, and "flexible" force fields that account for structural changes in MOFs that occur upon molecular adsorption/desorption. Eight journal articles, twenty presentations at scientific conferences, and two patent applications resulted from the work. The project created a basis for continuing development of MOFs for many Sandia applications and succeeded in securing $2.75 M in

  14. Sulfur removal from low-sulfur gasoline and diesel fuel by metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Hagen, G.; Haemmerle, M.; Moos, R. [Functional Materials, University of Bayreuth, Bayreuth (Germany); Malkowsky, I.M.; Kiener, C. [BASF SE, Ludwigshafen (Germany); Achmann, S.

    2010-02-15

    Several materials in the class of metal-organic frameworks (MOF) were investigated to determine their sorption characteristics for sulfur compounds from fuels. The materials were tested using different model oils and common fuels such as low-sulfur gasoline or diesel fuel at room temperature and ambient pressure. Thiophene and tetrahydrothiophene (THT) were chosen as model substances. Total-sulfur concentrations in the model oils ranged from 30 mg/kg (S from thiophene) to 9 mg/kg (S from tetrahydrothiophene) as determined by elementary analysis. Initial sulfur contents of 8 mg/kg and 10 mg/kg were identified for low-sulfur gasoline and for diesel fuel, respectively, by analysis of the common liquid fuels. Most of the MOF materials examined were not suitable for use as sulfur adsorbers. However, a high efficiency for sulfur removal from fuels and model oils was noticed for a special copper-containing MOF (copper benzene-1,3,5-tricarboxylate, Cu-BTC-MOF). By use of this material, 78 wt % of the sulfur content was removed from thiophene containing model oils and an even higher decrease of up to 86 wt % was obtained for THT-based model oils. Moreover, the sulfur content of low-sulfur gasoline was reduced to 6.5 mg/kg, which represented a decrease of more than 22 %. The sulfur level in diesel fuel was reduced by an extent of 13 wt %. Time-resolved measurements demonstrated that the sulfur-sorption mainly occurs in the first 60 min after contact with the adsorbent, so that the total time span of the desulfurization process can be limited to 1 h. Therefore, this material seems to be highly suitable for sulfur reduction in commercial fuels in order to meet regulatory requirements and demands for automotive exhaust catalysis-systems or exhaust gas sensors. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  15. Stress-induced chemical detection using flexible metal-organic frameworks.

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Hesketh, Peter J. (Georgia Institute of Technology, Atlanta, GA); Gall, Kenneth A. (Georgia Institute of Technology, Atlanta, GA); Choudhury, A. (Georgia Institute of Technology, Atlanta, GA); Pikarsky, J. (Georgia Institute of Technology, Atlanta, GA); Andruszkiewicz, Leanne (Georgia Institute of Technology, Atlanta, GA); Houk, Ronald J. T.; Talin, Albert Alec (National Institute of Standards & Technology, Gaithersburg, MD)

    2009-09-01

    In this work we demonstrate the concept of stress-induced chemical detection using metal-organic frameworks (MOFs) by integrating a thin film of the MOF HKUST-1 with a microcantilever surface. The results show that the energy of molecular adsorption, which causes slight distortions in the MOF crystal structure, can be efficiently converted to mechanical energy to create a highly responsive, reversible, and selective sensor. This sensor responds to water, methanol, and ethanol vapors, but yields no response to either N{sub 2} or O{sub 2}. The magnitude of the signal, which is measured by a built-in piezoresistor, is correlated with the concentration and can be fitted to a Langmuir isotherm. Furthermore, we show that the hydration state of the MOF layer can be used to impart selectivity to CO{sub 2}. We also report the first use of surface-enhanced Raman spectroscopy to characterize the structure of a MOF film. We conclude that the synthetic versatility of these nanoporous materials holds great promise for creating recognition chemistries to enable selective detection of a wide range of analytes. A force field model is described that successfully predicts changes in MOF properties and the uptake of gases. This model is used to predict adsorption isotherms for a number of representative compounds, including explosives, nerve agents, volatile organic compounds, and polyaromatic hydrocarbons. The results show that, as a result of relatively large heats of adsorption (> 20 kcal mol{sup -1}) in most cases, we expect an onset of adsorption by MOF as low as 10{sup -6} kPa, suggesting the potential to detect compounds such as RDX at levels as low as 10 ppb at atmospheric pressure.

  16. Amino-functionalized metal-organic frameworks as tunable heterogeneous basic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, M.; Hartmann, M. [Erlangen-Nuernberg Univ., Erlangen (Germany). Erlangen Catalysis Resource Center

    2011-07-01

    Metal-organic framework (MOF) materials have been explored for applications in heterogeneous catalysis in recent years. In addition to the use of MOFs as supports for the deposition of highly dispersed metal particles, the incorporation of active centers such as coordinatively unsaturated metal sites and the functionalization of the organic linkers with acidic or basic groups seems to be most promising. In our contribution, three different MOFs carrying amino groups at their organic linkers, namely Fe-MIL-101-NH{sub 2} (S{sub BET} = 3438 m{sup 2}g{sup -1}), Al-MIL-101-NH{sub 2} (S{sub BET} = 3099 m{sup 2}g{sup -1}) and CAU-1 (S{sub BET} = 1492 m{sup 2}g{sup -1}), were synthesized and tested in the Knoevenagel condensation of benzaldehyde with malononitrile and with ethyl cyanoacetate, respectively. It is shown that the expected products benzylidenemalononitrile (BzMN) and ethyl a-cyanocinnamate (EtCC) are formed with selectivities of more than 99 % and yields of 90 to 95 % after 3 h (for BzMN). Due to the very small pore windows of CAU-1 (0.3 to 0.4 nm) the reaction proceeds much slower over this catalyst in comparison to the amino-MIL-101 derivatives, which possess open pore windows of up to 1.6 nm. Finally, leaching tests confirm that the reaction is heterogeneously catalyzed. Moreover, the catalysts are recyclable without significant loss of activity. (orig.)

  17. A Cooperative Copper Metal-Organic Framework-Hydrogel System Improves Wound Healing in Diabetes.

    Science.gov (United States)

    Xiao, Jisheng; Chen, Siyu; Yi, Ji; Zhang, Hao; Ameer, Guillermo A

    2017-01-05

    Chronic non-healing wounds remain a major clinical challenge that would benefit from the development of advanced, regenerative dressings that promote wound closure within a clinically relevant time frame. The use of copper ions has shown promise in wound healing applications possibly by promoting angiogenesis. However, reported treatments that use copper ions require multiple applications of copper salts or oxides to the wound bed, exposing the patient to potentially toxic levels of copper ions and resulting in variable outcomes. Herein we set out to assess whether copper metal organic framework nanoparticles (HKUST-1 NPs) embedded within an antioxidant thermoresponsive citrate-based hydrogel would decrease copper ion toxicity and accelerate wound healing in diabetic mice. HKUST-1 and poly-(polyethyleneglycol citrate-co- N -isopropylacrylamide) (PPCN) were synthesized and characterized. HKUST-1 NP stability in a protein solution with and without embedding them in PPCN hydrogel was determined. Copper ion release, cytotoxicity, apoptosis, and in vitro migration processes were measured. Wound closure rates and wound blood perfusion were assessed in vivo using the splinted excisional dermal wound diabetic mouse model. HKUST-1 NP disintegrated in protein solution while HKUST-1 NPs embedded in PPCN (H-HKUST-1) were protected from degradation and copper ions were slowly released. Cytotoxicity and apoptosis due to copper ion release were significantly reduced while dermal cell migration in vitro and wound closure rates in vivo were significantly enhanced. In vivo , H-HKUST-1 induced angiogenesis, collagen deposition, and re-epithelialization during wound healing in diabetic mice. These results suggest that a cooperatively stabilized, copper ion-releasing H-HKUST-1 hydrogel is a promising innovative dressing for the treatment of chronic wounds.

  18. Metal-Organic Frameworks for Resonant-Gravimetric Detection of Trace-Level Xylene Molecules.

    Science.gov (United States)

    Xu, Tao; Xu, Pengcheng; Zheng, Dan; Yu, Haitao; Li, Xinxin

    2016-12-20

    As one of typical VOCs, xylene is seriously harmful to human health. Nowadays, however, there is really lack of portable sensing method to directly detect environmental xylene that has chemical inertness. Especially when the concentration of xylene is lower than the human olfactory threshold of 470 ppb, people are indeed hard to be aware of and avoid this harmful vapor. Herein the metal-organic framework (MOF) of HKUST-1 is first explored for sensing to the nonpolar molecule of p-xylene. And the sensing mechanism is identified that is via host-guest interaction of MOF with xylene molecule. By loading MOFs on mass-gravimetric resonant-cantilevers, sensing experiments for four MOFs of MOF-5, HKUST-1, ZIF-8, and MOF-177 approve that HKUST-1 has the highest sensitivity to p-xylene. The resonant-gravimetric sensing experiments with our HKUST-1 based sensors have demonstrated that trace-level p-xylene of 400 ppb can be detected that is lower than the human olfactory threshold of 470 ppb. We analyze that the specificity of HKUST-1 to xylene comes from Cu 2+ -induced moderate Lewis acidity and the "like dissolves like" interaction of the benzene ring. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used to elucidate the adsorbing/sensing mechanism of HKUST-1 to p-xylene, where p-xylene adsorbing induced blue-shift phenomenon is observed that confirms the sensing mechanism. Our study also indicates that the sensor shows good selectivity to various kinds of common interfering gases. And the long-term repeatability and stability of the sensing material are also approved for the usage/storage period of two months. This research approves that the MOF materials exhibit potential usages for high performance chemical sensors applications.

  19. Surfactant media to grow new crystalline cobalt 1,3,5-benzenetricarboxylate metal-organic frameworks

    KAUST Repository

    Lu, Haisheng

    2014-08-18

    In this report, three new metal-organic frameworks (MOFs), [Co 3(μ3-OH)(HBTC)(BTC)2Co(HBTC)]·(HTEA) 3·H2O (NTU-Z30), [Co(BTC)] ·HTEA·H2O (NTU-Z31), [Co3(BTC) 4]·(HTEA)4 (NTU-Z32), where H3BTC = 1,3,5-benzenetricarboxylic acid, TEA = triethylamine, and NTU = Nanyang Technological University, have been successfully synthesized under surfactant media and have been carefully characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, and IR spectromtry. NTU-Z30 has an unusual trimeric [Co3(μ3-OH)(COO) 7] secondary building unit (SBU), which is different from the well-known trimeric [Co3O(COO)6] SBU. The topology studies indicate that NTU-Z30 and NTU-Z32 possess two new topologies, 3,3,6,7-c net and 2,8-c net, respectively, while NTU-Z31 has a known topology rtl type (3,6-c net). Magnetic analyses show that all three materials have weak antiferromagnetic behavior. Furthermore, NTU-Z30 has been selected as the heterogeneous catalyst for the aerobic epoxidation of alkene, and our results show that this material exhibits excellent catalytic activity as well as good stability. Our success in growing new crystalline cobalt 1,3,5- benzenetricarboxylate MOFs under surfactant media could pave a new road to preparing new diverse crystalline inorganic materials through a surfactant-thermal method. © 2014 American Chemical Society.

  20. Understanding the origins of metal-organic framework/polymer compatibility.

    Science.gov (United States)

    Semino, R; Moreton, J C; Ramsahye, N A; Cohen, S M; Maurin, G

    2018-01-14

    The microscopic interfacial structures for a series of metal-organic framework/polymer composites consisting of the Zr-based UiO-66 coupled with different polymers are systematically explored by applying a computational methodology that integrates density functional theory calculations and force field-based molecular dynamics simulations. These predictions are correlated with experimental findings to unravel the structure-compatibility relationship of the MOF/polymer pairs. The relative contributions of the intermolecular MOF/polymer interactions and the flexibility/rigidity of the polymer with respect to the microscopic structure of the interface are rationalized, and their impact on the compatibility of the two components in the resulting composite is discussed. The most compatible pairs among those investigated involve more flexible polymers, i.e. polyvinylidene fluoride (PVDF) and polyethylene glycol (PEG). These polymers exhibit an enhanced contact surface, due to a better adaptation of their configuration to the MOF surface. In these cases, the irregularities at the MOF surface are filled by the polymer, and even some penetration of the terminal groups of the polymer into the pores of the MOF can be observed. As a result, the affinity between the MOF and the polymer is very high; however, the pores of the MOF may be sterically blocked due to the strong MOF/polymer interactions, as evidenced by UiO-66/PEG composites. In contrast, composites involving polymers that exhibit higher rigidity, such as the polymer of intrinsic microporosity-1 (PIM-1) or polystyrene (PS), present interfacial microvoids that contribute to a decrease in the contact surface between the two components, thus reducing the MOF/polymer affinity.

  1. Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework.

    Science.gov (United States)

    Mohideen, M Infas H; Xiao, Bo; Wheatley, Paul S; McKinlay, Alistair C; Li, Yang; Slawin, Alexandra M Z; Aldous, David W; Cessford, Naomi F; Düren, Tina; Zhao, Xuebo; Gill, Rachel; Thomas, K Mark; Griffin, John M; Ashbrook, Sharon E; Morris, Russell E

    2011-04-01

    Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

  2. Crystal Engineering of Naphthalenediimide-Based Metal-Organic Frameworks: Structure-Dependent Lithium Storage.

    Science.gov (United States)

    Tian, Bingbing; Ning, Guo-Hong; Gao, Qiang; Tan, Li-Min; Tang, Wei; Chen, Zhongxin; Su, Chenliang; Loh, Kian Ping

    2016-11-16

    Metal-organic frameworks (MOFs) possess great structural diversity because of the flexible design of linker groups and metal nodes. The structure-property correlation has been extensively investigated in areas like chiral catalysis, gas storage and absorption, water purification, energy storage, etc. However, the use of MOFs in lithium storage is hampered by stability issues, and how its porosity helps with battery performance is not well understood. Herein, through anion and thermodynamic control, we design a series of naphthalenediimide-based MOFs 1-4 that can be used for cathode materials in lithium-ion batteries (LIBs). Complexation of the N,N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide (DPNDI) ligand and CdX 2 (X = NO 3 - or ClO 4 - ) produces complexes MOFs 1 and 2 with a one-dimensional (1D) nonporous network and a porous, noninterpenetrated two-dimensional (2D) square-grid structure, respectively. With the DPNDI ligand and Co(NCS) 2 , a porous 1D MOF 3 as a kinetic product is obtained, while a nonporous, noninterpenetrated 2D square-grid structure MOF 4 as a thermodynamic product is formed. The performance of LIBs is largely affected by the stability and porosity of these MOFs. For instance, the initial charge-discharge curves of MOFs 1 and 2 show a specific capacity of ∼47 mA h g -1 with a capacity retention ratio of >70% during 50 cycles at 100 mA g -1 , which is much better than that of MOFs 3 and 4. The better performances are assigned to the higher stability of Cd(II) MOFs compared to that of Co(II) MOFs during the electrochemical process, according to X-ray diffraction analysis. In addition, despite having the same Cd(II) node in the framework, MOF 2 exhibits a lithium-ion diffusion coefficient (D Li ) larger than that of MOF 1 because of its higher porosity. X-ray photoelectron spectroscopy and Fourier transform infrared analysis indicate that metal nodes in these MOFs remain intact and only the DPNDI ligand undergoes the revisible redox reaction

  3. Manufacture of highly loaded silica-supported cobalt Fischer–Tropsch catalysts from a metal organic framework

    KAUST Repository

    Sun, Xiaohui

    2017-11-16

    The development of synthetic protocols for the preparation of highly loaded metal nanoparticle-supported catalysts has received a great deal of attention over the last few decades. Independently controlling metal loading, nanoparticle size, distribution, and accessibility has proven challenging because of the clear interdependence between these crucial performance parameters. Here we present a stepwise methodology that, making use of a cobalt-containing metal organic framework as hard template (ZIF-67), allows addressing this long-standing challenge. Condensation of silica in the Co-metal organic framework pore space followed by pyrolysis and subsequent calcination of these composites renders highly loaded cobalt nanocomposites (~ 50 wt.% Co), with cobalt oxide reducibility in the order of 80% and a good particle dispersion, that exhibit high activity, C5 + selectivity and stability in Fischer-Tropsch synthesis.

  4. Particle size studies to reveal crystallization mechanisms of the metal organic framework HKUST-1 during sonochemical synthesis.

    Science.gov (United States)

    Armstrong, Mitchell R; Senthilnathan, Sethuraman; Balzer, Christopher J; Shan, Bohan; Chen, Liang; Mu, Bin

    2017-01-01

    Systematic studies of key operating parameters for the sonochemical synthesis of the metal organic framework (MOF) HKUST-1(also called CuBTC) were performed including reaction time, reactor volume, sonication amplitude, sonication tip size, solvent composition, and reactant concentrations analyzed through SEM particle size analysis. Trends in the particle size and size distributions show reproducible control of average particle sizes between 1 and 4μm. These results along with complementary studies in sonofragmentation and temperature control were conducted to compare these results to kinetic crystal growth models found in literature to develop a plausible hypothetical mechanism for ultrasound-assisted growth of metal-organic-frameworks composed of a competitive mechanism including constructive solid-on-solid (SOS) crystal growth and a deconstructive sonofragmentation. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. A template-free method for stable CuO hollow microspheres fabricated from a metal organic framework (HKUST-1).

    Science.gov (United States)

    Zhang, Suoying; Liu, Hong; Liu, Pengfei; Yang, Zhuhong; Feng, Xin; Huo, Fengwei; Lu, Xiaohua

    2015-06-07

    Uniform CuO hollow microspheres were successfully achieved from a non-uniform metal organic framework by using a template-free method. The process mechanism has been revealed to be spherical aggregation and Ostwald ripening. When tested in CO oxidation and heat treatment, these assembled microspheres exhibited an excellent catalytic performance and show a much better stability than the inherited hollow structure from MOFs.

  6. Solvothermal growth of a ruthenium metal-organic framework featuring HKUST-1 structure type as thin films on oxide surfaces.

    Science.gov (United States)

    Kozachuk, Olesia; Yusenko, Kirill; Noei, Heshmat; Wang, Yuemin; Walleck, Stephan; Glaser, Thorsten; Fischer, Roland A

    2011-08-14

    Phase-pure crystalline thin films of a mixed-valence Ru(2)(II,III) metal-organic framework with 1,3,5-benzenetricarboxylate (btc) as a linker were solvothermally grown on amorphous alumina and silica surfaces. Based on the Rietveld refinement, the structure of Ru-MOF was assigned to be analogous to [Cu(3)(btc)(2)] (HKUST-1). This journal is © The Royal Society of Chemistry 2011

  7. Synthesis and characterization of bimetallic metal-organic framework Cu-Ru-BTC with HKUST-1 structure.

    Science.gov (United States)

    Gotthardt, Meike A; Schoch, Roland; Wolf, Silke; Bauer, Matthias; Kleist, Wolfgang

    2015-02-07

    The bimetallic metal-organic framework Cu-Ru-BTC with the stoichiometric formula Cu2.75Ru0.25(BTC)2·xH2O, which is isoreticular to HKUST-1, was successfully prepared in a direct synthesis using mild reaction conditions. The partial substitution of Cu(2+) by Ru(3+) centers in the paddlewheel structure and the absence of other Ru-containing phases was proven using X-ray absorption spectroscopy.

  8. Polymer-Derived Silicoboron Carbonitride Foams for CO2 Capture: From Design to Application as Scaffolds for the in Situ Growth of Metal-Organic Frameworks.

    Science.gov (United States)

    Sandra, Fabien; Depardieu, Martin; Mouline, Zineb; Vignoles, Gérard L; Iwamoto, Yuji; Miele, Philippe; Backov, Rénal; Bernard, Samuel

    2016-06-06

    A template-assisted polymer-derived ceramic route is investigated for preparing a series of silicoboron carbonitride (Si/B/C/N) foams with a hierarchical pore size distribution and tailorable interconnected porosity. A boron-modified polycarbosilazane was selected to impregnate monolithic silica and carbonaceous templates and form after pyrolysis and template removal Si/B/C/N foams. By changing the hard template nature and controlling the quantity of polymer to be impregnated, controlled micropore/macropore distributions with mesoscopic cell windows are generated. Specific surface areas from 29 to 239 m(2)  g(-1) and porosities from 51 to 77 % are achieved. These foams combine a low density with a thermal insulation and a relatively good thermostructural stability. Their particular structure allowed the in situ growth of metal-organic frameworks (MOFs) directly within the open-cell structure. MOFs offered a microporosity feature to the resulting Si/B/C/N@MOF composite foams that allowed increasing the specific surface area to provide CO2 uptake of 2.2 %. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Insights into Surface Interactions between Metal Organic Frameworks and Gases during Transient Adsorption and Diffusion by In-Situ Small Angle X-ray Scattering

    Directory of Open Access Journals (Sweden)

    Ludovic F. Dumée

    2016-09-01

    Full Text Available The fabrication of molecular gas sieving materials with specific affinities for a single gas species and able to store large quantities of materials at a low or atmospheric pressure is desperately required to reduce the adverse effects of coal and oil usage in carbon capture. Fundamental understanding of the dynamic adsorption of gas, the diffusion mechanisms across thin film membranes, and the impact of interfaces play a vital role in developing these materials. In this work, single gas permeation tests across micro-porous membrane materials, based on metal organic framework crystals grown on the surface of carbon nanotubes (ZiF-8@CNT, were performed for the first time in-situ at the Australian Synchrotron on the small angle X-ray scattering beamline in order to reveal molecular sieving mechanisms and gas adsorption within the material. The results show that specific chemi-sorption of CO2 across the ZiF-8 crystal lattices affected the morphology and unit cell parameters, while the sieving of other noble or noble like gases across the ZiF-8@CNT membranes was found to largely follow Knudsen diffusion. This work demonstrates for the first time a novel and effective technique to assess molecular diffusion at the nano-scale across sub-nano-porous materials by probing molecular flexibility across crystal lattice and single cell units.

  10. Self and transport diffusivity of CO2 in the metal-organic framework MIL-47(V) explored by quasi-elastic neutron scattering experiments and molecular dynamics simulations.

    Science.gov (United States)

    Salles, Fabrice; Jobic, Hervé; Devic, Thomas; Llewellyn, Philip L; Serre, Christian; Férey, Gérard; Maurin, Guillaume

    2010-01-26

    Quasi-elastic neutron scattering measurements are combined with molecular dynamics simulations to determine the self-diffusivity, corrected diffusivity, and transport diffusivity of CO(2) in the metal-organic framework MIL-47(V) (MIL = Materials Institut Lavoisier) over a wide range of loading. The force field used for describing the host/guest interactions is first validated on the thermodynamics of the MIL-47(V)/CO(2) system, prior to being transferred to the investigations of the dynamics. A decreasing profile is then deduced for D(s) and D(o) whereas D(t) presents a non monotonous evolution with a slight decrease at low loading followed by a sharp increase at higher loading. Such decrease of D(t) which has never been evidenced in any microporous systems comes from the atypical evolution of the thermodynamic correction factor that reaches values below 1 at low loading. This implies that, due to intermolecular interactions, the CO(2) molecules in MIL-47(V) do not behave like an ideal gas. Further, molecular simulations enabled us to elucidate unambiguously a 3D diffusion mechanism within the pores of MIL-47(V).

  11. Assembly of a water-insoluble strontium metal-organic framework with luminescent properties

    Czech Academy of Sciences Publication Activity Database

    Lo, S.-H.; Liu, H.-K.; Zhan, J.-X.; Lin, W.-Ch.; Kao, Ch.-Ch.; Lin, Ch.-H.; Zima, Vítězslav

    2011-01-01

    Roč. 14, č. 10 (2011), 1602-1605 ISSN 1387-7003 R&D Projects: GA ČR GA203/08/0208 Institutional research plan: CEZ:AV0Z40500505 Keywords : structure * strontium * metal -organic Subject RIV: CA - Inorganic Chemistry Impact factor: 1.972, year: 2011

  12. Metal-organic frameworks in mixed-matrix membranes for gas separation.

    Science.gov (United States)

    Tanh Jeazet, Harold B; Staudt, Claudia; Janiak, Christoph

    2012-12-14

    Mixed-matrix membranes (MMMs) with metal-organic frameworks (MOFs) as additives (fillers) exhibit enhanced gas permeabilities and possibly also selectivities when compared to the pure polymer. Polyimides (Matrimid®) and polysulfones are popular polymer matrices for MOF fillers. Presently investigated MOFs for MMMs include [Cu(SiF(6))(4,4'-BIPY)(2)], [Cu(3)(BTC)(2)(H(2)O)(3)] (HKUST-1, Cu-BTC), [Cu(BDC)(DMF)], [Zn(4)O(BDC)(3)] (MOF-5), [Zn(2-methylimidazolate)(2)] (ZIF-8), [Zn(purinate)(2)] (ZIF-20), [Zn(2-carboxyaldehyde imidazolate)(2)] (ZIF-90), Mn(HCOO)(2), [Al(BDC)(μ-OH)] (MIL-53(Al)), [Al(NH(2)-BDC)(μ-OH)] (NH(2)-MIL-53(Al)) and [Cr(3)O(BDC)(3)(F,OH)(H(2)O)(2)] (MIL-101) (4,4'-BIPY = 4,4'-bipyridine, BTC = benzene-1,3,5-tricarboxylate, BDC = benzene-1,4-dicarboxylate, terephthalate). MOF particle adhesion to polyimide and polysulfone organic polymers does not represent a problem. MOF-polymer MMMs are investigated for the permeability of the single gases H(2), N(2), O(2), CH(4), CO(2) and of the gas mixtures O(2)/N(2), H(2)/CH(4), CO(2)/CH(4), H(2)/CO(2), CH(4)/N(2) and CO(2)/N(2) (preferentially permeating gas named first). Permeability increases can be traced to the MOF porosity. Since the porosity of MOFs can be tuned very precisely, which is not possible with polymeric material, MMMs offer the opportunity of significantly increasing the selectivity compared to the pure polymeric matrix. Additionally in most of the cases the permeability is increased for MMM membranes compared to the pure polymer. Addition of MOFs to polymers in MMMs easily yields performances similar to the best polymer membranes and gives higher selectivities than those reported to date for any pure MOF membrane for the same gas separation. MOF-polymer MMMs allow for easier synthesis and handability compared to pure MOF membranes.

  13. Synthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supports

    KAUST Repository

    Barankova, Eva

    2017-06-01

    Since the discovery of size-selective metal-organic frameworks (MOF) researchers have tried to manufacture them into gas separation membranes. ZIF-8 became the most studied MOF for membrane applications mainly because of its simple synthesis, good chemical and thermal stability, recent commercial availability and attractive pore size. The aim of this work is to develop convenient methods for growing ZIF thin layers on polymer supports to obtain defect-free ZIF membranes with good gas separation properties. We present new approaches for ZIF membranes preparation on polymers. We introduce zinc oxide nanoparticles in the support as a secondary metal source for ZIF-8 growth. Initially the ZnO particles were incorporated into the polymer matrix and later on the surface of the polymer by magnetron sputtering. In both cases, the ZnO facilitated to create more nucleation opportunities and improved the ZIF-8 growth compared to the synthesis without using ZnO. By employing the secondary seeded growth method, we were able to obtain thin (900 nm) ZIF-8 layer with good gas separation performance. Next, we propose a metal-chelating polymer as a suitable support for growing ZIF layers. Defect-free ZIF-8 films with a thickness of 600 nm could be obtained by a contra-diffusion method. ZIF-8 membranes were tested for permeation of hydrogen and hydrocarbons, and one of the highest selectivities reported so far for hydrogen/propane, and propylene/propane was obtained. Another promising method to facilitate the growth of MOFs on polymeric supports is the chemical functionalization of the support surface with functional groups, which can complex metal ions and which can covalently bond the MOF crystals. We functionalized the surface of a common porous polymeric membrane with amine groups, which took part in the reaction to form ZIF-8 nanocrystals. We observed an enhancement in adhesion between the ZIF layer and the support. The effect of parameters of the contra-diffusion experiment

  14. Minimal Edge-Transitive Nets for the Design and Construction of Metal-Organic Frameworks

    KAUST Repository

    Eddaoudi, Mohamed

    2017-04-05

    Highly-connected and minimal edge-transitive nets (with one or two kinds of edge) can be regarded as ideal blueprints for the rational design and construction of metal-organic frameworks (MOFs). Here we report and affirm the prominence of highly-connected nets as suitable targets in reticular chemistry for the design and synthesis of MOFs. Of special interest are augmented highly-connected binodal edge-transitive nets embedding a unique and precise positioning and connectivity of the net vertex figures, regarded as net-coded building units (net-cBUs). Explicitly, a definite net-cBU encompasses precise geometrical information that codes uniquely and matchlessly a selected net, a compelling perquisite for the rational design of MOFs. Interestingly, the double six-membered ring (d6R) building unit offers great prospective to be deployed as a net-cBU for the deliberate reticulation of the sole two edge-transitive nets with a vertex figure as a d6R, namely the (4,12)-coordinated shp net (square and hexagonal prism) and the (6,12)-coordinated alb net (aluminium diboride, hexagonal prism and trigonal prism). Conceivably, we envisioned and proposed various MOF structures based on the derived shp and alb nets. Gaining access to the requisite net-cBUs is essential for the successful practice of reticular chemistry; correspondingly organic and organic chemistries were deployed to afford concomitant molecular building blocks (MBBs) with the looked-for shape and connectivity. Practically, the combination of the 12-connected (12-c) rare-earth (RE) polynuclear, points of extension matching the 12 vertices of the hexagonal prism (d6R) with a 4-connected tetracarboxylate ligand or a 6-connected hexacarboxylate ligand afforded the targeted shp-MOF or alb-MOF, respectively. Intuitively, a dodecacarboxylate ligand can be conceived and purported as a compatible 12-c MBB, plausibly affording the positioning of the carbon centers of the twelve carboxylate groups on the vertices of the

  15. Investigating the gas sorption mechanism in an rht -metal-organic framework through computational studies

    KAUST Repository

    Pham, Tony T.

    2014-01-09

    Grand canonical Monte Carlo (GCMC) simulations were performed to investigate CO2 and H2 sorption in an rht-metal-organic framework (MOF) that was synthesized with a ligand having a nitrogen-rich trigonal core through trisubstituted triazine groups and amine functional groups. This MOF was synthesized by two different groups, each reporting their own distinct gas sorption measurements and crystal structure. Electronic structure calculations demonstrated that the small differences in the atomic positions between each group\\'s crystal structure resulted in different electrostatic parameters about the Cu2+ ions for the respective unit cells. Simulations of CO2 sorption were performed with and without many-body polarization effects and using our recently developed CO2 potentials, in addition to a well-known bulk CO2 model, in both crystallographic unit cells. Simulated CO2 sorption isotherms and calculated isosteric heats of adsorption, Qst, values were in excellent agreement with the results reported previously by Eddaoudi et al. for both structures using the polarizable CO2 potential. For both crystal structures, the initial site for CO2 sorption were the Cu 2+ ions that had the higher positive charge in the unit cell, although the identity of this electropositive Cu2+ ion was different in each case. Simulations of H2 sorption were performed with three different hydrogen potentials of increasing anisotropy in both crystal structures and the results, especially with the highest fidelity model, agreed well with Eddaoudi et al.\\'s experimental data. The preferred site of H 2 sorption at low loading was between two Cu2+ ions of neighboring paddlewheels. The calculation of the normalized hydrogen dipole distribution for the polarizable model in both crystal structures aided in the identification of four distinct sorption sites in the MOF, which is consistent to what was observed in the experimental inelastic neutron scattering (INS) spectra. Lastly, while the

  16. Hydrogen storage in metal-organic frameworks: An investigation of structure-property relationships

    Science.gov (United States)

    Rowsell, Jesse

    Metal-organic frameworks (MOFs) have been identified as candidate hydrogen storage materials due to their ability to physisorb large quantities of small molecules. Thirteen compounds (IRMOF-1, -2, -3, -6, -8, -9, -11, -13, -18, -20, MOF-74, MOF-177 and HKUST-1) have been prepared and fully characterized for the evaluation of their dihydrogen (H2) adsorption properties. All compounds display approximately type I isotherms with no hysteresis at 77 K up to 1 atm. The amount adsorbed ranges from 0.89 to 2.54 wt%; however, saturation is not achieved under these conditions. The influences of link functionalization, catenation and topology are examined for the eleven MOFs composed of Zn4O(O2C-)6 clusters. Enhanced H2 uptake by catenated compounds is rationalized by increased overlap of the surface potentials within their narrower pores. This is corroborated by the larger isosteric heat of adsorption of IRMOF-11 compared to IRMOF-1. Inelastic neutron scattering spectroscopic analysis of four Zn4O-based materials (IRMOF-1, -8, -11, and MOF-74) under a range of H2 loading suggests the presence of multiple localized adsorption sites on both the inorganic and organic moieties. To determine the structural details of the adsorption sites, variable temperature single crystal X-ray diffraction was used to analyze adsorbed argon and dinitrogen molecules in IRMOF-1. The principle binding site was found to be the same for both adsorbates and is located on faces of the octahedral Zn4O(O2C-)6 clusters with close contacts to three carboxylate groups. A total of eight symmetry-independent adsorption sites were identified for argon at 30 K. Similar sites were observed for dinitrogen, suggesting that they are good model adsorbates for the behaviour of dihydrogen. Two additional materials composed of inorganic clusters with coordinatively unsaturated metal sites (MOF-74, HKUST-1) were examined and their increased capacities and isosteric heats of adsorption provide further evidence that the

  17. Stability of metal organic frameworks and interaction of small gas molecules in these materials

    Science.gov (United States)

    Tan, Kui

    The work in this dissertation combines spectroscopy ( in-situ infrared absorption and Raman), powder X-ray diffraction and DFT calculations to study the stability of metal organic frameworks materials (MOFs) in the presence of water vapor and other corrosive gases (e.g., SO 2, NO2 NO), and the interaction and competitive co-adsorption of several gases within MOFs by considering two types of prototypical MOFs: 1) a MOF with saturated metal centers based on paddlewheel secondary building units: M(bdc)(ted)0.5 [M=Cu, Zn, Ni, Co, bdc = 1,4-benzenedicarboxylate, ted = triethylenediamine], and 2) a MOF with unsaturated metal centers: M2(dobdc) [M=Mg2+, Zn2+, Ni2+, Co2+ and dobdc = 2,5-dihydroxybenzenedicarboxylate]. We find that the stability of MOFs to water vapor critically depends on their structure and the specific metal cation in the building units. For M(bdc)(ted)0.5, the metal-bdc bond is the most vulnerable for Cu(bdc)(ted)0.5, while the metal-ted bond is first attacked for the Zn and Co analogs. In contrast, Ni(bdc)(ted)0.5 remains stable under the same conditions. For M2(dobdc), or MOF-74, the weak link is the dobdc-metal bond. The water molecule is dissociatively adsorbed at the metal-oxygen group with OH adsorption directly on the metal center and H adsorption on the bridging O of the phenolate group in the dobdc linker. Other technologically important molecules besides water, such as NO, NO2, SO2, tend to poison M2(dobdc) through dissociative or molecular adsorption onto the open metal sites. A high uptake SO2 capacity was measured in M(bdc)(ted)0.5, attributed to multipoint interactions between the guest SO2 molecule and the MOF host. In the case of competitive co-adsorption between CO2 and other small molecules, we find that binding energy alone is not a good indicator of molecular site occupation within the MOF (i.e., it cannot successfully predict and evaluate the displacement of CO2 by other molecules). Instead, we show that the kinetic barrier for the

  18. Toward Developing Made-to-Order Metal-Organic Frameworks: Design, Synthesis and Applications

    KAUST Repository

    Ashri, Lubna Y.

    2016-05-26

    Synthesis of materials with certain properties for targeted applications is an ongoing challenge in materials science. One of the most interesting classes of solid-state materials that have been recently introduced with the potential to address this is metal-organic frameworks (MOFs). MOFs chemistry offers a higher degree of control over materials to be synthesized utilizing various new design strategies, such as the molecular building blocks (MBBs) and the supermolecular building layers (SBLs) approaches. Depending on using predetermined building blocks, these strategies permit the synthesis of MOFs with targeted topologies and enable fine tuning of their properties. This study examines a number of aspects of the design and synthesis of MOFs while exploring their possible utilization in two diverse fields related to energy and pharmaceutical applications. Concerning MOFs design and synthesis, the work presented here explores the rational design of various MOFs with predicted topologies and tunable cavities constructed by pillaring pre-targeted 2-periodic SBLs using the ligand-to-axial and six-connected axial-to-axial pillaring strategies. The effect of expanding the confined spaces in prepared MOFs or modifying their functionalities, while preserving the underlying network topology, was investigated. Additionally, The MBBs approach was employed to discover new modular polynuclear rare earth (RE)-MBBs in the presence of different angular polytopic ligands containing carboxylate and nitrogen moieties with the aid of a modulator. The goal was to assess the diverse possible coordination modes and construct highly-connected nets for utility in the design of new MOFs and enhance the predictability of structural outcomes. The effect of adjusting ligands’ length-to-width ratio on the prepared MOFs was also evaluated. As a result, the reaction conditions amenable for reliable formation of the unprecedented octadecanuclear, octanuclear and double tetranuclear RE-MBBs were

  19. Porphyrinic metal-organic framework/macroporous carbon composites for electrocatalytic applications

    International Nuclear Information System (INIS)

    Yin, Duanduan; Liu, Jian; Bo, Xiangjie; Li, Mian; Guo, Liping

    2017-01-01

    Graphical abstract: Zr-PorMOF/MPC composites were prepared, which used to detect H 2 O 2 and simultaneously detect UA, XA and HX Display Omitted -- Highlights: •Preparing Zr-PorMOF/MPC composites by a simple one-step solvothermal reaction. •Enhanced electrocatalytic activity at Zr-PorMOF/MPC than Zr-PorMOF and MPC. •A low detection limit, short response time and low applied potential towards H 2 O 2 reduction. •Simultaneous determination of UA, XA and HX. -- Abstract: In this work, a novel porphyrinic metal-organic framework-based composite has been successfully synthesized by a simple one-step solvothermal method through growing Zr-PorMOF on macroporous carbon (MPC). Porphyrin-base MOFs combining the structural adjustable of MOFs and the specific catalytic activity of biomimetic catalysts play an important role in electrocatalysis. A series of characterization show that the roles of MPC as follow: (1) MPC could avoid the agglomeration of Zr-PorMOF particles and increase the specific surface area; (2) MPC could improve the electrochemical stability of Zr-PorMOF particles; (3) MPC could reduce the electron transfer resistance. Therefore, MPC plays the role of the conductive bridges to provide facile charge transport. The obtained Zr-PorMOF/MPC composites exhibit much better electrocatalytic activity for the reduction of hydrogen peroxide (H 2 O 2 ) than the pristine Zr-PorMOF due to the synergy of Zr-PorMOF and MPC. This enzyme-free H 2 O 2 sensor shows two linear relationships in the ranges 0.5–137 μM (R 2 = 0.991, sensitivity = 66 μA mM −1 ) and 137–3587 μM (R 2 = 0.993, sensitivity = 16 μA mM −1 ), with a low over-potential at −0.2 V, a fast response time within 1 s and a low limit of detection (LOD) of 0.18 μM. Moreover, Zr-PorMOF/MPC composites were used to simultaneously detect uric acid (UA), xanthine (XA) and hypoxanthine (HX). These three substances are degradation products of purine metabolism. In addition, Zr-PorMOF/MPC composites

  20. Reliably Modeling the Mechanical Stability of Rigid and Flexible Metal-Organic Frameworks.

    Science.gov (United States)

    Rogge, Sven M J; Waroquier, Michel; Van Speybroeck, Veronique

    2018-01-16

    Over the past two decades, metal-organic frameworks (MOFs) have matured from interesting academic peculiarities toward a continuously expanding class of hybrid, nanoporous materials tuned for targeted technological applications such as gas storage and heterogeneous catalysis. These oft-times crystalline materials, composed of inorganic moieties interconnected by organic ligands, can be endowed with desired structural and chemical features by judiciously functionalizing or substituting these building blocks. As a result of this reticular synthesis, MOF research is situated at the intriguing intersection between chemistry and physics, and the building block approach could pave the way toward the construction of an almost infinite number of possible crystalline structures, provided that they exhibit stability under the desired operational conditions. However, this enormous potential is largely untapped to date, as MOFs have not yet found a major breakthrough in technological applications. One of the remaining challenges for this scale-up is the densification of MOF powders, which is generally achieved by subjecting the material to a pressurization step. However, application of an external pressure may substantially alter the chemical and physical properties of the material. A reliable theoretical guidance that can presynthetically identify the most stable materials could help overcome this technological challenge. In this Account, we describe the recent research the progress on computational characterization of the mechanical stability of MOFs. So far, three complementary approaches have been proposed, focusing on different aspects of mechanical stability: (i) the Born stability criteria, (ii) the anisotropy in mechanical moduli such as the Young and shear moduli, and (iii) the pressure-versus-volume equations of state. As these three methods are grounded in distinct computational approaches, it is expected that their accuracy and efficiency will vary. To date

  1. Screening metal-organic frameworks for selective noble gas adsorption in air: effect of pore size and framework topology.

    Science.gov (United States)

    Parkes, Marie V; Staiger, Chad L; Perry, John J; Allendorf, Mark D; Greathouse, Jeffery A

    2013-06-21

    The adsorption of noble gases and nitrogen by sixteen metal-organic frameworks (MOFs) was investigated using grand canonical Monte Carlo simulation. The MOFs were chosen to represent a variety of net topologies, pore dimensions, and metal centers. Three commercially available MOFs (HKUST-1, AlMIL-53, and ZIF-8) and PCN-14 were also included for comparison. Experimental adsorption isotherms, obtained from volumetric and gravimetric methods, were used to compare krypton, argon, and nitrogen uptake with the simulation results. Simulated trends in gas adsorption and predicted selectivities among the commercially available MOFs are in good agreement with experiment. In the low pressure regime, the expected trend of increasing adsorption with increasing noble gas polarizabilty is seen. For each noble gas, low pressure adsorption correlates with several MOF properties, including free volume, topology, and metal center. Additionally, a strong correlation exists between the Henry's constant and the isosteric heat of adsorption for all gases and MOFs considered. Finally, we note that the simulated and experimental gas selectivities demonstrated by this small set of MOFs show improved performance compared to similar values reported for zeolites.

  2. Monitoring the solid-state electrochemistry of Cu(2,7-AQDC) (AQDC = anthraquinone dicarboxylate) in a lithium battery: coexistence of metal and ligand redox activities in a metal-organic framework.

    Science.gov (United States)

    Zhang, Zhongyue; Yoshikawa, Hirofumi; Awaga, Kunio

    2014-11-19

    By adopting a facile synthetic strategy, we obtained a microporous redox-active metal-organic framework (MOF), namely, Cu(2,7-AQDC) (2,7-H2AQDC = 2,7-anthraquinonedicarboxylic acid) (1), and utilized it as a cathode active material in lithium batteries. With a voltage window of 4.0-1.7 V, both metal clusters and anthraquinone groups in the ligands exhibited reversible redox activity. The valence change of copper cations was clearly evidenced by in situ XANES analysis. By controlling the voltage window of operation, extremely high recyclability of batteries was achieved, suggesting the framework was robust. This MOF is the first example of a porous material showing independent redox activity on both metal cluster nodes and ligand sites.

  3. Elucidating the breathing of the metal-organic framework MIL-53(Sc) with ab initio molecular dynamics simulations and in situ X-ray powder diffraction experiments.

    Science.gov (United States)

    Chen, Linjiang; Mowat, John P S; Fairen-Jimenez, David; Morrison, Carole A; Thompson, Stephen P; Wright, Paul A; Düren, Tina

    2013-10-23

    Ab initio molecular dynamics (AIMD) simulations have been used to predict structural transitions of the breathing metal-organic framework (MOF) MIL-53(Sc) in response to changes in temperature over the range 100-623 K and adsorption of CO2 at 0-0.9 bar at 196 K. The method has for the first time been shown to predict successfully both temperature-dependent structural changes and the structural response to variable sorbate uptake of a flexible MOF. AIMD employing dispersion-corrected density functional theory accurately simulated the experimentally observed closure of MIL-53(Sc) upon solvent removal and the transition of the empty MOF from the closed-pore phase to the very-narrow-pore phase (symmetry change from P2(1)/c to C2/c) with increasing temperature, indicating that it can directly take into account entropic as well as enthalpic effects. We also used AIMD simulations to mimic the CO2 adsorption of MIL-53(Sc) in silico by allowing the MIL-53(Sc) framework to evolve freely in response to CO2 loadings corresponding to the two steps in the experimental adsorption isotherm. The resulting structures enabled the structure determination of the two CO2-containing intermediate and large-pore phases observed by experimental synchrotron X-ray diffraction studies with increasing CO2 pressure; this would not have been possible for the intermediate structure via conventional methods because of diffraction peak broadening. Furthermore, the strong and anisotropic peak broadening observed for the intermediate structure could be explained in terms of fluctuations of the framework predicted by the AIMD simulations. Fundamental insights from the molecular-level interactions further revealed the origin of the breathing of MIL-53(Sc) upon temperature variation and CO2 adsorption. These simulations illustrate the power of the AIMD method for the prediction and understanding of the behavior of flexible microporous solids.

  4. Straightforward Generation of Pillared, Microporous Graphene Frameworks for Use in Supercapacitors.

    Science.gov (United States)

    Yuan, Kai; Xu, Yazhou; Uihlein, Johannes; Brunklaus, Gunther; Shi, Lei; Heiderhoff, Ralf; Que, Mingming; Forster, Michael; Chassé, Thomas; Pichler, Thomas; Riedl, Thomas; Chen, Yiwang; Scherf, Ullrich

    2015-11-01

    Microporous, pillared graphene-based frameworks are generated in a simple functionalization/coupling procedure starting from reduced graphene oxide. They are used for the fabrication of high-performance supercapacitor devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. Computational evaluation of metal-organic frameworks for carbon dioxide capture

    Science.gov (United States)

    Yu, Jiamei

    Metal-organic frameworks (MOFs), a new class of porous solids comprised of metal-containing nodes linked by organic ligands, have become promising materials for gas separations. In particular, their flexible chemistry makes them attractive for CO2 capture from flue gas streams in post-combustion plants. Although numerous efforts have been exerted on the investigation of MOFs for CO2 capture, the exploration of the effects from coexisting components present in very dilute proportions in flue gases is limited because of the experimental difficulty to determine the coadsorption of CO2 with trace components. In this regard, molecular simulations show superiority. In this study, molecular simulations are used to estimate the influence of impurities: water, O2, and SO2 on post-combustion CO2 capture in MOFs. Firstly, two MOFs with coordinatively unsaturated metal sites (CUMs), HKUST-1 and Mg-MOF-74 are explored. Increase of CO 2 adsorption is observed for hydrated HKUST-1; on the contrary, the opposite water adsorption behavior is observed in hydrated Mg-MOF-74, leading to decrease of CO2 adsorption. Further, water effects on CO 2 capture in M-HKUST1 (M = Mg, Zn, Co, Ni) are evaluated to test whether comparing the binding energy could be a general method to evaluate water effects in MOFs with CUMs. It is found that the method works well for Zn-, Co-, and Ni-HKUST1 but partially for Mg-HKUST1. In addition, the effects of O2 and SO2 on CO2 capture in MOFs are also investigated for the first time, showing that the effects of O2 may be negligible but SO2 has negative effects in the CO 2 capture process in HKUST-1 systems. Secondly, the influences of water on CO2 capture in three UiO-66 MOFs with functional groups, --NH2, --OH and --Br are explored, respectively. For UiO-66-NH2 and -OH, the presence of water lowers CO2 adsorption significantly; in contrast, water shows much smaller effects in UiO-66-Br. Moreover, the presence of SO 2 decreases water adsorption but enhances CO

  7. On the Peculiar Molecular Shape and Size Dependence of the Dynamics of Fluids confined in a Small-Pore Metal-Organic Framework

    KAUST Repository

    Skarmoutsos, Ioannis; Eddaoudi, Mohamed; Maurin, Guillaume

    2018-01-01

    .e. the Metal-Organic Framework SIFSIX-2-Cu-i. These computations unveil an unprecedented molecular symmetry dependence of the translational and rotational dynamics of fluids confined in channel-like nanoporous materials. In particular this peculiar behaviour

  8. Enhanced binding affinity, remarkable selectivity, and high capacity of CO 2 by dual functionalization of a rht-type metal-organic framework

    KAUST Repository

    Li, Baiyan; Zhang, Zhijuan; Li, Yi; Yao, Kexin; Zhu, Yihan; Deng, Zhiyong; Yang, Fen; Zhou, Xiaojing; Li, Guanghua; Wu, Haohan; Nijem, Nour; Chabal, Yves Jean; Lai, Zhiping; Han, Yu; Shi, Zhan; Feng, Shouhua; Li, Jing

    2011-01-01

    Open and friendly: The smallest member of the rht-type metal-organic frameworks (MOFs, see picture) constructed by a hexacarboxylate ligand with a nitrogen-rich imino triazine backbone shows a significantly enhanced gas binding affinity relative

  9. Hierarchical mesoporous/microporous carbon with graphitized frameworks for high-performance lithium-ion batteries

    Directory of Open Access Journals (Sweden)

    Yingying Lv

    2014-11-01

    Full Text Available A hierarchical meso-/micro-porous graphitized carbon with uniform mesopores and ordered micropores, graphitized frameworks, and extra-high surface area of ∼2200 m2/g, was successfully synthesized through a simple one-step chemical vapor deposition process. The commercial mesoporous zeolite Y was utilized as a meso-/ micro-porous template, and the small-molecule methane was employed as a carbon precursor. The as-prepared hierarchical meso-/micro-porous carbons have homogeneously distributed mesopores as a host for electrolyte, which facilitate Li+ ions transport to the large-area micropores, resulting a high reversible lithium ion storage of 1000 mA h/g and a high columbic efficiency of 65% at the first cycle.

  10. Highly stable ni-m f6-nh2o/onpyrazine2(solvent)x metal organic frameworks and methods of use

    KAUST Repository

    Eddaoudi, Mohamed

    2016-10-13

    Provided herein are metal organic frameworks comprising metal nodes and N-donor organic ligands. Methods for capturing chemical species from fluid compositions comprise contacting a metal organic framework characterized by the formula [MaMbF6-n(O/H2O)w(Ligand)x(solvent)y]z with a fluid composition and capturing one or more chemical species from the fluid composition.

  11. Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal-organic frameworks for catalytic oxidative desulfurization.

    Science.gov (United States)

    Wang, Xu-Sheng; Huang, Yuan-Biao; Lin, Zu-Jin; Cao, Rong

    2014-08-21

    Highly dispersed Keggin-type phosphotungstic acid (H3PW12O40, PTA) encapsulated in the mesocages of amine-functionalized metal-organic frameworks MIL-101(Cr)-NH2 has been prepared by an anion-exchange method. PTA anions (PW12O40(3-)) are stabilized in the mesocages via the electrostatic interaction with amino groups of the MIL-101(Cr)-NH2. The obtained catalyst (denoted PTA@MIL-101(Cr)-NH2) exhibits high catalytic activity in the extractive and catalytic oxidative desulfurization (ECODS) system under mild conditions. Moreover, it can be easily recovered and recycled several times without leaching and loss of activity.

  12. Exact matrix treatment of statistical mechanical lattice model of adsorption induced gate opening in metal-organic frameworks

    International Nuclear Information System (INIS)

    Dunne, Lawrence J; Manos, George

    2015-01-01

    Here we present a statistical mechanical lattice model which is exactly solvable using a matrix method and allows treatment of adsorption induced gate opening structural transformations of metal-organic frameworks which are nanoporous materials with exceptional adsorption properties. Modelling of these structural changes presents a serious theoretical challenge when the solid and gas species are treated in an even handed way. This exactly solvable model complements other simulation based approaches. The methodology presented here highlights the competition between the potential for adsorption and the energy required for structural transition as a driving force for the features in the adsorption isotherms. (paper)

  13. Postsynthesis Modification of a Metallosalen-Containing Metal-Organic Framework for Selective Th(IV)/Ln(III) Separation.

    Science.gov (United States)

    Guo, Xiang-Guang; Qiu, Sen; Chen, Xiuting; Gong, Yu; Sun, Xiaoqi

    2017-10-16

    An uncoordinated salen-containing metal-organic framework (MOF) obtained through postsynthesis removal of Mn(III) ions from a metallosalen-containing MOF material has been used for selective separation of Th(IV) ion from Ln(III) ions in methanol solutions for the first time. This material exhibited an adsorption capacity of 46.345 mg of Th/g. The separation factors (β) of Th(IV)/La(III), Th(IV)/Eu(III), and Th(IV)/Lu(III) were 10.7, 16.4, and 10.3, respectively.

  14. Prediction of molecular separation of polar-apolar mixtures on heterogeneous metal-organic frameworks: HKUST-1.

    Science.gov (United States)

    Van Assche, Tom R C; Duerinck, Tim; Van der Perre, Stijn; Baron, Gino V; Denayer, Joeri F M

    2014-07-08

    Due to the combination of metal ions and organic linkers and the presence of different types of cages and channels, metal-organic frameworks often possess a large structural and chemical heterogeneity, complicating their adsorption behavior, especially for polar-apolar adsorbate mixtures. By allocating isotherms to individual subunits in the structure, the ideal adsorbed solution theory (IAST) can be adjusted to cope with this heterogeneity. The binary adsorption of methanol and n-hexane on HKUST-1 is analyzed using this segregated IAST (SIAST) approach and offers a significant improvement over the standard IAST model predictions. It identifies the various HKUST-1 cages to have a pronounced polar or apolar adsorptive behavior.

  15. Metal-organic framework thin films on a surface of optical fibre long period grating for chemical sensing

    Science.gov (United States)

    Hromadka, J.; Tokay, B.; James, S.; Korposh, S.

    2017-04-01

    An optical fibre long period grating (LPG) modified with a thin film of HKUST-1, a material from metal organic framework (MOF) family, was employed for the detection of carbon dioxide. The sensing mechanism is based on the measurement of the change of the refractive index (RI) of the coating that is induced by the penetration of CO2 molecules into the HKUST-1 pores. The responses of the resonance bands in the transmission spectrum of an LPG modified with 40 layers of HKUST-1 upon exposure to carbon dioxide in mixture with nitrogen were investigated.

  16. Positional isomerism-driven two 3D pillar-layered metal-organic frameworks: Syntheses, topological structures and photoluminescence properties

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yayong; Zhao, Siwei; Ma, Haoran; Han, Yi; Liu, Kang; Wang, Lei, E-mail: inorchemwl@126.com

    2016-06-15

    Two novel three-dimensional (3D) pillar-layered metal-organic frameworks (MOFs), namely [Zn{sub 2}(μ{sub 2}-OH)(boaba)(1,4-bmimb)]{sub n} (1) and {[Zn_5K_2(μ_2-H_2O)_2(boaba)_4(1,2-bmimb)_2(H_2O)_2]·H_2O}{sub n} (2), were prepared by hydrothermal reactions (H{sub 3}boaba=3,5-bis-oxyacetate-benzoic acid; 1,4-bmimb=1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene; 1,2-bmimb =1,2-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene). Notably, 1 exhibits a (3,5)-connected binodal (6{sup 3})(6{sup 9}·8)-gra net with binuclear [Zn{sub 2}(μ{sub 2}-OH)(COO)]{sup 2+} clusters, while 2 shows a novel (4,4,5,9)-connected 4-nodal net constructed from the unique Zn(II)-K(I) heterometal rod-like substructures. The results indicate that the disposition of the 2-methylimidazolyl groups of bis(imidazole) ligands have a significant effect on structural diversity. Moreover, the photoluminescence properties of 1 and 2 have been investigated. - Graphical abstract: Two novel 3D pillar-layered metal-organic coordination networks with aromatic multicarboxylate anion and bis(imidazole) ligands have been synthesized and structurally characterized. Display Omitted - Highlights: • It is rarely reported that metal-organic frameworks prepared with 3,5-bis-oxyacetate-benzoic acid. • Two metal-organic frameworks based on positional isomeric ligands were synthesized and structurally characterized. • Compond 1 displays unique (3,5)-connected binodal gra topology. • Compound 2 exhibits (4,4,5,9)-connected 4-nodal topology based on the Zn(II)-K(I) heterometal rod-like substructures. • The photoluminescence properties of compound 1 and 2 have been investigated.

  17. Luminescent Lanthanide Metal Organic Frameworks for cis-Selective Isoprene Polymerization Catalysis

    Directory of Open Access Journals (Sweden)

    Samantha Russell

    2015-11-01

    Full Text Available In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+ were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range.

  18. Mesoporous carbon-zirconium oxide nanocomposite derived from carbonized metal organic framework: A coating for solid-phase microextraction.

    Science.gov (United States)

    Saraji, Mohammad; Mehrafza, Narges

    2016-08-19

    In this paper, a mesoporous carbon-ZrO2 nanocomposite was fabricated on a stainless steel wire for the first time and used as the solid-phase microextraction coating. The fiber was synthesized with the direct carbonization of a Zr-based metal organic framework. With the utilization of the metal organic framework as the precursor, no additional carbon source was used for the synthesis of the mesoporous carbon-ZrO2 nanocomposite coating. The fiber was applied for the determination of BTEX compounds (benzene, toluene, ethylbenzene and m, p-xylenes) in different water samples prior to gas chromatography-flame ionization detection. Such important experimental factors as synthesis time and temperature, salt concentration, equilibrium and extraction time, extraction temperature, desorption time and desorption temperature were studied and optimized. Good linearity in the concentration range of 0.2-200μgL(-1) and detection limits in the range of 0.05-0.56μgL(-1) was achieved for BTEX compounds. The intra- and inter-day relative standard deviations were in the range of 3.5-4.8% and 4.9-6.7%, respectively. The prepared fiber showed high capability for the analysis of BTEX compounds in different water and wastewater samples with good relative recoveries in the range of 93-107%. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Selective fluorescence sensors for detection of nitroaniline and metal Ions based on ligand-based luminescent metal-organic frameworks

    International Nuclear Information System (INIS)

    Yu, Zongchao; Wang, Fengqin; Lin, Xiangyi; Wang, Chengmiao; Fu, Yiyuan; Wang, Xiaojun; Zhao, Yongnan; Li, Guodong

    2015-01-01

    Metal-organic frameworks (MOFs) are porous crystalline materials with high potential for applications in fluorescence sensors. In this work, two solvent-induced Zn(II)–based metal-organic frameworks, Zn_3L_3(DMF)_2 (1) and Zn_3L_3(DMA)_2(H_2O)_3 (2) (L=4,4′-stilbenedicarboxylic acid), were investigated as selective sensing materials for detection of nitroaromatic compounds and metal ions. The sensing experiments show that 1 and 2 both exhibit selective fluorescence quenching toward nitroaniline with a low detection limit. In addition, 1 exhibits high selectivity for detection of Fe"3"+ and Al"3"+ by significant fluorescence quenching or enhancement effect. While for 2, it only exhibits significant fluorescence quenching effect for Fe"3"+. The results indicate that 1 and 2 are both promising fluorescence sensors for detecting and recognizing nitroaniline and metal ions with high sensitivity and selectivity. - Graphical abstract: Two MOFs have been selected as the fluorescence sensing materials for selectively sensing mitroaromatic compounds and metal ions. The high selectivity makes them promising fluorescence sensors for detecting and recognizing nitroaniline and Fe"3"+ or Al"3"+.

  20. Low concentration CO2 capture using physical adsorbents: Are Metal-Organic Frameworks becoming the new benchmark materials?

    KAUST Repository

    Belmabkhout, Youssef

    2016-03-30

    The capture and separation of traces and concentrated CO2 from important commodities such as CH4, H2, O2 and N2, is becoming important in many areas related to energy security and environmental sustainability. While trace CO2 concentration removal applications have been modestly studied for decades, the spike in interest in the capture of concentrated CO2 was motivated by the need for new energy vectors to replace highly concentrated carbon fuels and the necessity to reduce emissions from fossil fuel-fired power plants. CO2 capture from various gas streams, at different concentrations, using physical adsorbents, such as activated carbon, zeolites, and metal-organic frameworks (MOFs), is attractive. However, the adsorbents must be designed with consideration of many parameters including CO2 affinity, kinetics, energetics, stability, capture mechanism, in addition to cost. Here, we perform a systematic analysis regarding the key technical parameters that are required for the best CO2 capture performance using physical adsorbents. We also experimentally demonstrate a suitable material model of Metal Organic Framework as advanced adsorbents with unprecedented properties for CO2 capture in a wide range of CO2 concentration. These recently developed class of MOF adsorbents represent a breakthrough finding in the removal of traces CO2 using physical adsorption. This platform shows colossal tuning potential for more efficient separation agents.

  1. Low concentration CO2 capture using physical adsorbents: Are Metal-Organic Frameworks becoming the new benchmark materials?

    KAUST Repository

    Belmabkhout, Youssef; Guillerm, Vincent; Eddaoudi, Mohamed

    2016-01-01

    The capture and separation of traces and concentrated CO2 from important commodities such as CH4, H2, O2 and N2, is becoming important in many areas related to energy security and environmental sustainability. While trace CO2 concentration removal applications have been modestly studied for decades, the spike in interest in the capture of concentrated CO2 was motivated by the need for new energy vectors to replace highly concentrated carbon fuels and the necessity to reduce emissions from fossil fuel-fired power plants. CO2 capture from various gas streams, at different concentrations, using physical adsorbents, such as activated carbon, zeolites, and metal-organic frameworks (MOFs), is attractive. However, the adsorbents must be designed with consideration of many parameters including CO2 affinity, kinetics, energetics, stability, capture mechanism, in addition to cost. Here, we perform a systematic analysis regarding the key technical parameters that are required for the best CO2 capture performance using physical adsorbents. We also experimentally demonstrate a suitable material model of Metal Organic Framework as advanced adsorbents with unprecedented properties for CO2 capture in a wide range of CO2 concentration. These recently developed class of MOF adsorbents represent a breakthrough finding in the removal of traces CO2 using physical adsorption. This platform shows colossal tuning potential for more efficient separation agents.

  2. Hydrogen storage studies on palladium-doped carbon materials (AC, CB, CNMs) @ metal-organic framework-5.

    Science.gov (United States)

    Viditha, V; Srilatha, K; Himabindu, V

    2016-05-01

    Metal organic frameworks (MOFs) are a rapidly growing class of porous materials and are considered as best adsorbents for their high surface area and extraordinary porosity. The MOFs are synthesized by using various chemicals like triethylamine, terepthalic acid, zinc acetate dihydrate, chloroform, and dimethylformamide (DMF). Synthesized MOFs are intercalated with palladium/activated carbon, carbon black, and carbon nanomaterials by chemical reduction method for the purpose of enhancing the hydrogen adsorption capacities. We have observed that the palladium doped activated carbon on MOF-5 showed high hydrogen storage capacity. This may be due to the affinity of the palladium toward hydrogen molecule. The samples are characterized by X-ray diffraction, scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis. We have observed a clear decrease in the BET surface area and pore volume. The obtained results show a better performance for the synthesized sample. To our best knowledge, no one has reported the work on palladium-doped carbon materials (activated carbon, carbon black, carbon nanomaterials) impregnated to the metal-organic framework-5. We have attempted to synthesize carbon nanomaterials using indigenously fabricated chemical vapor deposition (CVD) unit as a support. We have observed an increase in the hydrogen storage capacities.

  3. Toxic effect of zinc nanoscale metal-organic frameworks on rat pheochromocytoma (PC12) cells in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Fei, E-mail: paper_mail@126.com [Department of Pharmacy, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Yang, Baochun; Cai, Jing [Department of Pharmacy, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Jiang, Yaodong [Department of Urology, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Xu, Jun [Department of Health Economy Administration, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Wang, Shan [Department of Pharmacy, Winthrop University Hospital, Mineola, NY 11501 (United States)

    2014-04-01

    Highlights: • Metal-organic frameworks (MOFs) represent a newborn family of hybrid materials. • MOFs have already shown promise in a number of biological applications. • The biological applications of MOFs raise concerns for potential cytotoxicity. • Substantial information about MOF's neurotoxicity is still quite scarce. • This study reveals for the first time the interaction of MOFs with neural cells. - Abstract: Metal-organic frameworks (MOFs) possess unique properties desirable for delivery of drugs and gaseous therapeutics, but their uncharacterized interactions with cells raise increasing concerns of their safety in such biomedical applications. We evaluated the adverse effects of zinc nanoscale MOFs on the cell morphology, cytoskeleton, cell viability and expression of neurotrophin signaling pathway-associated GAP-43 protein in rat pheochromocytoma PC12 cells. At the concentration of 25 μg/ml, zinc MOFs did not significantly affect morphology, viability and membrane integrity of the cells. But at higher concentrations (over 100 μg/ml), MOFs exhibited a time- and concentration-dependent cytotoxicity, indicating their entry into the cells via endocytosis where they release Zn{sup 2+} into the cytosol to cause increased intracellular concentration of Zn{sup 2+}. We demonstrated that the toxicity of MOFs was associated with a disrupted cellular zinc homeostasis and down-regulation of GAP-43 protein, which might be the underlying mechanism for the improved differentiation in PC12 cells. These findings highlight the importance of cytotoxic evaluation of the MOFs before their biomedical application.

  4. Toxic effect of zinc nanoscale metal-organic frameworks on rat pheochromocytoma (PC12) cells in vitro

    International Nuclear Information System (INIS)

    Ren, Fei; Yang, Baochun; Cai, Jing; Jiang, Yaodong; Xu, Jun; Wang, Shan

    2014-01-01

    Highlights: • Metal-organic frameworks (MOFs) represent a newborn family of hybrid materials. • MOFs have already shown promise in a number of biological applications. • The biological applications of MOFs raise concerns for potential cytotoxicity. • Substantial information about MOF's neurotoxicity is still quite scarce. • This study reveals for the first time the interaction of MOFs with neural cells. - Abstract: Metal-organic frameworks (MOFs) possess unique properties desirable for delivery of drugs and gaseous therapeutics, but their uncharacterized interactions with cells raise increasing concerns of their safety in such biomedical applications. We evaluated the adverse effects of zinc nanoscale MOFs on the cell morphology, cytoskeleton, cell viability and expression of neurotrophin signaling pathway-associated GAP-43 protein in rat pheochromocytoma PC12 cells. At the concentration of 25 μg/ml, zinc MOFs did not significantly affect morphology, viability and membrane integrity of the cells. But at higher concentrations (over 100 μg/ml), MOFs exhibited a time- and concentration-dependent cytotoxicity, indicating their entry into the cells via endocytosis where they release Zn 2+ into the cytosol to cause increased intracellular concentration of Zn 2+ . We demonstrated that the toxicity of MOFs was associated with a disrupted cellular zinc homeostasis and down-regulation of GAP-43 protein, which might be the underlying mechanism for the improved differentiation in PC12 cells. These findings highlight the importance of cytotoxic evaluation of the MOFs before their biomedical application

  5. Hemin immobilized into metal-organic frameworks as an electrochemical biosensor for 2,4,6-trichlorophenol

    Science.gov (United States)

    Zhang, Ting; Wang, Lu; Gao, Congwei; Zhao, Chaoyue; Wang, Yang; Wang, Jianmin

    2018-02-01

    Hemin immobilized into copper-based metal-organic frameworks was successfully prepared and used as a new electrode material for sensitive electrochemical biosensing. X-ray diffraction patterns, Fourier transform infrared spectra, scanning electron microscopy, UV-vis absorption spectroscopy, and cyclic voltammetry were used to characterize the resultant composites. Due to the interaction between the copper atom groups and hemin, the constrained environment in Cu-MOF-74 acts as a matrix to avoid the dimerization of enzyme molecules and retain its biological activity. The hemin/Cu-MOF composites demonstrated enhanced electrocatalytical activity and high stability towards the oxidation of 2,4,6-trichlorophenol. Under optimum experimental conditions, the sensor showed a wide linear relationship over the range of 0.01-9 μmol L-1 with a detection limit (3σ) of 0.005 μmol L-1. The relative standard deviations were 4.6% and 3.5% for five repeated measurements of 0.5 and 5 μmol L-1 2,4,6-trichlorophenol, respectively. The detection platforms for 2,4,6-trichlorophenol developed here not only indicate that hemin/Cu-MOF-74 possesses intrinsic biological reactivity, but also enable further work to be conducted towards the application of enzyme-containing metal-organic frameworks in electrochemical biosensors.

  6. CO2 Capture Using the SIFSIX-2-Cu-i Metal-Organic Framework: A Computational Approach

    KAUST Repository

    Skarmoutsos, Ioannis

    2017-10-24

    The adsorption of carbon dioxide and its separation from mixtures with methane using the recently synthetized SIFSIX-2-Cu-i metal-organic framework (Nature, 2014, 495, 80-84) has been systematically studied by employing a variety of molecular simulation techniques. Quantum density functional theory calculations have been combined with force-field based Monte Carlo and molecular dynamics simulations in order to provide a deeper insight on the molecular-scale processes controlling the thermodynamic and dynamic adsorption selectivity of carbon dioxide over methane, giving particular emphasis on the mechanisms underlying the diffusion of the confined molecules in this porous hybrid material. The diffusion process was revealed to be mainly controlled by both (i) the residence dynamics around some specific interaction sites of the fluorinated metal-organic framework and (ii) the dynamics related to the process where faster molecules overtake slower ones in the narrow one-dimensional channel of SIFSIX-2-Cu-i. We further unveil a 1-dimensional diffusion behavior of both carbon dioxide and methane confined in this small pore MOF where single file diffusion is not observed.

  7. Synthesis of Hierarchically Structured Hybrid Materials by Controlled Self-Assembly of Metal-Organic Framework with Mesoporous Silica for CO2 Adsorption.

    Science.gov (United States)

    Chen, Chong; Li, Bingxue; Zhou, Lijin; Xia, Zefeng; Feng, Nengjie; Ding, Jing; Wang, Lei; Wan, Hui; Guan, Guofeng

    2017-07-12

    The HKUST-1@SBA-15 composites with hierarchical pore structure were constructed by in situ self-assembly of metal-organic framework (MOF) with mesoporous silica. The structure directing role of SBA-15 had an obvious impact on the growth of MOF crystals, which in turn affected the morphologies and structural properties of the composites. The pristine HKUST-1 and the composites with different content of SBA-15 were characterized by XRD, N 2 adsorption-desorption, SEM, TEM, FT-IR, TG, XPS, and CO 2 -TPD techniques. It was found that the composites were assembled by oriented growth of MOF nanocrystals on the surfaces of SBA-15 matrix. The interactions between surface silanol groups and metal centers induced structural changes and resulted in the increases in surface areas as well as micropore volumes of hybrid materials. Besides, the additional constraints from SBA-15 also restrained the expansion of HKUST-1, contributing to their smaller crystal sizes in the composites. The adsorption isotherms of CO 2 on the materials were measured and applied to calculate the isosteric heats of adsorption. The HS-1 composite exhibited an increase of 15.9% in CO 2 uptake capacity compared with that of HKUST-1. Moreover, its higher isosteric heats of CO 2 adsorption indicated the stronger interactions between the surfaces and CO 2 molecules. The adsorption rate of the composite was also improved due to the introduction of mesopores. Ten cycles of CO 2 adsorption-desorption experiments implied that the HS-1 had excellent reversibility of CO 2 adsorption. This study was intended to provide the possibility of assembling new composites with tailored properties based on MOF and mesoporous silica to satisfy the requirements of various applications.

  8. Two zeolite-type frameworks in one metal-organic framework with Zn24 @Zn104 cube-in-sodalite architecture.

    Science.gov (United States)

    Bu, Fei; Lin, Qipu; Zhai, Quanguo; Wang, Le; Wu, Tao; Zheng, Shou-Tian; Bu, Xianhui; Feng, Pingyun

    2012-08-20

    Two in one: A metal-organic framework obtained from three different inorganic building blocks (tetrameric Zn(4) O, trimeric Zn(3) OH, and monomeric Zn) posseses a nested cage-in-cage and framework-in-framework architecture. 24 Zn(4) O tetramers and eight Zn monomers form a sodalite cage into which a cubic cage made from eight Zn(3) (OH) trimers is nestled. Eight monomeric Zn(2+) centers interconnect these two cages. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. A metal-organic framework based on nanosized hexagonal channels as fluorescent indicator for detection of nitroaromatic explosives

    Science.gov (United States)

    Hu, Xiao-Li; Wang, Xin-Long; Su, Zhong-Min

    2018-02-01

    A novel Zn-MOF (metal organic framework) [Zn3(NTB)2(DMA)2]·12DMA (NTB = 4,4‧,4″-nitrilotrisbenzoic acid; DMA = N,N-dimethylacetamide) (1) was obtained under solvothermal condition. The resulted MOF which is based on {Zn3} SBU displays an interesting (3,6)-connected three-dimensional net with nanosized, hexagonal channels. Additionally, 1 can be a useful fluorescent indicator for the detection of nitroaromatic explosives qualitatively and quantitatively via a strong quenching effect, especially for picric acid (PA). With increasing - NO2 groups, energy transfer from the electron-donating framework to high electron deficiency becomes more, making the effect of fluorescence quenching more obvious. The result demonstrates that the photo-induced electron transfer (PET) is responsible for the emission quenching.

  10. Introduction of Molecular Building Blocks to Improve the Stability of Metal-Organic Frameworks for Efficient Mercury Removal.

    Science.gov (United States)

    Jiang, Shu-Yi; He, Wen-Wen; Li, Shun-Li; Su, Zhong-Min; Lan, Ya-Qian

    2018-05-08

    With expanding human needs, many heavy metals were mined, smelted, processed, and manufactured for commercialization, which caused serious environmental pollutions. Currently, many adsorption materials are applied in the field of adsorption of heavy metals. Among them, the principle of many mercury adsorbents is based on the interaction between mercury and sulfur. Here, a S-containing metal-organic framework NENU-400 was synthesized for effective mercury extraction. Unfortunately, the skeleton of NENU-400 collapsed easily when exposed to the mercury liquid solution. To improve the stability, a synthetic strategy installing molecular building blocks (MBBs) into the channels was used. Modified by the MBBs, a more stable nanoporous framework was synthesized, which not only exhibits a high capacity of saturation mercury uptake but also shows high selectivity and efficient recyclability.

  11. Achieving Amphibious Superprotonic Conductivity in a CuI Metal-Organic Framework by Strategic Pyrazinium Salt Impregnation.

    Science.gov (United States)

    Khatua, Sajal; Bar, Arun Kumar; Sheikh, Javeed Ahmad; Clearfield, Abraham; Konar, Sanjit

    2018-01-19

    Treatment of a pyrazine (pz)-impregnated Cu I metal-organic framework (MOF) ([1⊃pz]) with HCl vapor renders an interstitial pyrazinium chloride salt-hybridized MOF ([1⊃pz⋅6 HCl]) that exhibits proton conductivity over 10 -2  S cm -1 both in anhydrous and under humid conditions. Framework [1⊃pz⋅6 HCl] features the highest anhydrous proton conductivity among the lesser-known examples of MOF-based materials exhibiting proton conductivity under both anhydrous and humid conditions. Moreover, [1⊃pz] and corresponding pyrazinium sulfate- and pyrazinium phosphate-hybridized MOFs also exhibit superprotonic conductivity over 10 -2  S cm -1 under humid conditions. The impregnated pyrazinium ions play a crucial role in protonic conductivity, which occurs through a Grotthuss mechanism. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A malonitrile-functionalized metal-organic framework for hydrogen sulfide detection and selective amino acid molecular recognition

    Science.gov (United States)

    Li, Haiwei; Feng, Xiao; Guo, Yuexin; Chen, Didi; Li, Rui; Ren, Xiaoqian; Jiang, Xin; Dong, Yuping; Wang, Bo

    2014-03-01

    A novel porous polymeric fluorescence probe, MN-ZIF-90, has been designed and synthesized for quantitative hydrogen sulfide (H2S) fluorescent detection and highly selective amino acid recognition. This distinct crystalline structure, derived from rational design and malonitrile functionalization, can trigger significant enhancement of its fluorescent intensity when exposed to H2S or cysteine molecules. Indeed this new metal-organic framework (MOF) structure shows high selectivity of biothiols over other amino acids and exhibits favorable stability. Moreover, in vitro viability assays on HeLa cells show low cytotoxicity of MN-ZIF-90 and its imaging contrast efficiency is further demonstrated by fluorescence microscopy studies. This facile yet powerful strategy also offers great potential of using open-framework materials (i.e. MOFs) as the novel platform for sensing and other biological applications.

  13. Supramolecular Isomers of Metal-Organic Frameworks Derived from a Partially Flexible Ligand with Distinct Binding Motifs

    KAUST Repository

    Abdul Halim, Racha Ghassan

    2016-01-04

    Three novel metal-organic frameworks (MOFs) were isolated upon reacting a heterofunctional ligand 4 (pyrimidin-5 yl)benzoic acid (4,5-pmbc) with mixed valence Cu(I,II) under solvothermal conditions. X-ray crystal structural analysis reveals that the first compound is a layered structure composed of one type of inorganic building block, dinuclear paddlewheel [Cu2(O2C–)4], which are linked through 4,5-pmbc ligands. The two other supramolecular isomers are composed of the same Cu(II) dinuclear paddlewheel and a dinuclear Cu2I2 cluster, which are linked via the 4,5-pmbc linkers to yield two different 3-periodic frameworks with underlying topologies related to lvt and nbo. The observed structural diversity in these structures is due to the distinct coordination modes of the two coordinating moieties (the carboxylate group on the phenyl ring and the N-donor atoms from the pyrimidine moiety).

  14. Supramolecular Isomers of Metal-Organic Frameworks Derived from a Partially Flexible Ligand with Distinct Binding Motifs

    KAUST Repository

    AbdulHalim, Rasha; Shkurenko, Aleksander; Al Kordi, Mohamed; Eddaoudi, Mohamed

    2016-01-01

    Three novel metal-organic frameworks (MOFs) were isolated upon reacting a heterofunctional ligand 4 (pyrimidin-5 yl)benzoic acid (4,5-pmbc) with mixed valence Cu(I,II) under solvothermal conditions. X-ray crystal structural analysis reveals that the first compound is a layered structure composed of one type of inorganic building block, dinuclear paddlewheel [Cu2(O2C–)4], which are linked through 4,5-pmbc ligands. The two other supramolecular isomers are composed of the same Cu(II) dinuclear paddlewheel and a dinuclear Cu2I2 cluster, which are linked via the 4,5-pmbc linkers to yield two different 3-periodic frameworks with underlying topologies related to lvt and nbo. The observed structural diversity in these structures is due to the distinct coordination modes of the two coordinating moieties (the carboxylate group on the phenyl ring and the N-donor atoms from the pyrimidine moiety).

  15. Nanometric MIL-125-NH₂ Metal-Organic Framework as a Potential Nerve Agent Antidote Carrier.

    Science.gov (United States)

    Vilela, Sérgio M F; Salcedo-Abraira, Pablo; Colinet, Isabelle; Salles, Fabrice; de Koning, Martijn C; Joosen, Marloes J A; Serre, Christian; Horcajada, Patricia

    2017-10-12

    The three-dimensional (3D) microporous titanium aminoterephthalate MIL-125-NH₂ (MIL: Material of Institut Lavoisier) was successfully isolated as monodispersed nanoparticles, which are compatible with intravenous administration, by using a simple, safe and low-cost synthetic approach (100 °C/32 h under atmospheric pressure) so that for the first time it could be considered for encapsulation and the release of drugs. The nerve agent antidote 2-[(hydroxyimino)methyl]-1-methyl-pyridinium chloride (2-PAM or pralidoxime) was effectively encapsulated into the pores of MIL-125-NH₂ as a result of the interactions between 2-PAM and the pore walls being mediated by π-stacking and hydrogen bonds, as deduced from infrared spectroscopy and Monte Carlo simulation studies. Finally, colloidal solutions of MIL-125-NH₂ nanoparticles exhibited remarkable stability in different organic media, aqueous solutions at different pH and under relevant physiological conditions over time (24 h). 2-PAM was rapidly released from the pores of MIL-125-NH₂ in vitro.

  16. Superior capture of CO2 achieved by introducing extra-framework cations into N-doped microporous carbon

    KAUST Repository

    Zhao, Yunfeng; Liu, Xin; Yao, Kexin; Zhao, Lan; Han, Yu

    2012-01-01

    We designed and prepared a novel microporous carbon material (KNC-A-K) for selective CO2 capture. The combination of a high N-doping concentration (>10 wt %) and extra-framework cations, which were introduced into carbonaceous sorbents

  17. A novel cryogenic magnetic refrigerant metal-organic framework based on 1D gadolinium(III) chain

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Qun; Li, Peng-Fei [Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin, Guangxi 541004 (China); Zou, Zhi-Ming, E-mail: 2014005@glut.edu.cn [Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin, Guangxi 541004 (China); Liu, Zheng [Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin, Guangxi 541004 (China); Liu, Shu-Xia, E-mail: liusx@nenu.edu.cn [Key Laboratory of Polyoxometalate Science of Ministry of Education, College of Chemistry, Northeast Normal University, Changchun, Jilin 130024 (China)

    2017-02-15

    A metal-organic framework (MOF) based on gadolinium ion (Gd{sup 3+}) and tricarboxylate ligand, [Gd(BTPCA)(H{sub 2}O)]·2DMF·3H{sub 2}O (Gd-BTPCA) (H{sub 3}BTPCA =1,1′,1′-(benzene-1,3,5-triyl)tripiperidine-4-carboxylic acid; DMF=dimethylformamide), was synthesized and structurally characterized. The adjacent Gd{sup 3+} ions are intraconnected by the carboxylate groups of the BTPCA{sup 3-} ligands to form a 1D Gd{sup 3+} ion chain. The 1D Gd{sup 3+} ion chains are interconnected by the BTPCA{sup 3-} ligands, giving rise to a 3D framework with 1D open channel. The magnetic studies indicate that Gd-BTPCA exhibits weak ferromagnetic interactions, and acts as a cryogenic magnetic refrigerant having the magnetic entropy change (−ΔS{sub m}) of 20.40 J kg{sup −1} K{sup −1} for ΔH =7 T at 3 K. - Graphical abstract: A 1D gadolinium(III) chains-based metal-organic framework performed ferromagnetic coupling on the magnetic property. Magnetic investigation reveals that Gd-BTPCA exhibits the entropy change (−ΔS{sub m}) of 20.40 J kg{sup −1} K{sup −1} for ΔH =7 T at 3 K. - Highlights: • The MOF based on gadolinium ion and tricarboxylate ligand was synthesized. • This MOF is connected with 1D Gd{sup 3+} ions chain and the carboxylate groups of BTPCA{sup 3-} ligands. • The magnetic studies indicate that the MOF exhibits the weak ferromagnetic interactions. • Magnetic investigation reveals that the MOF exhibits the high entropy change.

  18. Conversion of invisible metal-organic frameworks to luminescent perovskite nanocrystals for confidential information encryption and decryption.

    Science.gov (United States)

    Zhang, Congyang; Wang, Bo; Li, Wanbin; Huang, Shouqiang; Kong, Long; Li, Zhichun; Li, Liang

    2017-10-31

    Traditional smart fluorescent materials, which have been attracting increasing interest for security protection, are usually visible under either ambient or UV light, making them adverse to the potential application of confidential information protection. Herein, we report an approach to realize confidential information protection and storage based on the conversion of lead-based metal-organic frameworks (MOFs) to luminescent perovskite nanocrystals (NCs). Owing to the invisible and controlled printable characteristics of lead-based MOFs, confidential information can be recorded and encrypted by MOF patterns, which cannot be read through common decryption methods. Through our conversion strategy, highly luminescent perovskite NCs can be formed quickly and simply by using a halide salt trigger that reacts with the MOF, thus promoting effective information decryption. Finally, through polar solvents impregnation and halide salt conversion, the luminescence of the perovskite NCs can be quenched and recovered, leading to reversible on/off switching of the luminescence signal for multiple information encryption and decryption processes.

  19. 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.

  20. Highly Sensitive and Selective Sensing of Free Bilirubin Using Metal-Organic Frameworks-Based Energy Transfer Process.

    Science.gov (United States)

    Du, Yaran; Li, Xiqian; Lv, Xueju; Jia, Qiong

    2017-09-13

    Free bilirubin, a key biomarker for jaundice, was detected with a newly designed fluorescent postsynthetically modified metal organic framework (MOF) (UIO-66-PSM) sensor. UiO-66-PSM was prepared based on the aldimine condensation reaction of UiO-66-NH 2 with 2,3,4-trihydroxybenzaldehyde. The fluorescence of UIO-66-PSM could be effectively quenched by free bilirubin via a fluorescent resonant energy transfer process, thus achieving its recognition of free bilirubin. It was the first attempt to design a MOF-based fluorescent probe for sensing free bilirubin. The probe exhibited fast response time, low detection limit, wide linear range, and high selectivity toward free bilirubin. The sensing system enabled the monitor of free bilirubin in real human serum. Hence, the reported free bilirubin sensing platform has potential applications for clinical diagnosis of jaundice.

  1. Experimental and theoretical investigations of the electronic band structure of metal-organic frameworks of HKUST-1 type

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Zhi-Gang [Institut für Funktionelle Grenzflächen (IFG), Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fuzhou (China); Heinke, Lars, E-mail: Lars.Heinke@KIT.edu; Wöll, Christof [Institut für Funktionelle Grenzflächen (IFG), Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Neumann, Tobias; Wenzel, Wolfgang; Li, Qiang; Fink, Karin [Institute of Nanotechnology (INT), Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Gordan, Ovidiu D.; Zahn, Dietrich R. T. [Semiconductor Physics, Technische Universität Chemnitz, 09107 Chemnitz (Germany)

    2015-11-02

    The electronic properties of metal-organic frameworks (MOFs) are increasingly attracting the attention due to potential applications in sensor techniques and (micro-) electronic engineering, for instance, as low-k-dielectric in semiconductor technology. Here, the band gap and the band structure of MOFs of type HKUST-1 are studied in detail by means of spectroscopic ellipsometry applied to thin surface-mounted MOF films and by means of quantum chemical calculations. The analysis of the density of states, the band structure, and the excitation spectrum reveal the importance of the empty Cu-3d orbitals for the electronic properties of HKUST-1. This study shows that, in contrast to common belief, even in the case of this fairly “simple” MOF, the excitation spectra cannot be explained by a superposition of “intra-unit” excitations within the individual building blocks. Instead, “inter-unit” excitations also have to be considered.

  2. Vapor-Phase Deposition and Modification of Metal-Organic Frameworks: State-of-the-Art and Future Directions.

    Science.gov (United States)

    Stassen, Ivo; De Vos, Dirk; Ameloot, Rob

    2016-10-04

    Materials processing, and thin-film deposition in particular, is decisive in the implementation of functional materials in industry and real-world applications. Vapor processing of materials plays a central role in manufacturing, especially in electronics. Metal-organic frameworks (MOFs) are a class of nanoporous crystalline materials on the brink of breakthrough in many application areas. Vapor deposition of MOF thin films will facilitate their implementation in micro- and nanofabrication research and industries. In addition, vapor-solid modification can be used for postsynthetic tailoring of MOF properties. In this context, we review the recent progress in vapor processing of MOFs, summarize the underpinning chemistry and principles, and highlight promising directions for future research. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Remarkably enhanced gas separation by partial self-conversion of a laminated membrane to metal-organic frameworks.

    Science.gov (United States)

    Liu, Yi; Pan, Jia Hong; Wang, Nanyi; Steinbach, Frank; Liu, Xinlei; Caro, Jürgen

    2015-03-02

    Separation methods based on 2D interlayer galleries are currently gaining widespread attention. The potential of such galleries as high-performance gas-separation membranes is however still rarely explored. Besides, it is well recognized that gas permeance and separation factor are often inversely correlated in membrane-based gas separation. Therefore, breaking this trade-off becomes highly desirable. Here, the gas-separation performance of a 2D laminated membrane was improved by its partial self-conversion to metal-organic frameworks. A ZIF-8-ZnAl-NO3 layered double hydroxide (LDH) composite membrane was thus successfully prepared in one step by partial conversion of the ZnAl-NO3 LDH membrane, ultimately leading to a remarkably enhanced H2 /CH4 separation factor and H2 permeance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 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.

  5. Conformational locking by design: relating strain energy with luminescence and stability in rigid metal-organic frameworks.

    Science.gov (United States)

    Shustova, Natalia B; Cozzolino, Anthony F; Dincă, Mircea

    2012-12-05

    Minimization of the torsional barrier for phenyl ring flipping in a metal-organic framework (MOF) based on the new ethynyl-extended octacarboxylate ligand H(8)TDPEPE leads to a fluorescent material with a near-dark state. Immobilization of the ligand in the rigid structure also unexpectedly causes significant strain. We used DFT calculations to estimate the ligand strain energies in our and all other topologically related materials and correlated these with empirical structural descriptors to derive general rules for trapping molecules in high-energy conformations within MOFs. These studies portend possible applications of MOFs for studying fundamental concepts related to conformational locking and its effects on molecular reactivity and chromophore photophysics.

  6. Enhancing the biofuel upgrade performance for Pd nanoparticles via increasing the support hydrophilicity of metal-organic frameworks.

    Science.gov (United States)

    Sun, Qi; Chen, Meng; Aguila, Briana; Nguyen, Nicholas; Ma, Shengqian

    2017-09-08

    In this work, the influence of the hydrophilic/hydrophobic nature of metal-organic framework (MOF) materials on the catalytic performance of supported Pd nanoparticles for biofuel upgrade was studied. We show that the introduction of hydrophilic groups on a MOF can greatly enhance the performance of the resultant catalyst. Specifically, Pd nanoparticles supported on MIL-101-SO 3 Na with superhydrophilicity (Pd/MIL-101-SO 3 Na) far outperforms pristine MIL-101 and the benchmark catalyst Pd/C in the hydrodeoxygenation reaction of vanillin, a model component of pyrolysis oil derived from the lignin fraction. This is attributed to a favorable mode of adsorption of the highly water soluble reactants on the more hydrophilic support in the vicinity of the catalytically active Pd nanoparticles, thereby promoting their transformation.

  7. Dual-Emitting UiO-66(Zr&Eu) Metal-Organic Framework Films for Ratiometric Temperature Sensing.

    Science.gov (United States)

    Feng, Ji-Fei; Liu, Tian-Fu; Shi, Jianlin; Gao, Shui-Ying; Cao, Rong

    2018-06-20

    A novel dual-emitting metal-organic framework based on Zr and Eu, named as UiO-66(Zr&Eu), was built using a clever strategy based on secondary building units. With the use of polymers, the obtained UiO-66(Zr&Eu) was subsequently deposited as thin films that can be utilized as smart thermometers. The UiO-66(Zr&Eu) polymer films can be used for the detection of temperature changes in the range of 237-337 K due to the energy transfer between the lanthanide ions (Eu in clusters) and the luminescent ligands, and the relative sensitivity reaches 4.26% K -1 at 337 K. Moreover, the sensitivity can be improved to 19.67% K -1 by changing the film thickness. In addition, the temperature-sensing performance of the films is superior to that of the powders, and the sensor can be reused 3 times without loss of performance.

  8. Probing adsorption sites of carbon dioxide in metal organic framework of [Zn(bdc)(dpds)]n: A molecular simulation study

    Science.gov (United States)

    Lu, Shih-I.; Liao, Jian-Min; Huang, Xiao-Zhuang; Lin, Chia-Hsun; Ke, Szu-Yu; Wang, Chih-Chieh

    2017-11-01

    We used force-field based grand-canonical Monte Carlo simulation method and density functional theory to study adsorption characteristics of carbon dioxide (CO2) molecules in a metal-organic framework (MOF) compound, [Zn(bdc)(dpds)]n. The studied MOF include a metal ion (Zn(II)), an anion organic linker (dianion of benzene dicarboxylicacid, bdc2-) and a neutral organic linker (4,4‧-dipyridyldisulfide, dpds). Results from calculated adsorption isotherms and enthalpies of adsorption agree with the experimental data. The interactions between the adsorbed CO2 and the organic linkers were examined in simulations. Calculated results show available absorption sites are surrounded by two dpds ligands in which an S-S bond as an N-N‧ spacer connect two pyridines. In contrast, the bdc2- ligand does not give a significant contribution to the substantial adsorption amount even though it contains the carboxylate group that provides available bonding site to CO2.

  9. 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.

  10. Ionic Exchange of Metal-Organic Frameworks to Access Single Nickel Sites for Efficient Electroreduction of CO2.

    Science.gov (United States)

    Zhao, Changming; Dai, Xinyao; Yao, Tao; Chen, Wenxing; Wang, Xiaoqian; Wang, Jing; Yang, Jian; Wei, Shiqiang; Wu, Yuen; Li, Yadong

    2017-06-21

    Single-atom catalysts often exhibit unexpected catalytic activity for many important chemical reactions because of their unique electronic and geometric structures with respect to their bulk counterparts. Herein we adopt metal-organic frameworks (MOFs) to assist the preparation of a catalyst containing single Ni sites for efficient electroreduction of CO 2 . The synthesis is based on ionic exchange between Zn nodes and adsorbed Ni ions within the cavities of the MOF. This single-atom catalyst exhibited an excellent turnover frequency for electroreduction of CO 2 (5273 h -1 ), with a Faradaic efficiency for CO production of over 71.9% and a current density of 10.48 mA cm -2 at an overpotential of 0.89 V. Our findings present some guidelines for the rational design and accurate modulation of nanostructured catalysts at the atomic scale.

  11. Dual Role of Water in Heterogeneous Catalytic Hydrolysis of Sarin by Zirconium-Based Metal-Organic Frameworks.

    Science.gov (United States)

    Momeni, Mohammad R; Cramer, Christopher J

    2018-05-22

    Recent experimental studies on Zr IV -based metal-organic frameworks (MOFs) have shown the extraordinary effectiveness of these porous materials for the detoxification of phosphorus-based chemical warfare agents (CWAs). However, pressing challenges remain with respect to characterizing these catalytic processes both at the molecular and crystalline levels. We here use theory to compare the reactivity of different zirconium-based MOFs for the catalytic hydrolysis of the CWA sarin, using both periodic and cluster modeling. We consider both hydrated and dehydrated secondary building units, as well as linker functionalized MOFs, to more fully understand and rationalize available experimental findings as well as to enable concrete predictions for achieving higher activities for the decomposition of CWAs.

  12. Metal-Organic Framework Derived Iron Sulfide-Carbon Core-Shell Nanorods as a Conversion-Type Battery Material

    DEFF Research Database (Denmark)

    Huang, Wei; Li, Shuo; Cao, Xianyi

    2017-01-01

    of a redox conversion-type lithium-ion battery, this composite material has demonstrated high lithium-ion storage capacity at 1148 mA h g-1 under the current rate of 500 mA g-1 for 170 cycles and an impressive rate-retention capability at 657 mA h g-1 with a current density of 2000 mA g-1. On the basis......We report the design and nanoengineering of carbon-film-coated iron sulfide nanorods (C@Fe7S8) as an advanced conversion-type lithium-ion storage material. The structural advantages of the iron-based metal-organic framework (MIL-88-Fe) as both a sacrificed template and a precursor are explored...

  13. Screening of metal-organic frameworks for carbon dioxide capture from flue gas using a combined experimental and modeling approach.

    Science.gov (United States)

    Yazaydin, A Ozgür; Snurr, Randall Q; Park, Tae-Hong; Koh, Kyoungmoo; Liu, Jian; Levan, M Douglas; Benin, Annabelle I; Jakubczak, Paulina; Lanuza, Mary; Galloway, Douglas B; Low, John J; Willis, Richard R

    2009-12-30

    A diverse collection of 14 metal-organic frameworks (MOFs) was screened for CO(2) capture from flue gas using a combined experimental and modeling approach. Adsorption measurements are reported for the screened MOFs at room temperature up to 1 bar. These data are used to validate a generalized strategy for molecular modeling of CO(2) and other small molecules in MOFs. MOFs possessing a high density of open metal sites are found to adsorb significant amounts of CO(2) even at low pressure. An excellent correlation is found between the heat of adsorption and the amount of CO(2) adsorbed below 1 bar. Molecular modeling can aid in selection of adsorbents for CO(2) capture from flue gas by screening a large number of MOFs.

  14. Mesoporous ZnO microcube derived from a metal-organic framework as photocatalyst for the degradation of organic dyes

    Science.gov (United States)

    Ban, Jin-jin; Xu, Guan-cheng; Zhang, Li; Lin, He; Sun, Zhi-peng; Lv, Yan; Jia, Dian-zeng

    2017-12-01

    A cube-like porous ZnO architecture was synthesized by direct two-step thermolysis of a zinc-based metal-organic framework [(CH3)2NH2][Zn(HCOO)3]. The obtained ZnO microcube was characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption and desorption isotherms. The mesoporous ZnO microcube was comprised by many nanoparticles, and inherited the cube shape from [(CH3)2NH2][Zn(HCOO)3] precursor. With large surface area and mesoporous structure, the ZnO microcube exhibits excellent photocatalytic activities against methyl orange (MO) and rhodamine B (RhB) under UV irradiation, and the degradation rates reached 99.7% and 98.1% within 120 min, respectively.

  15. Experimental and theoretical investigations of the electronic band structure of metal-organic frameworks of HKUST-1 type

    Science.gov (United States)

    Gu, Zhi-Gang; Heinke, Lars; Wöll, Christof; Neumann, Tobias; Wenzel, Wolfgang; Li, Qiang; Fink, Karin; Gordan, Ovidiu D.; Zahn, Dietrich R. T.

    2015-11-01

    The electronic properties of metal-organic frameworks (MOFs) are increasingly attracting the attention due to potential applications in sensor techniques and (micro-) electronic engineering, for instance, as low-k-dielectric in semiconductor technology. Here, the band gap and the band structure of MOFs of type HKUST-1 are studied in detail by means of spectroscopic ellipsometry applied to thin surface-mounted MOF films and by means of quantum chemical calculations. The analysis of the density of states, the band structure, and the excitation spectrum reveal the importance of the empty Cu-3d orbitals for the electronic properties of HKUST-1. This study shows that, in contrast to common belief, even in the case of this fairly "simple" MOF, the excitation spectra cannot be explained by a superposition of "intra-unit" excitations within the individual building blocks. Instead, "inter-unit" excitations also have to be considered.

  16. Experimental and theoretical investigations of the electronic band structure of metal-organic frameworks of HKUST-1 type

    International Nuclear Information System (INIS)

    Gu, Zhi-Gang; Heinke, Lars; Wöll, Christof; Neumann, Tobias; Wenzel, Wolfgang; Li, Qiang; Fink, Karin; Gordan, Ovidiu D.; Zahn, Dietrich R. T.

    2015-01-01

    The electronic properties of metal-organic frameworks (MOFs) are increasingly attracting the attention due to potential applications in sensor techniques and (micro-) electronic engineering, for instance, as low-k-dielectric in semiconductor technology. Here, the band gap and the band structure of MOFs of type HKUST-1 are studied in detail by means of spectroscopic ellipsometry applied to thin surface-mounted MOF films and by means of quantum chemical calculations. The analysis of the density of states, the band structure, and the excitation spectrum reveal the importance of the empty Cu-3d orbitals for the electronic properties of HKUST-1. This study shows that, in contrast to common belief, even in the case of this fairly “simple” MOF, the excitation spectra cannot be explained by a superposition of “intra-unit” excitations within the individual building blocks. Instead, “inter-unit” excitations also have to be considered

  17. Metal-Organic Framework Modified Glass Substrate for Analysis of Highly Volatile Chemical Warfare Agents by Paper Spray Mass Spectrometry.

    Science.gov (United States)

    Dhummakupt, Elizabeth S; Carmany, Daniel O; Mach, Phillip M; Tovar, Trenton M; Ploskonka, Ann M; Demond, Paul S; DeCoste, Jared B; Glaros, Trevor

    2018-03-07

    Paper spray mass spectrometry has been shown to successfully analyze chemical warfare agent (CWA) simulants. However, due to the volatility differences between the simulants and real G-series (i.e., sarin, soman) CWAs, analysis from an untreated paper substrate proved difficult. To extend the analytical lifetime of these G-agents, metal-organic frameworks (MOFs) were successfully integrated onto the paper spray substrates to increase adsorption and desorption. In this study, several MOFs and nanoparticles were tested to extend the analytical lifetimes of sarin, soman, and cyclosarin on paper spray substrates. It was found that the addition of either UiO-66 or HKUST-1 to the paper substrate increased the analytical lifetime of the G-agents from less than 5 min detectability to at least 50 min.

  18. Dual-Function Metal-Organic Framework as a Versatile Catalyst for Detoxifying Chemical Warfare Agent Simulants.

    Science.gov (United States)

    Liu, Yangyang; Moon, Su-Young; Hupp, Joseph T; Farha, Omar K

    2015-12-22

    The nanocrystals of a porphyrin-based zirconium(IV) metal-organic framework (MOF) are used as a dual-function catalyst for the simultaneous detoxification of two chemical warfare agent simulants at room temperature. Simulants of nerve agent (such as GD, VX) and mustard gas, dimethyl 4-nitrophenyl phosphate and 2-chloroethyl ethyl sulfide, have been hydrolyzed and oxidized, respectively, to nontoxic products via a pair of pathways catalyzed by the same MOF. Phosphotriesterase-like activity of the Zr6-containing node combined with photoactivity of the porphyrin linker gives rise to a versatile MOF catalyst. In addition, bringing the MOF crystals down to the nanoregime leads to acceleration of the catalysis.

  19. Urea-modified metal-organic framework of type MIL-101(Cr) for the preconcentration of phosphorylated peptides

    International Nuclear Information System (INIS)

    Yang, Xiaoqing; Xia, Yan

    2016-01-01

    Mass spectrometry (MS) is the most powerful tool in phosphoproteomics research. However, phosphopeptides usually are present in low concentrations and their preconcentration therefore is highly desired. We describe a two-step method for the synthesis of a metal organic framework of the type MIL-101(Cr) that is modified with urea (then designated as MIL-101(Cr)-UR 2 ). It possesses large surface area, good solvent stability and high affinity for some phosphates. Due to the presence of modified urea functions, this material allows for selective and effective enrichment of phosphorylated peptides. It was successfully applied to the enrichment of phosphopeptides from non-fat-milk. The method was applied to the detection of phosphopeptides in a tryptic digest of β-casein where is showed a detection sensitivity as low as 10 −10 M. (author)

  20. Structural characterization of framework-gas interactions in the metal-organic framework Co2(dobdc) by in situ single-crystal X-ray diffraction.

    Science.gov (United States)

    Gonzalez, Miguel I; Mason, Jarad A; Bloch, Eric D; Teat, Simon J; Gagnon, Kevin J; Morrison, Gregory Y; Queen, Wendy L; Long, Jeffrey R

    2017-06-01

    The crystallographic characterization of framework-guest interactions in metal-organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH 4 , N 2 , O 2 , Ar, and P 4 adsorption in Co 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate), a metal-organic framework bearing coordinatively unsaturated cobalt(ii) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(ii) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal-organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co-CH 4 and Co-Ar interactions observed in Co 2 (dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal-CH 4 interaction and the first crystallographically characterized metal-Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(ii) sites in Co 2 (dobdc), with differential enthalpies of adsorption as weak as -17(1) kJ mol -1 (for Ar). Moreover, the structures of Co 2 (dobdc)·3.8N 2 , Co 2 (dobdc)·5.9O 2 , and Co 2 (dobdc)·2.0Ar reveal the location of secondary (N 2 , O 2 , and Ar) and tertiary (O 2 ) binding sites in Co 2 (dobdc), while high-pressure CO 2 , CO, CH 4 , N 2 , and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.

  1. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks

    KAUST Repository

    Feng, Liang; Yuan, Shuai; Zhang, Liang-Liang; Tan, Kui; Li, Jia-Luo; Kirchon, Angelo; Liu, Ling-Mei; Zhang, Peng; Han, Yu; Chabal, Yves J.; Zhou, Hong-Cai

    2018-01-01

    strate-gy, linker thermolysis, to construct ultra-stable hierarchically porous metal−organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores

  2. Formation of bimetallic metal-organic framework nanosheets and their derived porous nickel-cobalt sulfides for supercapacitors.

    Science.gov (United States)

    Chen, Chen; Wu, Meng-Ke; Tao, Kai; Zhou, Jiao-Jiao; Li, Yan-Li; Han, Xue; Han, Lei

    2018-04-24

    Metal-organic frameworks (MOFs) show great advantages as new kinds of active materials for energy storage. In this study, bimetallic metal-organic frameworks (Ni/Co-MOFs) with nanosheet-assembled flower-like structures were synthesized by etching Ni-MOF microspheres in a cobalt nitrate solution. It can be clearly observed that the amount of Co(NO3)2 and etching time play crucial roles in the formation of Ni/Co-MOF nanosheets. The Ni/Co-MOFs were used as electrode materials for supercapacitors and the optimized Ni/Co-MOF-5 exhibited the highest capacitances of 1220.2 F g-1 and 986.7 F g-1 at current densities of 1 A g-1 and 10 A g-1, respectively. Ni/Co-MOF-5 was further sulfurized, and the derived Ni-Co-S electrode showed a higher specific capacitance of 1377.5 F g-1 at a current density of 1 A g-1 and a retention of 89.4% when the current density was increased to 10 A g-1, indicating superior rate capability. Furthermore, Ni/Co-MOF-5 and Ni-Co-S showed excellent cycling stability, i.e. about 87.8% and 93.7% of initial capacitance can be still maintained after 3000 cycles of charge-discharge. More interestingly, the Ni/Co-MOF-5//AC ASC shows an energy density of 30.9 W h kg-1 at a power density of 1132.8 W kg-1, and the Ni-Co-S//AC ASC displays a high energy density of 36.9 W h kg-1 at a power density of 1066.42 W kg-1. These results demonstrate that the as-synthesized bimetallic Ni/Co-MOF nanosheets and their derived nickel-cobalt sulfides have promising applications in electrochemical supercapacitors.

  3. 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].

  4. Dilute NiO/carbon nanofiber composites derived from metal organic framework fibers as electrode materials for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ying; Yang, Feng; Hu, Hongru; Lee, Sungsik; Wang, Yue; Zhao, Hairui; Zeng, Dehong; Zhou, Biao; Hao, Shijie

    2017-01-01

    A new type of carbon nanofiber (CNF) dominated electrode materials decorated with dilute NiO particles (NiO/CNF) has been in situ fabricated by direct pyrolysis of Ni, Zn-containing metal organic framework fibers, which are skillfully constructed by assembling different proportional NiCl2·6H2O and Zn(Ac)2·2H2O with trimesic acid in the presence of N,N-dimethylformamide. With elegant combination of advantages of CNF and evenly dispersed NiO particles, as well as successful modulation of conductivity and porosity of final composites, our NiO/CNF composites display well-defined capacitive features. A high capacitance of 14926 F g–1 was obtained in 6 M KOH electrolyte when the contribution from 0.43 wt% NiO was considered alone, contributing to over 35% of the total capacitance (234 F g–1 ). This significantly exceeds its theoretical specific capacitance of 2584 F g–1. It has been established from the Ragone plot that a largest energy density of 33.4 Wh kg–1 was obtained at the current density of 0.25 A g–1. Furthermore, such composite electrode materials show good rate capability and outstanding cycling stability up to 5000 times (only 10% loss). The present study provides a brand-new approach to design a high capacitance and stable supercapacitor electrode and the concept is extendable to other composite materials. Keywords: Metal organic framework; Nickel oxide; Carbon nanofiber; In situ synthesis; Capacitance

  5. Symbiosis of zeolite-like metal-organic frameworks (rho-ZMOF) and hydrogels: Composites for controlled drug release

    KAUST Repository

    Ananthoji, Ramakanth

    2011-01-01

    The design and synthesis of new finely tunable porous materials has spurred interest in developing novel uses in a variety of systems. Zeolites, inorganic materials with high thermal and mechanical stability, in particular, have been widely examined for use in applications such as catalysis, ion exchange and separation. A relatively new class of inorganic-organic hybrid materials known as metal-organic frameworks (MOFs) have recently surfaced, and many have exhibited their efficiency in potential applications such as ion exchange and drug delivery. A more recent development is the design and synthesis of a subclass of MOFs based on zeolite topologies (i.e. ZMOFs), which often exhibit traits of both zeolites and MOFs. Bio-compatible hydrogels already play an important role in drug delivery systems, but are often limited by stability issues. Thus, the addition of ZMOFs to hydrogel formulations is expected to enhance the hydrogel mechanical properties, and the ZMOF-hydrogel composites should present improved, symbiotic drug storage and release for delivery applications. Herein we present the novel composites of a hydrogel with a zeolite-like metal-organic framework, rho-ZMOF, using 2-hydroxyethyl methacrylate (HEMA), 2,3-dihydroxypropyl methacrylate (DHPMA), N-vinyl-2-pyrolidinone (VP) and ethylene glycol dimethacrylate (EGDMA), and the corresponding drug release. An ultraviolet (UV) polymerization method is employed to synthesize the hydrogels, VP 0, VP 15, VP 30, VP 45 and the ZMOF-VP 30 composite, by varying the VP content (mol%). The rho-ZMOF, VP 30, and ZMOF-VP 30 composite are all tested for the controlled release of procainamide (protonated, PH), an anti-arrhythmic drug, in phosphate buffer solution (PBS) using UV spectroscopy. © 2011 The Royal Society of Chemistry.

  6. Covalent organic framework-derived microporous carbon nanoparticles coated with conducting polypyrrole as an electrochemical capacitor

    Science.gov (United States)

    Kim, Dong Jun; Yoon, Jung Woon; Lee, Chang Soo; Bae, Youn-Sang; Kim, Jong Hak

    2018-05-01

    We report a high-performance electrochemical capacitor based on covalent organic framework (COF)-derived microporous carbon (MPC) nanoparticles and electrochemically polymerized polypyrrole (Ppy) as a pseudocapacitive material. The COF, Schiff-based network-1 (SNW-1) nanoparticles are prepared via a condensation reaction between melamine and terephthalaldehyde, and the resultant MPC film is prepared via a screen-printing method. The MPC film exhibits a bimodal porous structure with micropores and macropores, resulting in both a large surface area and good electrolyte infiltration. Ppy is synthesized potentio-statically (0.8 V vs. Ag/AgCl) by varying the reaction time, and successful synthesis of Ppy is confirmed via Raman spectroscopy. The specific capacitance with the Ppy coating is enhanced by up to 2.55 F cm-2 due to the synergetic effect of pseudocapacitance and reduced resistance.

  7. Three novel metal-organic frameworks based on flexible porphyrin tetracarboxylic acids as highly effective catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zengqi [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi’an, Shaanxi 710069 (China); Su, Xiaoqin [School of Materials and Chemical Engineering, Xi’an Technological University, Xi’an, Shaanxi 710021 (China); Yu, Fan; Li, Jun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi’an, Shaanxi 710069 (China)

    2016-06-15

    Targeted synthesis of metalloporphyrinic frameworks (MPFs) with Cu(II) (1), Ni(II) (2, 3) 5, 10, 15, 20-tetrakis[4-(carboxymethyleneoxy)phenyl]porphyrin (Cu(TCMOPP) and Ni(TCMOPP)) as building blocks afforded three new extended coordination polymers inter-linked by Zn(II) (1) and K(I) (2, 3). 1 shows 2D frameworks while 2, 3 are 3D frameworks. The open channel are 7–17 Å wide and accessible to guest/solvent molecules. Besides, the thermogravimetric analyses (TGA) indicate that the framework structures of the three compounds are stable until 300 °C. In addition, the catalytic activities of 1–3 to the alkylbenzenes oxidation are examined, and the results indicate that 1 exhibit high catalytic activity to oxidation of ethylbenzene and 1,2,3,4-tetrahydronaphthalene with conversion of 64.1% and 80.3% respectively. - Graphical abstract: Three novel metalloporphyrinic frameworks (1, 2, 3) were synthesized based on tetracarboxylic Cu(II) (1), Ni(II) (2, 3) metalloporphyrin inter-linked by Zn(II) (1) , K(I) (2, 3), and 1 shows high catalytic activity to oxidation reaction of alkylbenzenes with conversion 80.3%. Display Omitted.

  8. High proton conductivity in cyanide-bridged metal-organic frameworks: understanding the role of water

    NARCIS (Netherlands)

    Gao, Y.; Broersen, R.; Hageman, W.; Yan, N.; Mittelmeijer-Hazeleger, M.; Rothenberg, G.; Tanase, S.

    2015-01-01

    We investigate and discuss the proton conductivity properties of the cyanide-bridged metal–organic framework (MOF) [Nd(mpca)2Nd(H2O)6Mo(CN)8]·nH2O (where mpca is 5-methyl-2-pyrazinecarboxylate). This MOF is one of an exciting class of cyanide-bridged materials that can combine porosity with

  9. Photoswitchable metal organic frameworks: turn on the lights and close the windows

    NARCIS (Netherlands)

    Castellanos Ortega, S.; Kapteijn, F.; Gascon Sabate, J.

    2016-01-01

    The ability of modulating the properties of metal–organic frameworks (MOF) on demand by external light-stimuli is a most appealing pathway to enhance their performance in storage and separation and to render novel advanced applications. Photoswitchable linkers of different nature have been inserted

  10. Method for analyzing structural changes of flexible metal-organic frameworks induced by adsorbates

    NARCIS (Netherlands)

    Dubbeldam, D.; Krishna, R.; Snurr, R.Q.

    2009-01-01

    Metal−organic frameworks (MOFs) have crystal structures that exhibit unusual flexibility. An extreme example is that of the "breathing MOF" MIL-53 that expands or shrinks to admit guest molecules like CO2 and water. We present a powerful simulation tool to quickly calculate unit cell shape and size

  11. Microporous heptazine functionalized (3,24)-connected rht-metal-organic framework: Synthesis, structure, and gas sorption analysis

    KAUST Repository

    Luebke, Ryan

    2014-02-05

    Here we synthesized the highly porous rht-MOF-9 as the first example of an rht-MOF having a polycyclic central core. This material was synthesized from a predesigned polyheterocyclic nitrogen-rich hexacarboxylate (tri-isophthalate) ligand, which serves as the 3-connected, trigonal molecular building block (MBB). When reacted under the proper conditions, this ligand, having three coplanar isophthalic acid moieties, codes for the in situ formation of the targeted 24-connected copper-based supermolecular building block (SBB) having rhombicuboctahedral geometry. This combination of a 24-connected building block linked through 3-connected nodes results in a novel material with the singular rht topology. The rht-MOF-9 compound exhibits promising H2 and CO2 adsorption properties in comparison to previously reported rht-MOFs. © 2014 American Chemical Society.

  12. High performance gas adsorption and separation of natural gas in two microporous metal-organic frameworks with ternary building units.

    Science.gov (United States)

    Wang, Dongmei; Zhao, Tingting; Cao, Yu; Yao, Shuo; Li, Guanghua; Huo, Qisheng; Liu, Yunling

    2014-08-14

    Two novel MMOFs, JLU-Liu5 and JLU-Liu6, are based on ternary building units and exhibit high adsorption selectivity for CO2, C2H6 and C3H8 over CH4, which is attributed to steric effects and host-guest interactions. These MMOFs are promising materials for gas adsorption and natural gas purification.

  13. CFA-13 - a bifunctional perfluorinated metal-organic framework featuring active Cu(i) and Cu(ii) sites.

    Science.gov (United States)

    Fritzsche, J; Denysenko, D; Grzywa, M; Volkmer, D

    2017-11-07

    The synthesis and crystal structure of the mixed-valent perfluorinated metal-organic framework (Me 2 NH 2 )[CFA-13] (Coordination Framework Augsburg University-13), (Me 2 NH 2 )[CuCu(tfpc) 4 ] (H 2 -tfpc = 3,5-bis(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) is described. The copper-containing MOF crystallizes in the monoclinic crystal system within the space group P2 1 /n (no. 14) and the unit cell parameters are as follows: a = 22.3887(19), b = 13.6888(8), c = 21.1804(13) Å, β = 90.495(3)°, V = 6491.0(8) Å 3 . (Me 2 NH 2 )[CFA-13] features a porous 3-D structure constructed from two types of secondary building units (SBUs). Besides novel trinuclear [Cu(pz) 4 ] - coordination units, the network also exhibits Cu(ii) paddle-wheel SBUs. (Me 2 NH 2 )[CFA-13] is fully characterized by single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence, gas sorption measurements and pulse chemisorption experiments. M[CFA-13] (M = K + , Cs + ) frameworks were prepared by postsynthetic exchange of interchannel dimethylammonium cations. Moreover, it was shown that CO molecules can be selectively bound at Cu(i) sites of [Cu(pz) 4 ] - units, whereas Cu(ii) paddle-wheel units bind selectively NH 3 molecules.

  14. A flexible metal-organic framework with a high density of sulfonic acid sites for proton conduction

    Science.gov (United States)

    Yang, Fan; Xu, Gang; Dou, Yibo; Wang, Bin; Zhang, Heng; Wu, Hui; Zhou, Wei; Li, Jian-Rong; Chen, Banglin

    2017-11-01

    The design of stable electrolyte materials with high proton conductivity for use in proton exchange membrane fuel cells remains a challenge. Most of the materials explored have good conductivity at high relative humidity (RH), but significantly decreased conductivity at reduced RH. Here we report a chemically stable and structurally flexible metal-organic framework (MOF), BUT-8(Cr)A, possessing a three-dimensional framework structure with one-dimensional channels, in which high-density sulfonic acid (-SO3H) sites arrange on channel surfaces for proton conduction. We propose that its flexible nature, together with its -SO3H sites, could allow BUT-8(Cr)A to self-adapt its framework under different humid environments to ensure smooth proton conduction pathways mediated by water molecules. Relative to other MOFs, BUT-8(Cr)A not only has a high proton conductivity of 1.27 × 10-1 S cm-1 at 100% RH and 80 °C but also maintains moderately high proton conductivity at a wide range of RH and temperature.

  15. Metal-organic framework based on copper(I) sulfate and 4,4'-bipyridine catalyzes the cyclopropanation of styrene

    International Nuclear Information System (INIS)

    Shi Fanian; Silva, Ana Rosa; Rocha, Joao

    2011-01-01

    The hydrothermal synthesis of a new metal-organic framework (MOF) formulated as Cu 2 (4,4'-bpy) 2 SO 4 .6(H 2 O), [abbreviation: (1); bpy or 4,4'-bpy=4,4'-bipyridine; SO 4 2- =sulfate group] has been reported. The structure of this MOF consists of Cu + nodes connected via 4,4'-bpy to form infinite chains, with two neighboring chains further bridged on the nodes by SO 4 2- , resulting in a 1-D double chain network. Guest water molecules reside in between the chains and are hydrogen-bonded to the O and S atoms from the nearest sulfate groups, leading to the formation of a 3-D supramolecular framework. This MOF is good heterogeneous catalyst for the cyclopropanation of styrene, with high trans cyclopropane diastereoselectivity and was recycled and reused for three consecutive cycles without a significant loss of catalytic activity. - Graphical Abstract: A new MOF structure built up of 4,4 ' -bipyridine, sulphate and Cu(I), is an active heterogeneous catalyst for cyclopropanation of styrene with ethyldiazoacetate. Highlights: → The synthesis is different from solvothermal synthesis for other Cu(I) compounds. → The compound and the structure are new. → H bonds form infinite planes among water molecules and sulphate species. → H bonding interaction makes the structure into a 3D supramolecular framework. → Active catalytic property as heterogeneous catalyst for cyclopropanation of styrene.

  16. Protonated graphitic carbon nitride coated metal-organic frameworks with enhanced visible-light photocatalytic activity for contaminants degradation

    Science.gov (United States)

    Huang, Jie; Zhang, Xibiao; Song, Haiyan; Chen, Chunxia; Han, Fuqin; Wen, Congcong

    2018-05-01

    Most of the reported composites of g-C3N4/metal-organic frameworks (MOFs) were obtained via exfoliation of g-C3N4 and wrapping the nanosheets on MOFs with weak interaction. In this work, chemical protonation of g-C3N4 and dip-coating was adopted as a feasible pathway to achieve the real combination of g-C3N4 derivatives with a familiar MOF material MIL-100(Fe). Structural, chemical and photophysical properties of the novel hybrid photocatalysts were characterized and compared to those of the parent materials. It was verified that the protonated g-C3N4 species of appropriate content were uniformly coated along the frameworks of MIL-100(Fe) with strong interaction. The optimal materials maintained the intact framework structure, surface property and porosity of MIL-100(Fe), as well as the inherent structural units and physicochemical properties of C3N4. In comparison to the parent materials, the protonated g-C3N4 coated MIL-100(Fe) materials exhibited enhanced photocatalytic activity in degradation of rhodamine B or methylene blue dye, as well as in oxidative denitrogenation for pyridine by molecular oxygen under visible light. Introduction of protonated g-C3N4 on MOFs improved the adsorption ability for contaminant molecules. Furthermore, coating effect provided a platform for rapid photoexcited electrons transfer and superior separation of photogenerated electron-hole pairs. Photocatalytic conversion of the three contaminants followed different mechanisms.

  17. Graphitic carbon nitride nanosheet@metal-organic framework core-shell nanoparticles for photo-chemo combination therapy

    Science.gov (United States)

    Chen, Rui; Zhang, Jinfeng; Wang, Yu; Chen, Xianfeng; Zapien, J. Antonio; Lee, Chun-Sing

    2015-10-01

    Recently, nanoscale metal-organic frameworks (NMOFs) have started to be developed as a promising platform for bioimaging and drug delivery. On the other hand, combination therapies using multiple approaches are demonstrated to achieve much enhanced efficacy. Herein, we report, for the first time, core-shell nanoparticles consisting of a photodynamic therapeutic (PDT) agent and a MOF shell while simultaneously carrying a chemotherapeutic drug for effective combination therapy. In this work, core-shell nanoparticles of zeolitic-imadazolate framework-8 (ZIF-8) as shell embedded with graphitic carbon nitride (g-C3N4) nanosheets as core are fabricated by growing ZIF-8 in the presence of g-C3N4 nanosheets. Doxorubicin hydrochloride (DOX) is then loaded into the ZIF-8 shell of the core-shell nanoparticles. The combination of the chemotherapeutic effects of DOX and the PDT effect of g-C3N4 nanosheets can lead to considerably enhanced efficacy. Furthermore, the red fluorescence of DOX and the blue fluorescence of g-C3N4 nanosheets provide the additional function of dual-color imaging for monitoring the drug release process.Recently, nanoscale metal-organic frameworks (NMOFs) have started to be developed as a promising platform for bioimaging and drug delivery. On the other hand, combination therapies using multiple approaches are demonstrated to achieve much enhanced efficacy. Herein, we report, for the first time, core-shell nanoparticles consisting of a photodynamic therapeutic (PDT) agent and a MOF shell while simultaneously carrying a chemotherapeutic drug for effective combination therapy. In this work, core-shell nanoparticles of zeolitic-imadazolate framework-8 (ZIF-8) as shell embedded with graphitic carbon nitride (g-C3N4) nanosheets as core are fabricated by growing ZIF-8 in the presence of g-C3N4 nanosheets. Doxorubicin hydrochloride (DOX) is then loaded into the ZIF-8 shell of the core-shell nanoparticles. The combination of the chemotherapeutic effects of DOX

  18. Force-Field Prediction of Materials Properties in Metal-Organic Frameworks

    Science.gov (United States)

    2016-01-01

    In this work, MOF bulk properties are evaluated and compared using several force fields on several well-studied MOFs, including IRMOF-1 (MOF-5), IRMOF-10, HKUST-1, and UiO-66. It is found that, surprisingly, UFF and DREIDING provide good values for the bulk modulus and linear thermal expansion coefficients for these materials, excluding those that they are not parametrized for. Force fields developed specifically for MOFs including UFF4MOF, BTW-FF, and the DWES force field are also found to provide accurate values for these materials’ properties. While we find that each force field offers a moderately good picture of these properties, noticeable deviations can be observed when looking at properties sensitive to framework vibrational modes. This observation is more pronounced upon the introduction of framework charges. PMID:28008758

  19. Towards high water permeability in triazine-framework-based microporous membranes for dehydration of ethanol.

    Science.gov (United States)

    Tang, Yu Pan; Wang, Huan; Chung, Tai Shung

    2015-01-01

    The microstructural evolution of a series of triazine framework-based microporous (TFM) membranes under different conditions has been explored in this work. The pristine TFM membrane is in situ fabricated in the course of polymer synthesis via a facile Brønsted-acid-catalyzed cyclotrimerizaiton reaction. The as-synthesized polymer exhibits a microporous network with high thermal stability. The free volume size of the TFM membranes gradually evolved from a unimodal distribution to a bimodal distribution under annealing, as analyzed by positron annihilation lifetime spectroscopy (PALS). The emergence of the bimodal distribution is probably ascribed to the synergetic effect of quenching and thermal cyclization reaction. In addition, the fractional free volume (FFV) of the membranes presents a concave trend with increasing annealing temperature. Vapor sorption tests reveal that the mass transport properties are closely associated with the free volume evolution, which provides an optimal condition for dehydration of biofuels. A promising separation performance with extremely high water permeability has been attained for dehydration of an 85 wt % ethanol aqueous solution at 45 °C. The study on the free volume evolution of the TFM membranes may provide useful insights about the microstructure and mass transport behavior of the microporous polymeric materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 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

  1. A Biomimetic Approach to New Adsorptive Hydrogen Storage Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Hongcai J [Texas A& M University

    2015-08-12

    In the past decades, there has been an escalation of interest in the study of MOFs due to their fascinating structures and intriguing application potentials. Their exceptionally high surface areas, uniform yet tunable pore sizes, and well-defined adsorbate-MOF interaction sites make them suitable for hydrogen storage. Various strategies to increase the hydrogen capacity of MOFs, such as constructing pore sizes comparable to hydrogen molecules, increasing surface area and pore volume, utilizing catenation, and introducing coordinatively unsaturated metal centers (UMCs) have been widely explored to increase the hydrogen uptake of the MOFs. MOFs with hydrogen uptake approaching the DOE gravimetric storage goal under reasonable pressure but cryo- temperature (typically 77 K) were achieved. However, the weak interaction between hydrogen molecules and MOFs has been the major hurdle limiting the hydrogen uptake of MOFs at ambient temperature. Along the road, we have realized both high surface area and strong interaction between framework and hydrogen are equally essential for porous materials to be practically applicable in Hydrogen storage. Increasing the isosteric heats of adsorption for hydrogen through the introduction of active centers into the framework could have great potential on rendering the framework with strong interaction toward hydrogen. Approaches on increasing the surface areas and improving hydrogen affinity by optimizing size and structure of the pores and the alignment of active centers around the pores in frameworks have been pursued, for example: (a) the introduction of coordinatively UMC (represents a metal center missing multiple ligands) with potential capability of multiple dihydrogen-binding (Kubas type, non-dissociative) per UMC, (b) the design and synthesis of proton-rich MOFs in which a + H3 binds dihydrogen just like a metal ion does, and (c) the preparation of MOFs and PPNs with well aligned internal electric fields. We believe the

  2. The Cooperativity of Fe3O4 and Metal-Organic Framework as Multifunctional Nanocomposites for Laser Desorption Ionization Process.

    Science.gov (United States)

    Fu, Chung-Wei; Lirio, Stephen; Shih, Yung-Han; Liu, Wan-Ling; Lin, Chia-Her; Huang, Hsi-Ya

    2018-05-10

    We report a novel and facile strategy for developing a water stable magnetic metal organic framework nanocomposite (Fe3O4@MOF), in which a Keggin polyoxometalate, phosphotungstic acid (HPW), was encapsulated within the MOF framework via one-pot synthesis method. The combination of HPW-embedded MOF and Fe3O4 endowed the composite with high surface area, strong UV absorption, good hydrophilicity, and enhanced water stability. With these unique properties, the Fe3O4@MOF embedded HPW were served as adsorbent as well as matrix for (surface-assisted laser desorption ionization mass spectrometry) SALDI-MS analysis of polar and non-polar compounds. The synergistic effect of Fe3O4 and MOF showed an interference-free background at low mass region than the pristine MOF or Fe3O4 counterpart. This simple approach can be used as new platform in developing magnetic MOF composites without the time consuming and labor-intensive preparation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Investigating H₂ Sorption in a Fluorinated Metal-Organic Framework with Small Pores Through Molecular Simulation and Inelastic Neutron Scattering.

    Science.gov (United States)

    Forrest, Katherine A; Pham, Tony; Georgiev, Peter A; Pinzan, Florian; Cioce, Christian R; Unruh, Tobias; Eckert, Juergen; Space, Brian

    2015-07-07

    Simulations of H2 sorption were performed in a metal-organic framework (MOF) consisting of Zn(2+) ions coordinated to 1,2,4-triazole and tetrafluoroterephthalate ligands (denoted [Zn(trz)(tftph)] in this work). The simulated H2 sorption isotherms reported in this work are consistent with the experimental data for the state points considered. The experimental H2 isosteric heat of adsorption (Qst) values for this MOF are approximately 8.0 kJ mol(-1) for the considered loading range, which is in the proximity of those determined from simulation. The experimental inelastic neutron scattering (INS) spectra for H2 in [Zn(trz)(tftph)] reveal at least two peaks that occur at low energies, which corresponds to high barriers to rotation for the respective sites. The most favorable sorption site in the MOF was identified from the simulations as sorption in the vicinity of a metal-coordinated H2O molecule, an exposed fluorine atom, and a carboxylate oxygen atom in a confined region in the framework. Secondary sorption was observed between the fluorine atoms of adjacent tetrafluoroterephthalate ligands. The H2 molecule at the primary sorption site in [Zn(trz)(tftph)] exhibits a rotational barrier that exceeds that for most neutral MOFs with open-metal sites according to an empirical phenomenological model, and this was further validated by calculating the rotational potential energy surface for H2 at this site.

  4. Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

    Science.gov (United States)

    Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

    2017-09-27

    A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

  5. CO 2 adsorption in mono-, di- and trivalent cation-exchanged metal-organic frameworks: A molecular simulation study

    KAUST Repository

    Chen, Yifei

    2012-02-28

    A molecular simulation study is reported for CO 2 adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, and Al 3+). The isosteric heat and Henry\\'s constant at infinite dilution increase monotonically with increasing charge-to-diameter ratio of cation (Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ < Al 3+). At low pressures, cations act as preferential adsorption sites for CO 2 and the capacity follows the charge-to-diameter ratio. However, the free volume of framework becomes predominant with increasing pressure and Mg-rho-ZMOF appears to possess the highest saturation capacity. The equilibrium locations of cations are observed to shift slightly upon CO 2 adsorption. Furthermore, the adsorption selectivity of CO 2/H 2 mixture increases as Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ ≈ Al 3+. At ambient conditions, the selectivity is in the range of 800-3000 and significantly higher than in other nanoporous materials. In the presence of 0.1% H 2O, the selectivity decreases drastically because of the competitive adsorption between H 2O and CO 2, and shows a similar value in all of the cation-exchanged rho-ZMOFs. This simulation study provides microscopic insight into the important role of cations in governing gas adsorption and separation, and suggests that the performance of ionic rho-ZMOF can be tailored by cations. © 2012 American Chemical Society.

  6. Rapid and selective adsorption of cationic dyes by a unique metal-organic framework with decorated pore surface

    Science.gov (United States)

    Zhang, Jie; Li, Fan; Sun, Qian

    2018-05-01

    Organic dye pollutants become a big headache due to their toxic nature to the environment, and it should be one of the best solutions if we can remove and separate them. Here, a metal-organic framework (MOF) (denoted as Zn-MOF) with carbonyl group based on fluorenone-2,7-dicarboxylate ligand, was directly synthesized without post-synthesis method and applied to selectively absorb cationic dyes such as MB, CV, RhB from aqueous solution, while anionic or neutral dyes were excluded. Characterization of the Zn-MOF was achieved by X-ray diffraction, scanning electron microscope, Fourier transform infrared spectrometry and elemental analysis. The Zn-MOF mainly possesses open pore channels, high surface area, big pore volume, and most important, the pore surface is furnished with carbonyl groups arising from the ligand and pointing toward the centers of the large chambers of the framework, which are benefit for the adsorption of the cationic dyes. The MB maximum adsorption capacities can attain 326 mg g-1, which is probably due to the suitable pore size, higher solvent-accessible void, and the prominent adsorption capacity of the mesoporous material. The dye adsorption process for the material is proven to be charge-selective and size-selective, and the adsorption isotherms, as well as kinetics characteristic of dye adsorption onto the Zn-MOF were also investigated.

  7. Metal-Organic Framework Thin Film Coated Optical Fiber Sensors: A Novel Waveguide-Based Chemical Sensing Platform.

    Science.gov (United States)

    Kim, Ki-Joong; Lu, Ping; Culp, Jeffrey T; Ohodnicki, Paul R

    2018-02-23

    Integration of optical fiber with sensitive thin films offers great potential for the realization of novel chemical sensing platforms. In this study, we present a simple design strategy and high performance of nanoporous metal-organic framework (MOF) based optical gas sensors, which enables detection of a wide range of concentrations of small molecules based upon extremely small differences in refractive indices as a function of analyte adsorption within the MOF framework. Thin and compact MOF films can be uniformly formed and tightly bound on the surface of etched optical fiber through a simple solution method which is critical for manufacturability of MOF-based sensor devices. The resulting sensors show high sensitivity/selectivity to CO 2 gas relative to other small gases (H 2 , N 2 , O 2 , and CO) with rapid (optical fiber platform which results in an amplification of inherent optical absorption present within the MOF-based sensing layer with increasing values of effective refractive index associated with adsorption of gases.

  8. Fixed distance photoinduced electron transfer between Fe and Zn porphyrins encapsulated within the Zn HKUST-1 metal organic framework.

    Science.gov (United States)

    Larsen, Randy W; Wojtas, Lukasz

    2015-02-21

    An attractive strategy for the development of photocatalytic metal organic framework (MOF) materials is to co-encapsulate a photoactive electron donor with a catalytic electron acceptor within the MOF. Here we report the co-encapsulation of both Zn(ii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Zn4SP) and Fe(iii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Fe4SP) into an HKUST-1 (Zn) MOF and demonstrate photoinduced electron transfer (ET) between the co-encapsulated guest. Photo-excitation of the Zn4SP results in fixed-distance inter-molecular ET between the encapsulated (3)Zn4SP and the Fe(iii)4SP as evident by the reduction in the encapsulated (3)Zn4SP lifetime from 890 μs (kobs = 1.1 × 10(3) s(-1)) to 83 μs (kobs = 1.2 × 10(4) s(-1)) in the presence of Fe4SP giving a kET ∼ 1.1 × 10(4) s(-1). The data are consistent with ET taking place between encapsulated porphyrins that are two cages apart in distance with a reorganizational energy of ∼1.65 eV, β = 1.25 and ΔG° = -0.97 eV (within a semi-classical Marcus theory framework).

  9. Two Water Stable Copper Metal-Organic Frameworks with Performance in the Electrocatalytic Activity for Water Oxidation

    Directory of Open Access Journals (Sweden)

    Liu Xiuping

    2018-01-01

    Full Text Available Two novel water stable metal-organic frameworks, [Cu(L·(4,4′-bipy·(ClO4]n (1, [Cu(L·(phen·(ClO4·(H2O]2 (2, have been constructed by HL=[5-Mercapto-1-methyl] tetrazole acetic acid and Cu (II salt in the presence of assistant N-containing ligands. MOF 1 and MOF 2 with open CuII sites, resulting the framework 1 and 2 show electrocatalytic activity for water oxidation in alkaline solution. The electrochemical properties of complex for oxygen evolution reaction (OER were evaluated by linear sweep voltammetry (LSV and the Tafel slopes. Complex 1 has a higher LSV activity with a lower over potential of 1.54 V and a much higher increase in current density. Meanwhile, the Tafel slope of complex 1 (122.0 mV dec-1 is much lower than complex 2 (243.5 mV dec-1. This phenomenon makes complex 1 a promising porous material for electrocatalytic activity.

  10. Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production

    Science.gov (United States)

    Tian, Jia; Xu, Zi-Yue; Zhang, Dan-Wei; Wang, Hui; Xie, Song-Hai; Xu, Da-Wen; Ren, Yuan-Hang; Wang, Hao; Liu, Yi; Li, Zhan-Ting

    2016-05-01

    Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy)3]2+-based precursor and cucurbit[8]uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy)3]2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.

  11. Glucose recovery from aqueous solutions by adsorption in metal-organic framework MIL-101: a molecular simulation study.

    Science.gov (United States)

    Gupta, Krishna M; Zhang, Kang; Jiang, Jianwen

    2015-08-05

    A molecular simulation study is reported on glucose recovery from aqueous solutions by adsorption in metal-organic framework MIL-101. The F atom of MIL-101 is identified to be the most favorable adsorption site. Among three MIL-101-X (X = H, NH2 or CH3), the parent MIL-101 exhibits the highest adsorption capacity and recovery efficacy. Upon functionalization by -NH2 or -CH3 group, the steric hindrance in MIL-101 increases; consequently, the interactions between glucose and framework become less attractive, thus reducing the capacity and mobility of glucose. The presence of ionic liquid, 1-ethyl-3-methyl-imidazolium acetate, as an impurity reduces the strength of hydrogen-bonding between glucose and MIL-101, and leads to lower capacity and mobility. Upon adding anti-solvent (ethanol or acetone), a similar adverse effect is observed. The simulation study provides useful structural and dynamic properties of glucose in MIL-101, and it suggests that MIL-101 might be a potential candidate for glucose recovery.

  12. 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.

  13. Three-dimensional Printed Acrylonitrile Butadiene Styrene Framework Coated with Cu-BTC Metal-organic Frameworks for the Removal of Methylene Blue

    Science.gov (United States)

    Wang, Zongyuan; Wang, Jiajun; Li, Minyue; Sun, Kaihang; Liu, Chang-jun

    2014-01-01

    Three-dimensional (3D) printing was applied for the fabrication of acrylonitrile butadiene styrene (ABS) framework. Functionalization of the ABS framework was then performed by coating of porous Cu-BTC (BTC = benzene tricarboxylic acid) metal-organic frameworks on it using a step-by-step in-situ growth. The size of the Cu-BTC particles on ABS was ranged from 200 nm to 900 nm. The Cu-BTC/ABS framework can take up most of the space of the tubular reactor that makes the adsorption effective with no need of stirring. Methylene blue (MB) can be readily removed from aqueous solution by this Cu-BTC/ABS framework. The MB removal efficiency for solutions with concentrations of 10 and 5 mg/L was 93.3% and 98.3%, respectively, within 10 min. After MB adsorption, the Cu-BTC/ABS composite can easily be recovered without the need for centrifugation or filtration and the composite is reusable. In addition the ABS framework can be recovered for subsequent reuse. A significant advantage of 3D-printed frameworks is that different frameworks can be easily fabricated to meet the needs of different applications. This is a promising strategy to synthesize new frameworks using MOFs and polymers to develop materials for applications beyond adsorption. PMID:25089616

  14. Four new 3D metal-organic frameworks constructed by the asymmetrical pentacarboxylate: gas sorption behaviour and magnetic properties.

    Science.gov (United States)

    Yan, Yang-Tian; Zhang, Wen-Yan; Wu, Yun-Long; Li, Jiang; Xi, Zheng-Ping; Wang, Yao-Yu; Hou, Lei

    2016-10-04

    By using an asymmetrical rigid pentacarboxylic acid ligand, 2,4-di(3',5'-dicarboxylphenyl)benzoic acid (H 5 L), four new three-dimensional (3D) metal-organic frameworks (MOFs), namely {[Cu 2 (HL)(H 2 O) 2 ]·2DMF·2H 2 O} n (1), {[Co 2 (L)(DMA)]·H 2 N(Me) 2 } n (2), {[Co 2 (L)(H 2 O)]·H 2 N(Me) 2 } n (3), {[Mn 2 (L)(DMF)(H 2 O)]·H 2 N(Me) 2 } n (4), were solvothermally synthesized. H 5 L in 1-4 shows different coordination modes and can easily form various metal clusters (secondary building units, SBUs) in the final structures. 1 is a 3D porous framework with a (4,4)-connected pts topology based on the [Cu 2 (COO) 4 ] paddlewheel SBU, wherein six SBUs are connected by twelve HL 4- to get an unprecedented Cu 12 hendecahedron nanocage. 2-4 possess similar dinuclear [M 2 (COO) 5 ] SBUs (M = Co, Mn), which are further extended by L 5- to give rise to 3D frameworks with the uncommon (5,5)-connected nia-5,5-P2 1 /c and bnn topologies. In addition, the desolvated framework of 1 contains polar channels decorated with uncoordinated carboxylate groups, leading to selective adsorption for CO 2 over CH 4 at 195, 273 and 298 K. Moreover, the magnetic properties of 1-4 show that there exist antiferromagnetic interactions between metal ions.

  15. Highly Active Non-PGM Catalysts Prepared from Metal Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Heather M. Barkholtz

    2015-06-01

    Full Text Available Finding inexpensive alternatives to platinum group metals (PGMs is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs. Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/Nx/C prepared from iron doped zeolitic imidazolate frameworks (ZIFs are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/Nx/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR electrocatalytic activity must be demonstrated in membrane-electrode assemblies (MEAs of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.

  16. Fluorescent molecule incorporated metal-organic framework for fluoride sensing in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Xudong, E-mail: zhaoxd_tykj@163.com; Wang, Yuanyang; Hao, Xiuli; Liu, Wen, E-mail: 13700509372@163.com

    2017-04-30

    Highlights: • Fluorescein sodium was successfully encapsulated in UiO-66 via in-situ synthesis. • FS@UiO-66 is one of the few Zr-MOF-based probes for fluoride so far. • FS@UiO-66 is a highly effective, fast-response and naked-eye sensor for fluoride. - Abstract: In this work, the fluorescent molecule (fluorescein sodium, FS) was successfully incorporated in the zirconium-based MOF (UiO-66) via in-situ synthesis method, which can be confirmed by FTIR spectra and fluorescence microscopic images. Based on this in-situ synthesis strategy, FS molecule can be immobilized tightly in the framework. Furthermore, the resulting FS@UiO-66 demonstrates to be a highly selective, real-time and naked-eye chemical sensor for fluoride in aqueous solution, which is mainly due to the release of FS molecule from FS@UiO-66 into the aqueous solution. Meanwhile, to the best of our knowledge, such Zr-MOF-based fluoride sensor is very rare so far. These results provide a promising approach to rationally design novel MOF-based fluorescent sensor for the target molecules.

  17. Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Shaoyang; Pineda-Galvan, Yuliana; Maza, William A.; Epley, Charity C.; Zhu, Jie; Kessinger, Matthew C.; Pushkar, Yulia; Morris, Amanda J. (VP); (Purdue)

    2016-12-15

    Water oxidation, a key component in artificial photosynthesis, requires high overpotentials and exhibits slow reaction kinetics that necessitates the use of stable and efficient heterogeneous water-oxidation catalysts (WOCs). Here, we report the synthesis of UiO-67 metal–organic framework (MOF) thin films doped with [Ru(tpy)(dcbpy)OH2]2+ (tpy=2,2':6',2''-terpyridine, dcbpy=5,5'-dicarboxy-2,2'-bipyridine) on conducting surfaces and their propensity for electrochemical water oxidation. The electrocatalyst oxidized water with a turnover frequency (TOF) of (0.2±0.1) s-1 at 1.71 V versus the normal hydrogen electrode (NHE) in buffered solution (pH~7) and exhibited structural and electrochemical stability. The electroactive sites were distributed throughout the MOF thin film on the basis of scan-ratedependent voltammetry studies. This work demonstrates a promising way to immobilize large concentrations of electroactive WOCs into a highly robust MOF scaffold and paves the way for future photoelectrochemical water-splitting systems.

  18. Electrochemical investigation of gold nanoparticles incorporated zinc based metal-organic framework for selective recognition of nitrite and nitrobenzene

    International Nuclear Information System (INIS)

    Yadav, Dharmendra Kumar; Ganesan, Vellaichamy; Sonkar, Piyush Kumar; Gupta, Rupali; Rastogi, Pankaj Kumar

    2016-01-01

    Highlights: • Gold nanoparticles incorporated zinc based metal-organic framework is synthesized. • It electro-catalyzes nitrite oxidation and nitrobenzene reduction. • Nitrite and nitrobenzene is determined with high sensitivity. • Hydrodynamic voltammetry studies of nitrite oxidation and nitrobenzene reduction are reported. - Abstract: An electrochemical sensing platform which comprises gold nanoparticles (Au NPs) incorporated zinc based metal-organic framework (MOF-5) is developed for the sensitive determination of nitrite and nitrobenzene. MOF-5 and Au NPs incorporated MOF-5 (Au-MOF-5) are synthesized and characterized by UV-vis absorption, powder X-ray diffraction, FT-IR, scanning electron microscopy with energy dispersive X-ray analysis and elemental mapping, transmission electron microscopy and atomic force microscopy. Oxidation of nitrite is effectively electrocatalyzed at Au-MOF-5 with significant increase in oxidation current (41 and 38% in comparison with bare glassy carbon (GC) and MOF-5 coated GC (GC/MOF-5) electrodes, respectively) and with considerable decrease in the oxidation potential (0. 17 and 0.25 V in comparison with bare GC and GC/MOF-5 electrodes, respectively). The electrocatalytic reduction of nitrobenzene at GC/Au-MOF-5 is confirmed by an appreciable increase in the reduction current (79 and 36% in comparison with bare GC and GC/MOF-5 electrodes, respectively) and a small shift in the reduction potential (20 mV in comparison with GC/MOF-5). The detection limit is calculated as 1.0 μM with a sensitivity of 0.23 μAμM"−"1 cm"−"2 for nitrite and 15.3 μM with a sensitivity of 0.43 μAμM"−"1cm"−"2 for nitrobenzene determinations. The Au-MOF-5 based electrochemical sensing platform shows high stability and selectivity even in the presence of several interferences (including phenols, inorganic ions and biologically important molecules) with a broad calibration range. Certain kinetic parameters of nitrite oxidation and

  19. Cu-Hemin Metal-Organic-Frameworks/Chitosan-Reduced Graphene Oxide Nanocomposites with Peroxidase-Like Bioactivity for Electrochemical Sensing

    International Nuclear Information System (INIS)

    Wang, Li; Yang, Han; He, Juan; Zhang, Yayun; Yu, Jie; Song, Yonghai

    2016-01-01

    Graphical abstract: A simple, sensitive and effective method to detect hydrogen peroxide based on a hybrid Cu-hemin metal-organic-frameworks (MOFs)/chitosan-functionalized reduced graphene oxide (CS-rGO) nanocomposite was achieved via Cu-hemin MOFs constructing with CS-rGO in room temperature. The Cu-hemin MOFs/CS-rGO nanomaterials exhibited a unique peroxidase-like activity and good electrical conductivity as well as some novel properties. And the as-prepared electrode resulted in a perfect electrochemical performance towards reduction of hydrogen peroxide which was superior to natural enzymes and some inorganic mimic enzymes. - Highlights: • A hybrid Cu-hemin MOF/CS-rGO with a unique peroxidase-like activity was prepared. • The CS-rGO improved electrical conductivity of the nanocomposites greatly. • The 3D porous structure enhanced the catalytic activity of hemin for H 2 O 2 . • A novel sensitive electrochemical biosensing for H 2 O 2 detection was achieved. - Abstract: Herein, a Cu-hemin metal-organic-frameworks (MOFs)/chitosan (CS)-reduced graphene oxide (CS-rGO) nanocomposite with unique peroxidase-like bioactivity and good electrical conductivity was prepared for electrochemical H 2 O 2 sensing for the first time. The prepared Cu-hemin MOFs/CS-rGO nanocomposites were well characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray powder diffraction, UV–vis spectroscopy and electrochemical techniques. The results showed that after the Cu-hemin MOFs were formed on the CS-rGO surface, the crystalline structure of the Cu-hemin MOFs was kept while the size of Cu-hemin MOFs was decreased and the electrical conductivity of the nanocomposites was enhanced greatly as compared with that of Cu-hemin MOFs. The unique peroxidase-like bioactivity and good electrical conductivity as well as some novel properties of Cu-hemin MOFs/CS-rGO nanocomposites resulted in

  20. Fabrication and non-covalent modification of highly oriented thin films of a zeolite-like metal-organic framework (ZMOF) with rho topology

    KAUST Repository

    Shekhah, Osama; Cadiau, Amandine; Eddaoudi, Mohamed

    2015-01-01

    Here we report the fabrication of the first thin film of a zeolite-like metal-organic framework (ZMOF) with rho topology (rho-ZMOF-1, ([In48(HImDC)96]48-)n) in a highly oriented fashion on a gold-functionalized substrate. The oriented rho-ZMOF-1