Single-Site Active Iron-Based Bifunctional Oxygen Catalyst for a Compressible and Rechargeable Zinc-Air Battery.

Science.gov (United States)

Ma, Longtao; Chen, Shengmei; Pei, Zengxia; Huang, Yan; Liang, Guojin; Mo, Funian; Yang, Qi; Su, Jun; Gao, Yihua; Zapien, Juan Antonio; Zhi, Chunyi

2018-02-27

The exploitation of a high-efficient, low-cost, and stable non-noble-metal-based catalyst with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) simultaneously, as air electrode material for a rechargeable zinc-air battery is significantly crucial. Meanwhile, the compressible flexibility of a battery is the prerequisite of wearable or/and portable electronics. Herein, we present a strategy via single-site dispersion of an Fe-N x species on a two-dimensional (2D) highly graphitic porous nitrogen-doped carbon layer to implement superior catalytic activity toward ORR/OER (with a half-wave potential of 0.86 V for ORR and an overpotential of 390 mV at 10 mA·cm -2 for OER) in an alkaline medium. Furthermore, an elastic polyacrylamide hydrogel based electrolyte with the capability to retain great elasticity even under a highly corrosive alkaline environment is utilized to develop a solid-state compressible and rechargeable zinc-air battery. The creatively developed battery has a low charge-discharge voltage gap (0.78 V at 5 mA·cm -2 ) and large power density (118 mW·cm -2 ). It could be compressed up to 54% strain and bent up to 90° without charge/discharge performance and output power degradation. Our results reveal that single-site dispersion of catalytic active sites on a porous support for a bifunctional oxygen catalyst as cathode integrating a specially designed elastic electrolyte is a feasible strategy for fabricating efficient compressible and rechargeable zinc-air batteries, which could enlighten the design and development of other functional electronic devices.

High-Activity Dealloyed Catalysts

Energy Technology Data Exchange (ETDEWEB)

Kongkanand, Anusorn [General Motors LLC, Pontiac, MI (United States)

2014-09-30

Reduction of costly Pt usage in proton exchange membrane fuel cell electrodes is one of the major challenges towards development and commercialization of fuel cell vehicles. Although few have met the initial-kinetic activity requirements in a realistic fuel cell device, no catalyst material has ever met the demanding fuel cell durability targets set by DOE. In this project, a team of 4 universities and 2 companies came together to investigate a concept that appeared promising in preliminary non-fuel cell tests then to further develop the catalyst to a mature level ready for vehicle implementation. The team consists of academia with technical leadership in their respective areas, a catalyst supplier, and a fuel cell system integrator.The tightly collaborative project enabled development of a highly active and durable catalyst with performance that significantly exceeds that of previous catalysts and meets the DOE targets for the first time (Figure 1A). The catalyst was then further evaluated in full-active-area stack in a realistic vehicle operating condition (Figure 1B). This is the first public demonstration that one can realize the performance benefit and Pt cost reduction over a conventional pure Pt catalyst in a long-term realistic PEMFC system. Furthermore, systematic analyses of a range of catalysts with different performance after fuel cell testing allowed for correlation between catalyst microstructure and its electrocatalytic activity and durability. This will in turn aid future catalyst development.

Pt Nanostructures/N-Doped Carbon hybrid, an Efficient Catalyst for Hydrogen Evolution/Oxidation Reactions: Enhancing its Base Media Activity through Bifunctionality of the Catalyst.

Science.gov (United States)

Barman, Sudip; Kundu, Manas; Bhowmik, Tanmay; Mishra, Ranjit

2018-06-04

Design and synthesis of active catalyst for HER/HOR are important for the development of hydrogen based renewable technologies. We report synthesis of Pt nanostructures-N-doped carbon hybrid (Pt-(PtO2)-NSs/C) for HER/HOR applications. The HER activity of this Pt-(PtOx)-NSs/C catalyst is 4 and 6.5 times better than commercial Pt/C in acid and base. The catalyst exhibits a current density of 10 mA/cm2 at overpotentials of 5 and 51 mV with tafel slopes of 29 and 64mV/dec in in 0.5 M H2SO4 and 0.5 M KOH. This catalyst also showed superior HOR activity at all pH values. The HER/HOR activity of Pt-(PtOx)-NSs/C and PtOx-free Pt-Nanostructures/C (PtNSs/C) catalysts are comparable in acid. The presence of PtOx in Pt-(PtOx)-NSs/C makes this Pt-catalyst more HER/HOR active in base media. The activity of Pt-(PtOx)NSs/C catalyst is 5 fold higher than that of PtNSs/C catalyst in basic medium although their activity is comparable in acid. Hydrogen binding energy and oxophilicity are the two equivalent descriptors for HER/HOR in basic media. We propose a bi-functional mechanism for the enhanced alkaline HER/HOR activity of Pt(PtOx)-NSs/C catalyst. In bi-functional Pt-(PtOx)-NSs/C catalyst, PtOx provide an active site for OH- adsorption to form OHads which reacts with hydrogen intermediate (Hads), present at neighbouring Pt sites to form H2O leading to enhancement of HOR activity in basic medium This work may provide opportunity to develop catalysts for various renewable energy technologies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Communicating catalysts

Science.gov (United States)

Weckhuysen, Bert M.

2018-06-01

The beauty and activity of enzymes inspire chemists to tailor new and better non-biological catalysts. Now, a study reveals that the active sites within heterogeneous catalysts actively cooperate in a fashion phenomenologically similar to, but mechanistically distinct, from enzymes.

Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

KAUST Repository

Mazoyer, Etienne

2011-12-02

1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

The concept, reality and utility of single-site heterogeneous catalysts (SSHCs).

Science.gov (United States)

Thomas, John Meurig

2014-05-07

Very substantial advances have recently been made in the design and construction of solid catalysts and in elucidating both their mode of operation and the factors that determine their selectivity and longevity. This Perspective explains how and why such progress has been made. One important factor, the deployment of single-site heterogeneous and enzymatic catalysts, used either alone or in conjunction with other strategies, including metabolic engineering, enables a multitude of new products (for example, environmentally clean jet fuel) to be readily manufactured. In a practical sense SSHCs enable the advantages of homogeneous and to a lesser degree enzymatic catalysts to be united with those of heterogeneous ones. With the aid of the vastly increasing families of nanoporous solids, desired catalytically active sites may be engineered in atomic detail on their inner, accessible surfaces, thereby opening up new possibilities in synthetic organic chemistry - as in the smooth formation of C-C and C[double bond, length as m-dash]N bonds in a number of intermolecular reactions - as well as in photocatalysts and in fluidized catalytic cracking of hydrocarbons.

On factors controlling activity of submonolayer bimetallic catalysts: Nitrogen desorption

Energy Technology Data Exchange (ETDEWEB)

Guo, Wei; Vlachos, Dionisios G., E-mail: vlachos@udel.edu [Center for Catalytic Science and Technology, Catalysis Center for Energy Innovation, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware 19716 (United States)

2014-01-07

We model N{sub 2} desorption on submonolayer bimetallic surfaces consisting of Co clusters on Pt(111) via first-principles density functional theory-based kinetic Monte Carlo simulations. We find that submonolayer structures are essential to rationalize the high activity of these bimetallics in ammonia decomposition. We show that the N{sub 2} desorption temperature on Co/Pt(111) is about 100 K higher than that on Ni/Pt(111), despite Co/Pt(111) binding N weaker at low N coverages. Co/Pt(111) has substantially different lateral interactions than single metals and Ni/Pt. The lateral interactions are rationalized with the d-band center theory. The activity of bimetallic catalysts is the result of heterogeneity of binding energies and reaction barriers among sites, and the most active site can differ on various bimetallics. Our results are in excellent agreement with experimental data and demonstrate for the first time that the zero-coverage descriptor, used until now, for catalyst activity is inadequate due not only to lacking lateral interactions but importantly to presence of multiple sites and a complex interplay of thermodynamics (binding energies, occupation) and kinetics (association barriers) on those sites.

Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

Directory of Open Access Journals (Sweden)

Subbarao Duvvuri

2011-11-01

Full Text Available Abstract This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR, temperature-programmed oxidation (TPO, CO-chemisorption, transmission electron microscopy (TEM, field emission scanning electron microscopy (FESEM-EDX and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low, 650°C (medium and 731°C (high. The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1% while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%.

Mechanisms of catalytic activity in heavily coated hydrocracking catalysts

Energy Technology Data Exchange (ETDEWEB)

Millan, M.; Adell, C.; Hinojosa, C.; Herod, A.A.; Kandiyoti, R. [University of London Imperial College Science Technology & Medicine, London (United Kingdom). Dept. of Chemical Engineering

2008-01-15

Catalyst deactivation by coke deposition has a direct impact on the economic viability of heavy hydrocarbon upgrading processes, such as coal liquefaction and oil residue hydroprocessing. Coke deposition is responsible for rapid loss of catalytic activity and it mostly takes place in the early stages of hydrocracking. The effect of carbonaceous deposition on the catalytic activity of a chromium pillared montmorillonite has been studied in the present work. Its catalytic activity in hydrocracking a coal extract was evaluated based on the boiling point distributions of feed and products obtained by thermogravimetric analysis (TGA), and their characterisation by size exclusion chromatography (SEC) and UV-Fluorescence spectroscopy (UV-F). A large deposition on the catalyst was observed after two successive 2-hour long runs in which the catalyst recovered from the first run was reused in the second. The pillared clay retained its activity even though it showed high carbon loading, a large drop in surface area and complete apparent pore blockage. Some observations may contribute to explain this persistent catalytic activity. First, there is evidence suggesting the dynamic nature of the carbonaceous deposits, which continuously exchange material with the liquid, allowing catalytic activity to continue. Secondly, Scanning Electron Microscopy (SEM) on the used Cr montmorillonite has shown preferential deposition on some regions of the catalyst, which leaves a fraction of the surface relatively exposed. Finally, evidence from SEM coupled to X-ray microanalysis also suggest that deposits are thinner in areas where the active phase of the catalyst is present in higher concentrations. Hydrogenation on the active sites would make the deposits more soluble in the liquid cleaning of surrounding area from deposits.

Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis

Energy Technology Data Exchange (ETDEWEB)

Mouat, Aidan R.; Lohr, Tracy L.; Wegener, Evan C.; Miller, Jeffrey T.; Delferro, Massimiliano; Stair, Peter C.; Marks, Tobin J.

2016-08-23

A single-site molybdenum dioxo catalyst, (O_c)₂Mo(=O)₂@C, was prepared via direct grafting of MoO₂Cl₂(dme) (dme = 1,2-dimethoxyethane) on high-surface- area activated carbon. The physicochemical and chemical properties of this catalyst were fully characterized by N₂ physisorption, ICP-AES/OES, PXRD, STEM, XPS, XAS, temperature-programmed reduction with H₂ (TPR-H₂), and temperature-programmed NH₃ desorption (TPD-NH₃). The single-site nature of the Mo species is corroborated by XPS and TPR-H₂ data, and it exhibits the lowest reported MoO_x Tmax of reduction reported to date, suggesting a highly reactive MoVI center. (O_c)₂Mo(=O)₂@C catalyzes the transesterification of a variety of esters and triglycerides with ethanol, exhibiting high activity at moderate temperatures (60-90 °C) and with negligible deactivation. (O_c)₂Mo(=O)₂@C is resistant to water and can be recycled at least three times with no loss of activity. The transesterification reaction is determined experimentally to be first order in [ethanol] and first order in [Mo] with ΔH = 10.5(8) kcal mol^-1 and ΔS = -32(2) eu. The low energy of activation is consistent with the moderate conditions needed to achieve rapid turnover. This highly active carbon-supported single-site molybdenum dioxo species is thus an efficient, robust, and lowcost catalyst with significant potential for transesterification processes.

Activating catalysts with mechanical force

NARCIS (Netherlands)

Piermattei, A.; Karthikeyan, S.; Sijbesma, R.P.

2009-01-01

Homogeneously catalysed reactions can be ‘switched on’ by activating latent catalysts. Usually, activation is brought about by heat or an external chemical agent. However, activation of homogeneous catalysts with a mechanical trigger has not been demonstrated. Here, we introduce a general method to

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

Science.gov (United States)

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-01-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal−air batteries. Herein, we report the novel system of nickel−aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles. PMID:27650532

Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure.

Science.gov (United States)

Jarupatrakorn, Jonggol; Don Tilley, T

2002-07-17

A molecular precursor approach involving simple grafting procedures was used to produce site-isolated titanium-supported epoxidation catalysts of high activity and selectivity. The tris(tert-butoxy)siloxy titanium complexes Ti[OSi(O(t)Bu)(3)](4) (TiSi4), ((i)PrO)Ti[OSi(O(t)Bu)(3)](3) (TiSi3), and ((t)BuO)(3)TiOSi(O(t)Bu)(3) (TiSi) react with the hydroxyl groups of amorphous Aerosil, mesoporous MCM-41, and SBA-15 via loss of HO(t)Bu and/or HOSi(O(t)Bu)(3) and introduction of titanium species onto the silica surface. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared, and diffuse reflectance ultraviolet spectroscopies were used to investigate the structures and chemical natures of the surface-bound titanium species. The titanium species exist mainly in isolated, tetrahedral coordination environments. Increasing the number of siloxide ligands in the molecular precursor decreases the amount of titanium that can be introduced this way, but also enhances the catalytic activity and selectivity for the epoxidation of cyclohexene with cumene hydroperoxide as oxidant. In addition, the high surface area mesoporous silicas (MCM-41 and SBA-15) are more effective than amorphous silica as supports for these catalysts. Supporting TiSi3 on the SBA-15 affords highly active cyclohexene epoxidation catalysts (0.25-1.77 wt % Ti loading) that provide turnover frequencies (TOFs) of 500-1500 h(-1) after 1 h (TOFs are reduced by about half after calcination). These results demonstrate that oxygen-rich siloxide complexes of titanium are useful as precursors to supported epoxidation catalysts.

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Hanguang [Department; Hwang, Sooyeon [Center; Wang, Maoyu [School; Feng, Zhenxing [School; Karakalos, Stavros [Department; Luo, Langli [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Qiao, Zhi [Department; Xie, Xiaohong [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wang, Chongmin [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Su, Dong [Center; Shao, Yuyan [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wu, Gang [Department

2017-09-26

To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that is determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Karakalos, Stavros; Luo, Langli; Qiao, Zhi; Xie, Xiaohong; Wang, Chongmin; Su, Dong; Shao, Yuyan; Wu, Gang (BNL); (Oregon State U.); (SC); (PNNL); (Buffalo)

2017-09-26

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability

Direct instrumental identification of catalytically active surface sites

Science.gov (United States)

Pfisterer, Jonas H. K.; Liang, Yunchang; Schneider, Oliver; Bandarenka, Aliaksandr S.

2017-09-01

The activity of heterogeneous catalysts—which are involved in some 80 per cent of processes in the chemical and energy industries—is determined by the electronic structure of specific surface sites that offer optimal binding of reaction intermediates. Directly identifying and monitoring these sites during a reaction should therefore provide insight that might aid the targeted development of heterogeneous catalysts and electrocatalysts (those that participate in electrochemical reactions) for practical applications. The invention of the scanning tunnelling microscope (STM) and the electrochemical STM promised to deliver such imaging capabilities, and both have indeed contributed greatly to our atomistic understanding of heterogeneous catalysis. But although the STM has been used to probe and initiate surface reactions, and has even enabled local measurements of reactivity in some systems, it is not generally thought to be suited to the direct identification of catalytically active surface sites under reaction conditions. Here we demonstrate, however, that common STMs can readily map the catalytic activity of surfaces with high spatial resolution: we show that by monitoring relative changes in the tunnelling current noise, active sites can be distinguished in an almost quantitative fashion according to their ability to catalyse the hydrogen-evolution reaction or the oxygen-reduction reaction. These data allow us to evaluate directly the importance and relative contribution to overall catalyst activity of different defects and sites at the boundaries between two materials. With its ability to deliver such information and its ready applicability to different systems, we anticipate that our method will aid the rational design of heterogeneous catalysts.

ACTIVITY TEST AND REGENERATION OF NiMo/Z CATALYST FOR HYDROCRACKING OF WASTE PLASTIC FRACTION TO GASOLINE FRACTION

Directory of Open Access Journals (Sweden)

Rodiansono Rodiansono

2010-06-01

Full Text Available Activity test and regeneration of NiMo/active natural zeolite catalyst for hydrocracking of waste plastic fraction of polyprophylene (PP type have been carried out. The catalysts was prepared by loading Mo followed by Ni Metals onto the natural zeolite (Z sample, then calcined at 500oC, oxidized and reduced at 400oC under nitrogen, oxygen and hydrogen stream, respectively. The characterization of catalysts including spesific surface area, average pore radius, and total pore volume were performed by gas sorption analyzer, amount of total acid sites was determined by gas sorption method, and acid site strength was confirmed by IR spectroscopy. The hydrocracking process was carried out in a semi-flow reactor system at 360 oC and catalyst:feed ratio 0.5 under hydrogen stream (150 mL/hour. The feed was vaporized from the pyrolisis reactor into the hydrocracking reactor. A liquid product was collected and analyzed by gas chromatography (GC and gas chromatography-mass spectroscopy (GC-MS. The characterization results showed that spesific surface area, average pore radius, and total pore volume of the Z sample decreased after loading of the Ni and Mo metals. Amount of total acid sites of the NiMo/Z catalyst was higher than that of the Z sample. The activity of NiMo/Z catalyst decreased after several continously runs. Its regeneration produced the NiMo/Z reg catalyst with similar activity and selectivity to the fresh catalyst (NiMo/Z. The activity of catalysts at the optimum condition followed the order of NiMo/Z reg>NiMo/Z>Z (conversion of hydrocarbon C>12 and NiMo/Z reg>NiMo/Z>Z (total yield of gasoline fraction. The selectivity of catalysts for C7-C8 product followed the order of Z>NiMo/Z>NiMo/Z reg. Keywords: activity, polyprophylene, catalyst, gasoline fraction.

Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

Energy Technology Data Exchange (ETDEWEB)

Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

2015-01-01

ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

Patched bimetallic surfaces are active catalysts for ammonia decomposition.

Science.gov (United States)

Guo, Wei; Vlachos, Dionisios G

2015-10-07

Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core-shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core-shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

Deactivation-resistant catalyst for selective catalyst reduction of NOx

DEFF Research Database (Denmark)

2011-01-01

The present invention relates to a catalyst for selective catalytic reduction of NOx in alkali metal containing flue gas using ammonia as reductant, the catalyst comprising a surface with catalytically active sites, wherein the surface is at least partly coated with a coating comprising at least...... one metal oxide. In another aspect the present invention relates to the use of said catalyst and to a method of producing said catalyst. In addition, the present invention relates to a method of treating an catalyst for conferring thereon an improved resistance to alkali poisoning....

Elucidating the Origin of Hydrogen Evolution Reaction Activity in Mono- and Bimetallic Metal- and Nitrogen-Doped Carbon Catalysts (Me-N-C).

Science.gov (United States)

Shahraei, Ali; Moradabadi, Ashkan; Martinaiou, Ioanna; Lauterbach, Stefan; Klemenz, Sebastian; Dolique, Stephanie; Kleebe, Hans-Joachim; Kaghazchi, Payam; Kramm, Ulrike I

2017-08-02

In this work, we present a comprehensive study on the role of metal species in MOF-based Me-N-C (mono- and bimetallic) catalysts for the hydrogen evolution reaction (HER). The catalysts are investigated with respect to HER activity and stability in alkaline electrolyte. On the basis of the structural analysis by X-ray diffraction, X-ray-induced photoelectron spectroscopy, and transmission electron microscopy, it is concluded that MeN 4 sites seem to dominate the HER activity of these catalysts. There is a strong relation between the amount of MeN 4 sites that are formed and the energy of formation related to these sites integrated at the edge of a graphene layer, as obtained from density functional theory (DFT) calculations. Our results show, for the first time, that the combination of two metals (Co and Mo) in a bimetallic (Co,Mo)-N-C catalyst allows hydrogen production with a significantly improved overpotential in comparison to its monometallic counterparts and other Me-N-C catalysts. By the combination of experimental results with DFT calculations, we show that the origin of the enhanced performance of our (Co,Mo)-N-C catalyst seems to be provided by an improved hydrogen binding energy on one MeN 4 site because of the presence of a second MeN 4 site in its close vicinity, as investigated in detail for our most active (Co,Mo)-N-C catalyst. The outstanding stability and good activity make especially the bimetallic Me-N-C catalysts interesting candidates for solar fuel applications.

Highly Stable and Active Catalyst for Sabatier Reactions

Science.gov (United States)

Hu, Jianli; Brooks, Kriston P.

2012-01-01

Highly active Ru/TiO2 catalysts for Sabatier reaction have been developed. The catalysts have shown to be stable under repeated shutting down/startup conditions. When the Ru/TiO2 catalyst is coated on the engineered substrate Fe-CrAlY felt, activity enhancement is more than doubled when compared with an identically prepared engineered catalyst made from commercial Degussa catalyst. Also, bimetallic Ru-Rh/TiO2 catalysts show high activity at high throughput.

Productions of palm oil bio diesel whit heterogeneous basic catalysts compared to conventional homogeneous catalysts

International Nuclear Information System (INIS)

Rios, Luis A; Franco C, Alexander; Zuleta S, Ernesto

2009-01-01

The conventional process to produce biodiesel involves the presence of homogeneous basic catalysts. However, these catalysts have disadvantages associated to the need of purification steps, which increase the cost of the final product and generate pollution problems caused by the effluents. This paper compares different homogeneous and heterogeneous catalysts for the biodiesel production from palm oil. For this, heterogeneous catalysts supported on alumina were prepared and characterized by nitrogen adsorption, scanning electron microscopy, energy dispersive X ray spectroscopy and X ray diffraction. Transesterification of palm oil with methanol was accomplished at 60 celsius degrade and one hour, varying methanol/oil ratio, the type of catalyst and its concentration. Yields of the reaction and purity of the so obtained biodiesel were evaluated. Comparing the catalysts performance, based on the amount, was found that sodium methoxide (CH 3 ONa) and potassium carbonate supported on alumina (K 2 CO 3 /Al 2 O 3 ) were the catalysts that give the higher purity of biodiesel (96.8 and 95.85% respectively). When was determined the active site quality, by dividing the performance by each mole of active sites, it was found that calcined Na 2 SO 4 /Al 2 O 3 has the most active sites.

Process of activation of a palladium catalyst system

Science.gov (United States)

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-08-02

Improved processes for activating a catalyst system used for the reduction of nitrogen oxides are provided. In one embodiment, the catalyst system is activated by passing an activation gas stream having an amount of each of oxygen, water vapor, nitrogen oxides, and hydrogen over the catalyst system and increasing a temperature of the catalyst system to a temperature of at least 180.degree. C. at a heating rate of from 1-20.degree./min. Use of activation processes described herein leads to a catalyst system with superior NOx reduction capabilities.

Preparation and characterization of the perovskite catalysts : activity studies for diesel surrogate (dodecane) reforming

Energy Technology Data Exchange (ETDEWEB)

Kondakindi, R.; Kundu, A.; Karan, K.; Peppley, B. [Queen' s-RMC Fuel Cell Research Centre, Kingston, ON (Canada)

2009-07-01

Canada's northern communities rely on diesel fuel for generating electricity. The process of converting diesel to electricity in internal combustion engines is not efficient and generates significant amounts of unwanted products. This paper presented an alternative process whereby diesel is reformed into hydrogen-rich reformate which can then be fed to a solid oxide fuel cell. This alternative process converts energy more efficiently and eliminates the formation of nitrogen oxides (NOx) and soot. This study focused on the development of LaFeO{sub 3} based perovskite catalysts for diesel reforming. The activity of the perovskite catalysts was assessed for steam reforming of dodecane, a surrogate for diesel. In order to study the effect on catalytic activity, various perovskite materials were prepared by doping the perovskite at A-site to minimize the coke deposition and at B-site to improve the activity. Preliminary results for dodecane reforming for selected perovskites were promising. Additional testing is underway regarding catalyst activity and stability studies as well carbon and sulphur poisoning.

Effects of preparation method and active metal content on of Ni/kieselguhr catalyst activity

International Nuclear Information System (INIS)

Galuh Widiyarti; Wuryaningsih Sri Rahayu

2010-01-01

The preparation and the active metal content influence the activity of catalyst. Study has been conducted to see the activity of Ni/kieselguhr based on preparation method and Nickel (Ni) contents in the catalyst in the laboratory scale. The Ni/kieselguhr catalyst were prepared by impregnation and precipitation methods, with Ni active contents of 10, 20, and 30 % by weight. The catalysts characterization was analyzed using X-Ray Diffraction (XRD). Catalysts activities were analyzed based on decreasing of iodine number from hydrogenation of crude palm oil for 2 hours. The activity tests results show that precipitation catalysts are more active than impregnation catalysts. The decreasing in iodine number of fatty acid after 2 hours of hydrogenation process using precipitation catalysts and impregnation catalysts are 51.53 and 21.85 %, respectively. In addition, the catalysts are more active with increasing Ni contents. (author)

Active Iron Sites of Disordered Mesoporous Silica Catalyst FeKIL-2 in the Oxidation of Volatile Organic Compounds (VOC

Directory of Open Access Journals (Sweden)

Mojca Rangus

2014-05-01

Full Text Available Iron-functionalized disordered mesoporous silica (FeKIL-2 is a promising, environmentally friendly, cost-effective and highly efficient catalyst for the elimination of volatile organic compounds (VOCs from polluted air via catalytic oxidation. In this study, we investigated the type of catalytically active iron sites for different iron concentrations in FeKIL-2 catalysts using advanced characterization of the local environment of iron atoms by a combination of X-ray Absorption Spectroscopy Techniques (XANES, EXAFS and Atomic-Resolution Scanning Transmission Electron Microscopy (AR STEM. We found that the molar ratio Fe/Si ≤ 0.01 leads to the formation of stable, mostly isolated Fe3+ sites in the silica matrix, while higher iron content Fe/Si > 0.01 leads to the formation of oligonuclear iron clusters. STEM imaging and EELS techniques confirmed the existence of these clusters. Their size ranges from one to a few nanometers, and they are unevenly distributed throughout the material. The size of the clusters was also found to be similar, regardless of the nominal concentration of iron (Fe/Si = 0.02 and Fe/Si = 0.05. From the results obtained from sample characterization and model catalytic tests, we established that the enhanced activity of FeKIL-2 with the optimal Fe/Si = 0.01 ratio can be attributed to: (1 the optimal concentration of stable isolated Fe3+ in the silica support; and (2 accelerated diffusion of the reactants in disordered mesoporous silica (FeKIL-2 when compared to ordered mesoporous silica materials (FeSBA-15, FeMCM-41.

Non-PGM cell catalysts

Energy Technology Data Exchange (ETDEWEB)

Colon-Mercado, H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Elvington, M. [Savannah River Consulting, Aiken, SC (United States); Ganesan, P. [Savannah River Consulting, Aiken, SC (United States)

2017-09-27

A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFCs. Iron based functionalities have been engineered into a variety of catalysts to evaluate their impact on activity for the ORR. A series of high surface area catalysts were synthesized and the impact of the chemical structure on the electrochemical and electrocatalytic properties was investigated. Elemental and surface analyses of the prepared catalysts reveal the incorporation of iron in a targeted and controlled manner. A high surface area framework catalyst was prepared that shows exceptional activity, comparable to state-of-the-art materials. The results of this research project provided critical seed data for the newly awarded ElectroCat project, which focuses on rationally designed framework catalysts for the oxygen reduction reaction.

Uniformly active phase loaded selective catalytic reduction catalysts (V_2O_5/TNTs) with superior alkaline resistance performance

International Nuclear Information System (INIS)

Wang, Haiqiang; Wang, Penglu; Chen, Xiongbo; Wu, Zhongbiao

2017-01-01

Highlights: • VOSO_4 exhibited better synergistic effect with titanate nanotubes than NH_4VO_3. • Ion-exchange reaction occurs between VOSO_4 and titanate nanotubes. • Ion-exchange resulting in uniformly vanadium distribution on titanate nanotubes. • VOSO_4-based catalyst exhibited impressive SCR activity and alkaline resistance. - Abstract: In this work, protonated titanate nanotubes was performed as a potential useful support and different vanadium precursors (NH_4VO_3 and VOSO_4) were used to synthesize deNO_x catalysts. The results showed that VOSO_4 exhibited better synergistic effect with titanate nanotubes than NH_4VO_3, which was caused by the ion-exchange reaction. Then high loading content of vanadium, uniformly active phase distribution, better dispersion of vanadium, more acid sites, better V"5"+/V"4"+ redox cycles and superior oxygen mobility were achieved. Besides, VOSO_4-based titanate nanotubes catalysts also showed enhanced alkaline resistance than particles (P25) based catalysts. It was strongly associated with its abundant acid sites, large surface area, flexible redox cycles and oxygen transfer ability. For the loading on protonated titanate nanotubes, active metal with cation groups was better precursors than anion ones. V_2O_5/TNTs catalyst was a promising substitute for the commercial vanadium catalysts and the work conducted herein provided a useful idea to design uniformly active phase loaded catalyst.

Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

KAUST Repository

Ou, Yiwei

2011-11-01

The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

KAUST Repository

Ou, Yiwei; Kumagai, Hiromu; Yin, Fengxiang; Okada, Saori; Hatasawa, Haruna; Morioka, Hiroyuki; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

2011-01-01

The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

Directory of Open Access Journals (Sweden)

Khalid Khazzal Hummadi

2009-06-01

Full Text Available The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK, 10 atm (1013 kPa, with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a commercial catalyst; maximum selectivity (82.3% was obtained at 573oK when the conversion was 59.7%. Catalysts prepared by reacting iron (III and molybdate by kneading or precipitation followed by evaporation, omitting a filtration stage, were less active and less selective. The selectivity-activity relationships of these catalysts as a function of temperature were discussed in relation to the method of preparation, surface areas and composition. By combing this catalytic data with data from the patent literature we demonstrate a synergy between iron and molybdenum in regard to methanol oxidation to formaldehyde; the optimum composition corresponded to an iron mole fraction 0.2-0.3. The selectivity to formaldehyde was practically constant up to an iron mole fraction 0.3 and then decreased at higher iron concentrations. The iron component can be regarded as the activity promoter. The iron molybdate catalysts can thus be related to other two-component MoO3-based selective oxidation catalysts, e.g. bismuth and cobalt molybdates. The iron oxide functions as a relatively basic oxide abstracting, in the rate-controlling step, a proton from the methyl of a bound methoxy group of chemisorbed methanol. It was proposed that a crucial feature of the sought after iron(III molybdate catalyst is the presence of -O-Mo-O-Fe-O-Mo-O- groups as found in the compound Fe2(MoO43 and for Fe3+ well dispersed in MoO3 generally. At the higher iron(III concentrations the loss of

Petroleum residue upgrading with dispersed catalysts. Part 1. Catalysts activity and selectivity

Energy Technology Data Exchange (ETDEWEB)

Panariti, N.; Del Bianco, A.; Del Piero, G. [ENITECNOLOGIE S.p.A, Via Maritano 26, 20097 San Donato Mil. (Italy); Marchionna, M. [SNAMPROGETTI S.p.A, Via Maritano 26, 20097 San Donato Mil. (Italy)

2000-12-04

The results of a study aimed at the identification of the relevant chemical aspects involved in the process of upgrading heavy feedstocks in the presence of dispersed catalysts are discussed. The catalytic activity of different compounds was compared in terms of products yields and quality. Moreover, a detailed and systematic characterization of the catalysts recovered at the end of the reactions was achieved. The experimental work provided quite a large set of data, allowing to investigate the factors that may affect catalyst activity (precursor solubility, rate of activation, degree of dispersion, presence of promoters, etc.). The results of this study demonstrate that the best performances are obtained by the microcrystalline molybdenite generated in situ by oil-soluble precursors. The nature of the organic ligand does not play a very relevant role in influencing the hydrogenation activity. The presence of phosphorus, however, significantly enhances hydrodemetallation, at least in terms of vanadium removal. Bimetallic precursors show a slight synergistic effect towards the hydrodesulfurization reaction. Microsized powdered catalyst precursors have a much lower catalytic activity compared to the oil-soluble ones.

The activity of supported vanadium oxide catalysts for the selective reduction of NO with ammonia

NARCIS (Netherlands)

Bosch, H.; Janssen, Frans J.J.G.; van den Kerkhof, Frans M.G.; Oldenziel, Jaap; van Ommen, J.G.; Ross, Julian R.H.

1986-01-01

The activities of monolayer V2O5 catalysts for the selective reduction of NO with NH3 are compared with those of commercial available catalysts containing V and/or W. From steady state and pulse experiments it can be concluded that the reduction of surface sites proceeds either by NH3 + NO or by NH3

Activation of a Cu/ZnO catalyst for methanol synthesis

DEFF Research Database (Denmark)

Andreasen, Jens Wenzel; Rasmussen, F.B.; Helveg, S.

2006-01-01

The structural changes during activation by temperature-programmed reduction of a Cu/ZnO catalyst for methanol synthesis have been studied by several in situ techniques. The catalyst is prepared by coprecipitation and contains 4.76 wt% Cu, which forms a substitutional solid solution with Zn......O as determined by resonant X-ray diffraction. In situ resonant X-ray diffraction reveals that the Cu atoms are extracted from the solid solution by the reduction procedure, forming metallic Cu crystallites. Cu is redispersed in bulk or surface Zn lattice sites upon oxidation by heating in air. The results...... is highly dispersed and in intimate contact with the surface of the host ZnO particles. The possibility of re-forming the (Zn,Cu)O solid solution by oxidation may provide a means of redispersing Cu in a deactivated catalyst....

Active carbon catalyst for heavy oil upgrading

Energy Technology Data Exchange (ETDEWEB)

Fukuyama, Hidetsugu; Terai, Satoshi [Technology Research Center, Toyo Engineering Corporation, 1818 Azafujimi, Togo, Mobara-shi, Chiba 297-00017 (Japan); Uchida, Masayuki [Business Planning and Exploring Department, Overseas Business Development and Marketing Division, Toyo Engineering Corporation, 2-8-1 Akanehama, Narashino-shi, Chiba 275-0024 (Japan); Cano, Jose L.; Ancheyta, Jorge [Maya Crude Treatment Project, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas No. 152, Col. San Bartolo Atepehuacan, Mexico D.F. 07730 (Mexico)

2004-11-24

The active carbon (AC) catalyst was studied by hydrocracking of Middle Eastern vacuum residue (VR) for heavy oil upgrading. It was observed that the active carbon has the affinity to heavy hydrocarbon compounds and adsorption selectivity to asphaltenes, and exhibits better ability to restrict the coke formation during the hydrocracking reaction of VR. The mesopore of active carbon was thought to play an important role for effective conversion of heavy hydrocarbon compounds into lighter fractions restricting carbon formation. The performance of the AC catalyst was examined by continuous hydrocracking by CSTR for the removal of such impurities as sulfur and heavy metals (nickel and vanadium), which are mostly concentrated in the asphaltenes. The AC catalyst was confirmed to be very effective for the removal of heavy metals from Middle Eastern VR, Maya/Istmo VR and Maya VR. The extruded AC catalysts were produced by industrial manufacturing method. The application test of the extruded AC catalyst for ebullating-bed reactor as one of the commercially applicable reactors was carried out at the ebullating-bed pilot plant for 500h. The ebullition of the extruded AC catalyst was successfully traced and confirmed by existing {gamma}-ray density meter. The extruded AC catalyst showed stable performance with less sediment formation at an equivalent conversion by conventional alumina catalyst at commercial ebullating-bed unit. The degradation of the AC catalyst at the aging test was observed to be less than that of the conventional alumina catalyst. Thus, the AC catalyst was confirmed to be effective and suitable for upgrading of heavy oil, especially such heavy oils as Maya, which contains much heavy metals.

Effects of composition on structure and activity of PtRu/C catalysts.

Science.gov (United States)

Wiltshire, Richard J K; King, Colin R; Rose, Abigail; Wells, Peter P; Davies, Hazel; Hogarth, Martin P; Thompsett, David; Theobald, Brian; Mosselmans, Fredrick W; Roberts, Mark; Russell, Andrea E

2009-04-07

A series of carbon supported PtRu bimetallic catalysts with varying Pt:Ru ratio were prepared and characterised using ex situ and in situ XRD, in situ EXAFS at 0 V vs. RHE, ex situ XPS and monolayer CO stripping voltammetry. Although the catalysts were found to be well mixed/alloyed, with no evidence of unalloyed Ru (oxides) present, the surfaces of the electrocatalyst nanoparticles were found to be enriched with Pt compared to the nominal bulk composition. The methanol oxidation activities of the catalysts were determined in 1.0 mol dm(-3) H2SO4. In agreement with published studies of polycrystalline bulk PtRu alloys the catalyst with a 0.6 surface fraction of Pt was found to give the best methanol oxidation activity at 30 degrees C. However, at 80 degrees C a greater surface fraction of Ru could be tolerated, with some activity at low current densities found for a Pt surface fraction as low as 0.2. The results support the conclusion that a limited amount of methanol dehydrogenation occurs at Ru sites or Ru dominated surface ensembles at 80 degrees C.

Deactivation of solid catalysts in liquid media: the case of leaching of active sites in biomass conversion reactions

DEFF Research Database (Denmark)

Sádaba, Irantzu; Lopez Granados, Manuel; Riisager, Anders

2015-01-01

This review is aimed to be a brief tutorial covering the deactivation of solid catalysts in the liquid phase, with specific focus on leaching, which can be especially helpful to researchers not familiarized with catalytic processes in the liquid phase. Leaching refers to the loss of active species....... However, as a consequence of the development of new processes for biorefineries, an increasing number of reactions deal with liquid media, and thus, the stability and reusability of a solid catalyst in this situation represent a huge challenge that requires specific attention. Leaching of active phases...... is particularly problematic because of its irreversibility and it can be one of the main causes of catalyst deactivation in liquid media, threatening the sustainability of the process. This tutorial review presents a survey of the main aspects concerning the deactivation due to leaching of active species from...

Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C-H bond activation.

Science.gov (United States)

Zhang, Shengbo; Wang, Hua; Li, Mei; Han, Jinyu; Liu, Xiao; Gong, Jinlong

2017-06-01

Heterogeneous metal complex catalysts for direct C-H activation with high activity and durability have always been desired for transforming raw materials into feedstock chemicals. This study described the design and synthesis of one-dimensional organosilica nanotubes containing 2,2'-bipyridine (bpy) ligands in the framework (BPy-NT) and their post-synthetic metalation to provide highly active and robust molecular heterogeneous catalysts. By adjusting the ratios of organosilane precursors, very short BPy-NT with ∼50 nm length could be controllably obtained. The post-synthetic metalation of bipyridine-functionalized nanotubes with [IrCp*Cl(μ-Cl)] 2 (Cp* = η 5 -pentamethylcyclopentadienyl) and [Ir(cod)(OMe)] 2 (cod = 1,5-cyclooctadiene) afforded solid catalysts, IrCp*-BPy-NT and Ir(cod)-BPy-NT, which were utilized for C-H oxidation of heterocycles and cycloalkanes as well as C-H borylation of arenes. The cut-short nanotube catalysts displayed enhanced activities and durability as compared to the analogous homogeneous catalysts and other conventional heterogeneous catalysts, benefiting from the isolated active sites as well as the fast transport of substrates and products. After the reactions, a detailed characterization of Ir-immobilized BPy-NT via TEM, SEM, nitrogen adsorption, UV/vis, XPS, and 13 C CP MAS NMR indicated the molecular nature of the active species as well as stable structures of nanotube scaffolds. This study demonstrates the potential of BPy-NT with a short length as an integration platform for the construction of efficient heterogeneous catalytic systems for organic transformations.

Ethylbenzene dehydrogenation over FeOx/(Mg,Zn)(Al)O catalysts derived from hydrotalcites: Role of MgO as basic sites

KAUST Repository

Balasamy, Rabindran J.; Tope, Balkrishna B.; Khurshid, Alam; Al-Ali, Ali A S; Atanda, Luqman A.; Sagata, Kunimasa; Asamoto, Makiko; Yahiro, Hidenori; Nomura, Kiyoshi; Sano, Tsuneji; Takehira, Katsuomi; Al-Khattaf, Sulaiman S.

2011-01-01

A series of Mg3-xZnxFe0.5Al0.5 mixed oxide catalysts derived from hydrotalcites were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The catalysts were prepared by coprecipitation from the nitrates of metal components followed by calcination to mixed oxides at 550 °C. A part of Mg2+ in Mg 3Fe0.5Al0.5 mixed oxide was replaced with Zn2+ to test the effect of MgO as the support. The mixed oxides were composed of periclase and spinel-type compounds with a high surface area of 100-180m2gcat-1. Mössbauer and XPS measurements indicated the presence of Fe3+ on the catalysts and H2-TPR measurement suggested that the dehydrogenation reaction is catalyzed by the reduction-oxidation between Fe3+/Fe2+. The activity of Mg3-xZnxFe0.5Al0.5 mixed oxide decreased with increasing x, indicating an important role of MgO on the activity. Both CO2-TPD measurements as well as IR measurements of adsorbed CO2 clearly indicated the presence of basic sites of Mg 2+O2- on the catalysts. It seems that the combination of Mg2+O2- and Fe3+ was essential for the catalytic activity. It is concluded that the surface base sites generated on O2- bound Mg2+ near Fe3+ sites are responsible for H+-abstraction; the dehydrogenation of ethylbenzene was initiated by the H+ abstraction on Mg2+O2- basic sites, and accelerated by the reduction-oxidation of Fe3+/Fe2+ active species. © 2011 Elsevier B.V.

Ethylbenzene dehydrogenation over FeOx/(Mg,Zn)(Al)O catalysts derived from hydrotalcites: Role of MgO as basic sites

KAUST Repository

Balasamy, Rabindran J.

2011-05-01

A series of Mg3-xZnxFe0.5Al0.5 mixed oxide catalysts derived from hydrotalcites were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The catalysts were prepared by coprecipitation from the nitrates of metal components followed by calcination to mixed oxides at 550 °C. A part of Mg2+ in Mg 3Fe0.5Al0.5 mixed oxide was replaced with Zn2+ to test the effect of MgO as the support. The mixed oxides were composed of periclase and spinel-type compounds with a high surface area of 100-180m2gcat-1. Mössbauer and XPS measurements indicated the presence of Fe3+ on the catalysts and H2-TPR measurement suggested that the dehydrogenation reaction is catalyzed by the reduction-oxidation between Fe3+/Fe2+. The activity of Mg3-xZnxFe0.5Al0.5 mixed oxide decreased with increasing x, indicating an important role of MgO on the activity. Both CO2-TPD measurements as well as IR measurements of adsorbed CO2 clearly indicated the presence of basic sites of Mg 2+O2- on the catalysts. It seems that the combination of Mg2+O2- and Fe3+ was essential for the catalytic activity. It is concluded that the surface base sites generated on O2- bound Mg2+ near Fe3+ sites are responsible for H+-abstraction; the dehydrogenation of ethylbenzene was initiated by the H+ abstraction on Mg2+O2- basic sites, and accelerated by the reduction-oxidation of Fe3+/Fe2+ active species. © 2011 Elsevier B.V.

Structure and catalytic activity of regenerated spent hydrotreating catalysts

Energy Technology Data Exchange (ETDEWEB)

Kim, C.S.; Massoth, F.E.; Furimsky, E. (Utah University, Salt Lake City, UT (USA). Dept. of Fuels Engineering)

1992-11-01

Two spent catalysts, obtained from different hydrodemetallation operations, were regenerated by two different treatments, viz. 2% (V/V) O[sub 2]/N[sub 2] and air. One spent catalyst (B), contained 3 wt% V and 15 wt% C, while the other (H) contained 10 wt% V, 14 wt% C and 8 wt% Fe. After regeneration in the O[sub 2]/N[sub 2] stream, catalyst B showed essentially complete recovery of its original surface area, whereas catalyst H showed only 70% recovery. Both catalysts showed substantial losses in surface area by the air treatment. Catalytic activity tests on the regenerated catalysts for hydrodesulfurization of thiophene and for hydrogenation of 1-hexene showed low recovery of activities, even for the regenerated catalyst in which the surface area had been completely recovered. X-ray diffraction analyses of the spent-regenerated catalysts revealed substantial changes in catalyst structure. Surface area and catalytic activity results were qualitatively explained by these catalyst structural changes. 17 refs., 1 fig., 3 tabs.

Rejuvenation of the SCR catalyst at Mehrum

Energy Technology Data Exchange (ETDEWEB)

Nagai, Y.; Inatsume, Y.; Morita, I.; Kato, Y.; Yokoyama, K.; Ito, K. [Babcock Hitachi K.K., Kure-shi, Hiroshima-ken (Japan)

2004-07-01

Babcock Hitachi K.K. (BHK) received the contract of the rejuvenation of the SCR catalyst at the 750 MW coal-fired Mehrum Power Station (in Hohenhameln, Germany) in March 2003. The contractual coverage was 160 m{sup 3} of the entire catalyst layer. The catalyst, which had been in operation for 16 years since 1987, was originally supplied by BHK. The rejuvenation process developed for the Mehrum project consisted of two major steps: the first is to dust off the catalyst and remove the catalyst poison, and the second step is to add active material to enhance the catalyst activity. The catalyst must be dried after each washing. In order to minimize transportation cost and time, the rejuvenation work was done at the Mehrum station site. The scope of the rejuvenation work was shared between the owner and BHK. It took about one and a half months to complete the (total) on-site rejuvenation worked. The performance of the rejuvenated catalyst was superior to show the same level of activity as the unused catalyst and maintain the same SO{sub 2} conversion rate as the spent catalyst. This paper gives the details of the spent coal-fired SCR catalyst rejuvenation work. 13 figs., 1 tab.

Mesoporous PtSnO2/C Catalyst with Enhanced Catalytic Activity for Ethanol Electro-oxidation

Directory of Open Access Journals (Sweden)

Siyu Chen

2018-01-01

Full Text Available In this paper, we report the synthesis, characterization, and electrochemical evaluation of a mesoporous PtSnO2/C catalyst, called PtSnO2(M/C, with a nominal Pt : Sn ratio of 3 : 1. Brunauer–Emmett–Teller and transmission electron microscopy characterizations showed the obvious mesoporous structure of SnO2 in PtSnO2(M/C catalyst. X-ray photoelectron spectroscopy analysis exhibited the interaction between Pt and mesoporous SnO2. Compared with Pt/C and commercial PtSnO2/C catalysts, PtSnO2(M/C catalyst has a lower active site, but higher catalytic activity for ethanol electro-oxidation reaction (EOR. The enhanced activity could be attributed to Pt nanoparticles deposited on mesoporous SnO2 that could decrease the amount of poisonous intermediates produced during EOR by the interaction between Pt and mesoporous SnO2.

Intrinsic Activity of MnOx-CeO2 Catalysts in Ethanol Oxidation

Directory of Open Access Journals (Sweden)

Dimitrios Delimaris

2017-11-01

Full Text Available MnOx-CeO2 mixed oxides are considered efficient oxidation catalysts superior to the corresponding single oxides. Although these oxides have been the subject of numerous studies, their fundamental performance indicators, such as turnover frequency (TOF or specific activity, are scarcely reported. The purpose of the present work is to investigate the effect of catalyst composition on the concentration of active sites and intrinsic activity in ethanol oxidation by the employment of temperature-programmed desorption and oxidation of isotopically-labelled ethanol, 12CH313CH2OH. The transformation pathways of preadsorbed ethanol in the absence of gaseous oxygen refer to dehydrogenation to acetaldehyde followed by its dissociation combined with oxidation by lattice oxygen. In the presence of gaseous oxygen, lattice oxygen is rapidly restored and the main products are acetaldehyde, CO2, and water. CO2 forms less easily on mixed oxides than on pure MnOx. The TOF of ethanol oxidation has been calculated assuming that the amount of adsorbed ethanol and CO2 produced during temperature-programmed oxidation (TPO is a reliable indicator of the concentration of the active sites.

Catalytic activity of hydrophobic Pt/C/PTFE catalysts of different PTFE content for hydrogen-water liquid exchange reaction

International Nuclear Information System (INIS)

Hu Sheng; Xiao Chengjian; Zhu Zuliang; Luo Shunzhong; Wang Heyi; Luo Yangming; Wang Changbin

2007-01-01

10%Pt/C catalysts were prepared by liquid reduction method. PTFE and Pt/ C catalysts were adhered to porous metal and hydrophobic Pt/C/PTFE catalysts were prepared. The structure and size of Pt crystal particles of Pt/C catalysts were analyzed by XRD, and their mean size was 3.1 nm. The dispersion state of Pt/C and PTFE was analyzed by SEM, and they had good dispersion mostly, but PTFE membrane could be observed on local parts of Pt/C/PTFE surface. Because of low hydrophobicity, Pt/C/ PTFE catalysts have low activity when the mass ratio of PTFE and Pt/C is 0.5: 1, and their catalytic activity increases markedly when the ratio is 1:1. When the ratio increases again, more Pt active sites would be covered by PTFE and interior diffusion effect would increase, which result in the decrease of catalytic activity of Pt/C/PTFE. By PTFE pretreatment of porous metal carrier, the activity of Pt/C/PTFE catalysts decreases when the mass ratio of PTFE and Pt/C is 0.5:1, and their activity decreases when the mass ratio is 1:1. (authors)

Broadening of molecular weight distribution of polymers synthesized by metallocene-based dual-site catalysts; Alargamento da distribuicao de massa molar de polimeros sintetizados com catalisadores metalocenicos dual-site

Energy Technology Data Exchange (ETDEWEB)

Santos, Joao H.Z. dos [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica]. E-mail: jhzds@iq.ufrgs.br; Fisch, Adriano G.; Cardozo, Nilo S.M.; Secchi, Argimiro R. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Dept. de Engenharia Quimica

2008-07-01

The main topics related to the use of dual-site catalysts in the production of polymers with broad molecular weight distribution are reviewed. The polymerization using dual-site catalysts is more economical and allows to produce a higher quality product than other processes, such as polymer blend and multistage reactors. However, the formulation of these catalysts is quite complicated since the same catalyst must produce distinct polymer grades. In addition, the release of patents concerning the combination of metallocenes and new technologies for polymerization shows that polymerization processes using dual-site catalysts are of current industrial interest. (author)

Effect of W on activity of Pt-Ru/C catalyst for methanol electrooxidation in acidic medium

International Nuclear Information System (INIS)

Wang Zhenbo; Zuo Pengjian; Yin Geping

2009-01-01

The effect of W on the activity of Pt-Ru/C catalyst was investigated. The Pt-Ru-W/C and Pt-Ru/C-TR catalysts were prepared by thermal reduction method. Comparison was made to a homemade Pt-Ru/C-CR catalyst prepared by chemical reduction. Their performances were tested by using a glassy carbon thin film electrode through cyclic voltammetric and chronoamperometric curves. The particle size, structure, composition, and surface state of homemade catalyst were determined by means of X-ray diffraction (XRD), energy dispersive analysis of X-ray (EDAX), transmission electron microscopy (TEM), and X-ray photoelectron spectrometry (XPS). The result of XRD analysis shows that the homemade ternary catalyst exhibits face-centered cubic structure and has smaller lattice parameter than Pt-alone and homemade Pt-Ru/C catalysts. The particle size of Pt-Ru-W/C catalyst is relatively large of 6.5 nm. Its electrochemically active specific area is 20 m 2 g -1 less than that of Pt-Ru/C-CR, and much twice as big as that of Pt-Ru/C-TR. But, XPS analysis shows that the addition of W changes the surface state of Pt components in the alloy and can clean Pt surface active sites which are adsorbed by hydrogen. The electrocatalytic activity and tolerance performance to CO ads of Pt-Ru-W/C catalyst for methanol electrooxidation is the best due to the promoting function of W in comparison with homemade Pt-Ru/C ones.

Experimental research of technology activating catalysts for SCR DeNOx in boiler

Science.gov (United States)

Zeng, Xi; Yang, Zhengde; Li, Yan; Chen, Donglin

2018-01-01

In order to improve activity of the catalysts used in SCR DeNOx system of flue gas, a series of catalysts activated by different activating liquids under varied conditions in boiler directly were conducted. Then these catalysts were characterized by SEM, FT-IR and BET technology. And NO conversions of the activated catalysts were studied and compared with that of inactivated catalyst. The above experiment shows that NO conversion of the activated catalyst can be up to 99%, which 30% higher than that of inactivated catalyst, so activity of catalysts were improved greatly. Furthermore, optimal activating liquid labeled L2 and effective technology parameters were gained in the experiment.

Isospecific propylene polymerization with in situ generated bis(phenoxy-amine)zirconium and hafnium single site catalysts.

Science.gov (United States)

Makio, Haruyuki; Prasad, Aitha Vishwa; Terao, Hiroshi; Saito, Junji; Fujita, Terunori

2013-07-07

Bis(phenoxy-imine) Zr and Hf complexes were activated with (i)Bu3Al or (i)Bu2AlH in conjunction with Ph3CB(C6F5)4 and tested as catalysts for propylene polymerization with emphasis on the enantioselectivity of the isospecific species and the single site polymerization characteristics. The isoselective species was identified as the in situ generated bis(phenoxy-amine) complex whose isoselectivity was sensitive to subtle changes in ligand structure. By employing specific substituents at certain key positions the isotacticity reached an extremely high level comparable to high-end commercial isotactic polypropylenes (Tm > 160 °C). Single site polymerization characteristics depended upon the efficiency and selectivity of the in situ imine reduction which is sensitive to the substituent on the imine nitrogen and the reaction conditions. By using (i)Bu2AlH as a reducing agent, quantitative imine reduction can be achieved with a stoichiometric amount of the reducing agent. This lower alkylaluminum loading is beneficial for the catalyst and significantly enhances the polymerization activity and the molecular weight of the resultant polymer.

Uniformly active phase loaded selective catalytic reduction catalysts (V{sub 2}O{sub 5}/TNTs) with superior alkaline resistance performance

Energy Technology Data Exchange (ETDEWEB)

Wang, Haiqiang; Wang, Penglu [Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental & Resources Science, Zhejiang University, 310058 Hangzhou (China); Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310027 (China); Chen, Xiongbo [South China Institute of Environmental Sciences, Ministry of Environmental Protection, Guangzhou 510655 (China); Wu, Zhongbiao, E-mail: zbwu@zju.edu.cn [Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental & Resources Science, Zhejiang University, 310058 Hangzhou (China); Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310027 (China)

2017-02-15

Highlights: • VOSO{sub 4} exhibited better synergistic effect with titanate nanotubes than NH{sub 4}VO{sub 3}. • Ion-exchange reaction occurs between VOSO{sub 4} and titanate nanotubes. • Ion-exchange resulting in uniformly vanadium distribution on titanate nanotubes. • VOSO{sub 4}-based catalyst exhibited impressive SCR activity and alkaline resistance. - Abstract: In this work, protonated titanate nanotubes was performed as a potential useful support and different vanadium precursors (NH{sub 4}VO{sub 3} and VOSO{sub 4}) were used to synthesize deNO{sub x} catalysts. The results showed that VOSO{sub 4} exhibited better synergistic effect with titanate nanotubes than NH{sub 4}VO{sub 3}, which was caused by the ion-exchange reaction. Then high loading content of vanadium, uniformly active phase distribution, better dispersion of vanadium, more acid sites, better V{sup 5+}/V{sup 4+} redox cycles and superior oxygen mobility were achieved. Besides, VOSO{sub 4}-based titanate nanotubes catalysts also showed enhanced alkaline resistance than particles (P25) based catalysts. It was strongly associated with its abundant acid sites, large surface area, flexible redox cycles and oxygen transfer ability. For the loading on protonated titanate nanotubes, active metal with cation groups was better precursors than anion ones. V{sub 2}O{sub 5}/TNTs catalyst was a promising substitute for the commercial vanadium catalysts and the work conducted herein provided a useful idea to design uniformly active phase loaded catalyst.

Effect of impregnation protocol in the metallic sites of Pt–Ag/activated carbon catalysts for water denitration

Energy Technology Data Exchange (ETDEWEB)

Aristizábal, A. [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Av. Països Catalans 26, 43007 Tarragona (Spain); Contreras, S., E-mail: sandra.contreras@urv.cat [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Av. Països Catalans 26, 43007 Tarragona (Spain); Divins, N.J.; Llorca, J. [Institut de Tècniques Energètiques i Centre de Recerca en Nanoenginyeria, Universitat Politècnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Medina, F. [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Av. Països Catalans 26, 43007 Tarragona (Spain)

2014-04-01

Highlights: • Mean particle size is tuned by the Pt precursor. H{sub 2}PtCl{sub 6} leads to smaller size. • H{sub 2}PtCl{sub 6} leads to higher extent of Pt–Ag particles with a composition richer in silver. • Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2} leads to Ag{sup 0} particles and some Pt–Ag ensembles in less extent. • Nitrate and nitrite rates are linearly related to mean metal particle size. • Physical mixture of catalysts enhances N{sub 2} selectivities. - Abstract: The influence of the Pt precursor and the impregnation protocol in the catalytic behavior of 3%Pt–1.5%Ag supported on activated carbon for water denitration in a continuous reactor was studied. Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2} and H{sub 2}PtCl{sub 6} were selected as Pt precursors. Five protocols were investigated: sequential impregnations (both sequences), co-impregnation, physical mixture of monometallic catalysts, and physical mixture of a bimetallic catalyst with a Pt monometallic catalyst. The samples were characterized by XRD, XPS, TPR, HRTEM and physisorption. It was found that the catalytic activity strongly depends on the synthesis protocol and the Pt precursor, which modify the particle size. Higher nitrate rates are achieved using H{sub 2}PtCl{sub 6} than Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2}; this is mainly related to the smaller metal particle size of the former, evidenced by HRTEM. Nitrate consumption rate is directly related with the mean particle size. The physical mixture of monometallic catalysts resulted in the highest nitrogen rate.

Surface-Bound Ligands Modulate Chemoselectivity and Activity of a Bimetallic Nanoparticle Catalyst

KAUST Repository

Vu, Khanh B.

2015-04-03

"Naked" metal nanoparticles (NPs) are thermodynamically and kinetically unstable in solution. Ligands, surfactants, or polymers, which adsorb at a particle\\'s surface, can be used to stabilize NPs; however, such a mode of stabilization is undesirable for catalytic applications because the adsorbates block the surface active sites. The catalytic activity and the stability of NPs are usually inversely correlated. Here, we describe an example of a bimetallic (PtFe) NP catalyst stabilized by carboxylate surface ligands that bind preferentially to one of the metals (Fe). NPs stabilized by fluorous ligands were found to be remarkably competent in catalyzing the hydrogenation of cinnamaldehyde; NPs stabilized by hydrocarbon ligands were significantly less active. The chain length of the fluorous ligands played a key role in determining the chemoselectivity of the FePt NP catalysts. (Chemical Presented). © 2015 American Chemical Society.

Activation of molecular catalysts using semiconductor quantum dots

Science.gov (United States)

Meyer, Thomas J [Chapel Hill, NC; Sykora, Milan [Los Alamos, NM; Klimov, Victor I [Los Alamos, NM

2011-10-04

Photocatalytic materials based on coupling of semiconductor nanocrystalline quantum dots (NQD) and molecular catalysts. These materials have capability to drive or catalyze non-spontaneous chemical reactions in the presence of visible radiation, ultraviolet radiation, or both. The NQD functions in these materials as a light absorber and charge generator. Following light absorption, the NQD activates a molecular catalyst adsorbed on the surface of the NQD via transfer of one or more charges (either electrons or electron-holes) from the NQD to the molecular catalyst. The activated molecular catalyst can then drive a chemical reaction. A photoelectrolytic device that includes such photocatalytic materials is also described.

Catalytic Activity of Sulfated and Phosphated Catalysts towards the Synthesis of Substituted Coumarin

Directory of Open Access Journals (Sweden)

Nagi R. E. Radwan

2018-01-01

Full Text Available New modified acidic catalysts were prepared from the treatment of silica, titania and silica prepared from hydrolyzed tetraethyl orthosilicate (TEOS with sulfuric and phosphoric acid. The sulfated and phosphated silica synthesized from TEOS were calcined at 450 and 650 °C. These catalysts were characterized by X-ray diffraction (XRD, Fourier-transform infrared spectroscopy (FTIR, transmission electron microscope (TEM, and scanning electron microscope (SEM. The surface areas, total pore volume, and mean pore radius of the acidic catalysts were investigated, while the pore size distribution was determined by the Barrett, Joyner and Halenda (BJH method. The catalytic activity of the sulfated and phosphated silica and/or titania were examined with the Pechmann condensation reaction, in which different phenols reacted with ethyl acetoacetate as a neat reaction to obtain the corresponding coumarin derivatives. The results indicated that the treatment of the catalysts with sulfuric or phosphoric acid led to a decrease in the phases’ crystallinity to a certain degree. The morphology and the structure of the acidified catalysts were examined and their particle size was calculated. Furthermore, the amount of the used catalysts played a vital role in controlling the formation of the products as well as their performance was manipulated by the number and nature of the active acidic sites on their surfaces. The obtained results suggested that the highest catalytic conversion of the reaction was attained at 20 wt % of the catalyst and no further increase in the product yield was detected when the amount of catalyst exceeded this value. Meanwhile the phenol molecules were a key feature in obtaining the final product.

Characterization of Cu/CeO2/Al2O3 catalysts by temperature programmed reduction and activity for CO oxidation

International Nuclear Information System (INIS)

Cataluna, Renato; Baibich, Ione M.; Dallago, R.M.; Picinini, C.; Martinez-Arias, A.; Soria, J.

2001-01-01

The kinetic parameters for the CO oxidation reaction using copper/alumina-modified ceria as catalysts were determined. The catalysts with different concentrations of the metals were prepared using impregnation methods. In addition, the reduction-oxidation behaviour of the catalysts were investigated by temperature-programmed reduction. The activity results show that the mechanism for CO oxidation is bifunctional: oxygen is activated on the anionic vacancies of ceria surface, while carbon monoxide is adsorbed preferentially on the higher oxidation copper site. Therefore, the reaction occurs on the interfacial active centers. Temperatures-programmed Reduction patterns show a higher dispersion when cerium oxide is present. (author)

Cerium-containing catalysts for obtaining ethylene from ethanol

Directory of Open Access Journals (Sweden)

Kusman Dossumov

2014-10-01

Full Text Available The catalysts Се/γ-Al2O3 и Се-La/γ-Al2O3 were studied by methods of electron microscopy (EM and temperature-programmed desorption (TPD of ammonia. Their activity was studied in reaction of ethanol dehydration with formation of ethylene. Modification of Се/γ-Al2O3 catalyst by Lanthanum promotes dispersion of the catalyst and increases the amount of acidic sites. This modification positively affects the catalyst activity.

Flexibility Matters: Cooperative Active Sites in Covalent Organic Framework and Threaded Ionic Polymer.

Science.gov (United States)

Sun, Qi; Aguila, Briana; Perman, Jason; Nguyen, Nicholas; Ma, Shengqian

2016-12-07

The combination of two or more reactive centers working in concert on a substrate to facilitate the reaction is now considered state of the art in catalysis, yet there still remains a tremendous challenge. Few heterogeneous systems of this sort have been exploited, as the active sites spatially separated within the rigid framework are usually difficult to cooperate. It is now shown that this roadblock can be surpassed. The underlying principle of the strategy presented here is the integration of catalytic components with excellent flexibility and porous heterogeneous catalysts, as demonstrated by the placement of linear ionic polymers in close proximity to surface Lewis acid active sites anchored on the walls of a covalent organic framework (COF). Using the cycloaddition of the epoxides and CO 2 as a model reaction, dramatic activity improvements have been achieved for the composite catalysts in relation to the individual catalytic component. Furthermore, they also clearly outperform the benchmark catalytic systems formed by the combination of the molecular organocatalysts and heterogeneous Lewis acid catalysts, while affording additional recyclability. The extraordinary flexibility and enriched concentration of the catalytically active moieties on linear polymers facilitate the concerted catalysis, thus leading to superior catalytic performance. This work therefore uncovers an entirely new strategy for designing bifunctional catalysts with double-activation behavior and opens a new avenue in the design of multicapable systems that mimic biocatalysis.

Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

International Nuclear Information System (INIS)

Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

1977-01-01

Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

The role of reaction pathways and support interactions in the development of high activity hydrotreating catalysts

DEFF Research Database (Denmark)

Topsøe, Henrik; Hinnemann, Berit; Nørskov, Jens Kehlet

2005-01-01

structures may be present as single sulfide sheets. Thus, stacking is not an essential feature of Type II catalysts. The article illustrates how the new scientific insight has aided the introduction of the new high activity BRIM (TM) type catalysts for FCC pre-treatment and production of ultra low sulfur...... exhibiting a metallic character are observed to be involved in adsorption, hydrogenation and C-S bond cleavage. The insight is seen to provide a new framework for understanding the DDS and HYD pathways and the role of steric hindrance and poisons. Density functional theory (DFT) calculations have illustrated...... how support interactions may influence the activity of sulfided catalysts. The brim sites and the tendency to form vacancies are seen to differ in types I and II Co-Mo-S. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) studies show that the high activity Type II...

Preparation And Characterization Of Cr/Activated Carbon Catalyst From Palm Empty Fruit Bunch

Directory of Open Access Journals (Sweden)

Zainal Fanani

2016-02-01

Full Text Available Preparation and characterization of Cr/activated carbon catalyst from palm empty fruit bunch had been done. The research were to determine the effect of carbonization temperature towards adsorption of ammonia, iodine number, metilen blue number, and porosity of activated carbon and Cr/activated carbon catalyst. The determination of porosity include surface area, micropore volume and total pore volume. The results showed the best carbonization temperature activated carbon and Cr/activated carbon catalyst at 700°C. The adsorption ammonia of activated carbon and Cr/activated carbon catalyst as 6.379 mmol/g and 8.1624 mmol/g. The iodine number of activated carbon and Cr/activated carbon catalyst as 1520.16 mg/g and 1535.67 mg/g. The metilen blue number of activated carbon and Cr/activated carbon catalyst as 281.71 mg/g and 319.18 mg/g. The surface area of activated carbon and Cr/activated carbon catalyst as 1527.80 m2/g and 1652.58 m2/g. The micropore volume of activated carbon and Cr/activated carbon catalyst as 0.7460 cm3/g and 0.8670 cm3/g. The total pore volume of activated carbon and Cr/activated carbon catalyst as 0.8243 cm3/g and 0.8970 cm3/g.

Selective CO Methanation on Highly Active Ru/TiO2 Catalysts: Identifying the Physical Origin of the Observed Activation/Deactivation and Loss in Selectivity

DEFF Research Database (Denmark)

Abdel-Mageed, Ali M.; Widmann, Daniel; Olesen, Sine Ellemann

2018-01-01

Ru /TiO2 catalysts are highly active and selective in the selective methanation of CO in the presence of large amounts of CO2, but suffer from a considerable deactivation and loss of selectivity during time on stream. Aiming at a fundamental understanding of these processes, we have systematically...... different effects such as structural effects, adlayer effects such as site blocking effects and changes in the chemical (surface) composition of the catalysts. Operando XANES / EXAFS measurements revealed that an initial activation phase is largely due to the reduction of oxidized Ru species, together...

Deactivation of molybdate catalysts by nitrogen bases

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.

1982-10-01

Nitrogen bases present in petroleum deactivate the surface of molybdate catalysts. The detrimental effect is attributed either to interactions of the bases with Lewis sites via unpaired electrons on nitrogen or to their ability to remove proton from the surface. The later effect results in a decrease of concentration of Bronsted sites known to be active in catalytic reactions. This enhances rate of coke forming reactions. Resistence of molybdate catalysts to coke formation depends on the form and redistribution of active ingredients on the surface. This can be effected by conditions applied during preparation and pretreatment of the catalysts. Processing parameters used during catalytic hydrotreatment are also important; i.e., the coke formation is slow under conditions ensuring high rate of removal of basic nitrogen containing compounds.

Magnesium oxide prepared via metal-chitosan complexation method: Application as catalyst for transesterification of soybean oil and catalyst deactivation studies

Science.gov (United States)

Almerindo, Gizelle I.; Probst, Luiz F. D.; Campos, Carlos E. M.; de Almeida, Rusiene M.; Meneghetti, Simoni M. P.; Meneghetti, Mario R.; Clacens, Jean-Marc; Fajardo, Humberto V.

2011-10-01

A simple method to prepare magnesium oxide catalysts for biodiesel production by transesterification reaction of soybean oil with ethanol is proposed. The method was developed using a metal-chitosan complex. Compared to the commercial oxide, the proposed catalysts displayed higher surface area and basicity values, leading to higher yield in terms of fatty acid ethyl esters (biodiesel). The deactivation of the catalyst due to contact with CO2 and H2O present in the ambient air was verified. It was confirmed that the active catalytic site is a hydrogenocarbonate adsorption site.

Dynamics of Catalyst Nanoparticles

DEFF Research Database (Denmark)

Hansen, Thomas Willum; Cavalca, Filippo; Wagner, Jakob Birkedal

and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. In order to initiate a systematic study of the dynamics and sintering of nanoparticles, various catalytic systems have been...... under gas exposure, dynamic phenomena such as sintering and growth can be observed with sub-Ångstrøm resolution. Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals...

Theoretical investigation of active sites at the corners of Mgcl 2 crystallites in supported ziegler-natta catalysts

KAUST Repository

Correa, Andrea

2012-05-08

We present a theoretical study on possible models of catalytic active species corresponding to Ti-chloride species adsorbed at the corners of MgCl 2 crystallites. First we focused our efforts on the interaction between prototypes of three industrially relevant Lewis bases used as internal donors (1,3-diethers, alkoxysilanes and succinates) and MgCl 2 units at the corner of a MgCl 2 crystallite. Our calculations show that the energetic cost to extract MgCl 2 units at the corner of (104) edged MgCl 2 crystallites is not prohibitive, and that Lewis bases added during catalyst preparation make this process easier. After removal of one MgCl 2 unit, a short (110) stretch joining the (104) edges is formed. Adsorption of TiCl 4 on the generated vacancy originates a Ti-active species. In the second part of this manuscript, we report on the stereo- and regioselective behavior of this model of active species in the absence as well as in the presence of the three Lewis bases indicated above. Surface reconstruction due to the additional adsorption of an extra MgCl 2 layer is also considered. We show that, according to experimental data, Lewis bases coordinated in the proximity of the active Ti center confer a remarkable stereoselectivity. Moreover, surface reconstruction as well as donor coordination would improve regioselectivity by disfavoring secondary propene insertion. While still models of possible active species, our results indicate that defects, corners and surface reconstruction should be considered as possible anchoring sites for the catalytically active Ti-species. © 2012 American Chemical Society.

Steam dealkylation catalyst and a method for its activation

International Nuclear Information System (INIS)

Dorawala, T.; Reinhard, R.

1980-01-01

The method of activating a supported catalyst containing oxides of a group viii metal and of a group 1 a metal which comprises heating said catalyst at a rate of 10 0 to 500 0 F/hr to a temperature of 650 0 to 1400 0 F in a hydrogen atmosphere; maintaining said heated catalyst in a hydrogen atmosphere at 650 0 to 1400 0 F for 2 to 30 hours thereby forming a hydrogen-treated catalyst; and maintaining the hydrogen-treated catalyst in a steam-hydrogen atmosphere at 650 0 to 1400 0 F for 2 to 20 hours thereby forming a steamed hydrogen-treated catalyst

Differential active site loop conformations mediate promiscuous activities in the lactonase SsoPox.

Directory of Open Access Journals (Sweden)

Julien Hiblot

Full Text Available Enzymes are proficient catalysts that enable fast rates of Michaelis-complex formation, the chemical step and products release. These different steps may require different conformational states of the active site that have distinct binding properties. Moreover, the conformational flexibility of the active site mediates alternative, promiscuous functions. Here we focused on the lactonase SsoPox from Sulfolobus solfataricus. SsoPox is a native lactonase endowed with promiscuous phosphotriesterase activity. We identified a position in the active site loop (W263 that governs its flexibility, and thereby affects the substrate specificity of the enzyme. We isolated two different sets of substitutions at position 263 that induce two distinct conformational sampling of the active loop and characterized the structural and kinetic effects of these substitutions. These sets of mutations selectively and distinctly mediate the improvement of the promiscuous phosphotriesterase and oxo-lactonase activities of SsoPox by increasing active-site loop flexibility. These observations corroborate the idea that conformational diversity governs enzymatic promiscuity and is a key feature of protein evolvability.

Catalytic hydroprocessing of simulated coal tars. 1. Activity of a sulphided Ni-Mo/Al/sub 2/O/sub 3/ catalyst for the hydroconversion of model compounds

Energy Technology Data Exchange (ETDEWEB)

Lemberton, J.L.; Touzeyidio, M.; Guisnet, M. (Laboratoire de Catalyse en Chimie Organique CNRS, Poitiers (France))

1989-09-15

The conversion of tars from coal pyrolysis into light aromatics, such as BTX (benzene-toluene-xylenes) and naphthalene, requires the hydrocracking of heavy polyaromatics in the presence of nitrogen- and oxygen-containing compounds. The hydroconversion of phenanthrene, which occurs through bifunctional catalysis, was chosen as a model reaction. It was carried out over a sulphided Ni-Mo/Al/sub 2/O/sub 3/ catalyst (Ketjen 153) in the presence of carbazole and 1-naphthol. Carbazole poisons slightly through coking both the hydrogenating and the acid sites of the catalyst. 1-Naphthol has a more significant deactivating effect: the hydrogenating sites of the catalyst are poisoned by the water eliminated from 1-naphthol and the acid sites by coke generated by 1-naphthol. Lastly, the hydrogenating activity of the catalyst is not substantially affected in the presence of carbazole and 1-naphthol, but its cracking activity is much reduced, making it impossible for the catalyst to achieve the hydrocracking of phenanthrene into into light aromatics. 5 figs, 21 refs., 1 tab.

Templating Routes to Supported Oxide Catalysts by Design

Energy Technology Data Exchange (ETDEWEB)

Notestein, Justin M. [Northwestern Univ., Evanston, IL (United States)

2016-09-08

The rational design and understanding of supported oxide catalysts requires at least three advancements, in order of increasing complexity: the ability to quantify the number and nature of active sites in a catalytic material, the ability to place external controls on the number and structure of these active sites, and the ability to assemble these active sites so as to carry out more complex functions in tandem. As part of an individual investigator research program that is integrated with the Northwestern University Institute for Catalysis in Energy Processes (ICEP) as of 2015, significant advances were achieved in these three areas. First, phosphonic acids were utilized in the quantitative assessment of the number of active and geometrically-available sites in MO_x-SiO₂ catalysts, including nanocrystalline composites, co-condensed materials, and grafted structures, for M=Ti, Zr, Hf, Nb, and Ta. That work built off progress in understanding supported Fe, Cu, and Co oxide catalysts from chelating and/or multinuclear precursors to maximize surface reactivity. Secondly, significant progress was made in the new area of using thin oxide overcoats containing ‘nanocavities’ from organic templates as a method to control the dispersion and thermal stability of subsequently deposited metal nanoparticles or other catalytic domains. Similar methods were used to control surface reactivity in SiO₂-Al₂O₃ acid catalysts and to control reactant selectivity in Al₂O₃-TiO₂ photocatalysts. Finally, knowledge gained from the first two areas has been combined to synthesize a tandem catalyst for hydrotreating reactions and an orthogonal tandem catalyst system where two subsequent reactions in a reaction network are independently controlled by light and heat. Overall, work carried out under this project significantly advanced the knowledge of synthesis-structure-function relationships in supported

Catalyst design for clean and efficient fuels

DEFF Research Database (Denmark)

Šaric, Manuel

cobalt promoted MoS2 catalyst. Reactivity of a series of model molecules, found in oil prior to desulfurization, is studied on cobalt promoted MoS2. Such an approach has the potential to explain the underlying processes involved in the removal of sulfur at each specific site of the catalyst. The goal...... is to identify which sites are active towards specific molecules and in getting insight to what the ideal catalyst should look like in terms of morphology. Dimethyl carbonate is an environmentally benign compound that can be used as a solvent and precursor in chemical synthesis or as a fuel and fuel additive...... processes currently used. It is found that noble metals can be used as electrocatalysts for the synthesis of dimethyl carbonate, significantly lowering the potential when using copper instead of gold. Besides being active, copper was found to be selective towards dimethyl carbonate. A non-selective catalyst...

An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15

NARCIS (Netherlands)

Santen, van R.A.; Zhang, Lei; Abbenhuis, H.C.L.; Gerritsen, G.; Ní Bhriain, N.M.; Magusin, P.C.M.M.; Mezari, B.; Han, W.; Yang, Q.; Li, Can

2007-01-01

A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active

Activity and selectivity of three molybdenum catalysts for coal liquefaction reactions

Energy Technology Data Exchange (ETDEWEB)

Curtis, C.W.; Pellegrino, J.L.

The activity and selectivity of three different molybdenum catalysts for reactions occurring in coal liquefaction, specifically for hydrogenation (HYD), hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrocracking (HYC), have been examined. The three molybdenum catalysts used were molybdenum napthenate, molybdenum on ..gamma..-alumina, and a precipitated, disordered MoS/sub 2/. Molybdenum naphthenate was most selective for HYD and HDN. All three catalysts exhibited approximately equal activity for HDS and HDO and little selectivity for HYC of alkyl bridge structures. The activity and selectivity of the three molybdenum catalysts for producing hydrocarbons and removing heteroatoms from coal during liquefaction were determined and compared. Molybdenum naphthenate was the most active catalyst for hydrocarbon production and removal of nitrogen- and oxygen-containing species during coal liquefaction. 31 refs., 4 figs., 7 tabs.

Catalytic wet air oxidation of coke-plant wastewater on ruthenium-based eggshell catalysts in a bubbling bed reactor.

Science.gov (United States)

Yang, M; Sun, Y; Xu, A H; Lu, X Y; Du, H Z; Sun, C L; Li, C

2007-07-01

Catalytic wet air of coke-plant wastewater was studied in a bubbling bed reactor. Two types of supported Ru-based catalysts, eggshell and uniform catalysts, were employed. Compared with the results in the wet air oxidation of coke-plant wastewater, supported Ru uniform catalysts showed high activity for chemical oxygen demand (COD) and ammonia/ammonium compounds (NH3-N) removal at temperature of 250 degrees C and pressure of 4.8 MPa, and it has been demonstrated that the catalytic activity of uniform catalyst depended strongly on the distribution of active sites of Ru on catalyst. Compared to the corresponding uniform catalysts with the same Ru loading (0.25 wt.% and 0.1 wt.%, respectively), the eggshell catalysts showed higher activities for CODcr removal and much higher activities for NH3-N degradation. The high activity of eggshell catalyst for treatment of coke-plant wastewater can be attributed to the higher density of active Ru sites in the shell layer than that of the corresponding uniform catalyst with the same Ru loading. It has been also evidenced that the active Ru sites in the internal core of uniform catalyst have very little or no contribution to CODcr and NH3-N removal in the total oxidation of coke-plant wastewater.

Reactions of synthesis gas on silica supported transition metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Niemelae, M. [VTT Chemical Technology, Espoo (Finland). Lab. of Industrial Chemistry

1997-12-31

The effect of catalyst precursor and composition on the activation of CO was investigated using CO hydrogenation as a test reaction. The interrelations of preparation, pretreatment, characteristics and activity were clarified. For Co/SiO{sub 2} catalyst, MgO promotion increased the CO adsorption capacity and the hydrogen uptake, although the extent of reduction for cobalt remained the same or decreased. The conversion per active metallic cobalt site consequently increased in conjunction with MgO promotion, while the effect on overall performance per 1 g of catalyst remained moderate. The precursor affected the performance of Co/SiO{sub 2} considerably. CO was more strongly adsorbed on catalysts of carbonyl origin than on those derived from cobalt nitrate, the activity thus being higher. Although the nitrate derived Co/SiO{sub 2} appeared both to retain its activity and to regain its adsorption capacity better than the catalysts of carbonyl origin, the performance of the latter was superior with time on stream. For tetranuclear cluster based Co-Ru and Co-Rh catalysts, rhodium or ruthenium was in contact with the support and cobalt was enriched on top. On Co-Ru/SiO{sub 2} ruthenium enhanced deactivation, and no benefits in activity or oxygenate selectivity were achieved relative to the monometallic catalysts of cluster origin. The Co-Rh/SiO{sub 2} catalysts were also less active than those derived from monometallic clusters, but they exhibited higher selectivities to oxygenated compounds due to the presence of active sites on the perimeter of the cobalt particles located on rhodium. The highest selectivity to oxygenates was achieved by changing the decomposition atmosphere of Rh{sub 4}(CO){sub 12}/SiO{sub 2} from hydrogen to carbon monoxide. The results also showed two types of active sites to be operative in the formation of oxygenates - one for ethanol and another for aldehydes. (orig.) 69 refs.

Real-Time Visualization of Active Species in a Single-Site Metal–Organic Framework Photocatalyst

Energy Technology Data Exchange (ETDEWEB)

Yang, Sizhuo [Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States; Pattengale, Brian [Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States; Lee, Sungsik [X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60349, United States; Huang, Jier [Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States

2018-02-06

In this work, we report a new single-site photocatalyst (Co-Ru-UIO- 67(bpy)) based on a metal-organic framework platform with incorporated molecular photosensitizer and catalyst. We show that this catalyst not only demonstrates exceptional activity for light-driven H2 production but also can be recycled without loss of activity. Using the combination of optical transient absorption spectroscopy and in situ X-ray absorption spectroscopy, we not only captured the key CoI intermediate species formed after ultrafast charge transfer from the incorporated photosensitizer but also identified the rate-limiting step in the catalytic cycle, providing insight into the catalysis mechanism of these single-site metal-organic framework photocatalysts.

Enhanced activity of Pt/CNTs anode catalyst for direct methanol fuel cells using Ni2P as co-catalyst

Science.gov (United States)

Li, Xiang; Luo, Lanping; Peng, Feng; Wang, Hongjuan; Yu, Hao

2018-03-01

The direct methanol fuel cell is a promising energy conversion device because of the utilization of the state-of-the-art platinum (Pt) anode catalyst. In this work, novel Pt/Ni2P/CNTs catalysts were prepared by the H2 reduction method. It was found that the activity and stability of Pt for methanol oxidation reaction (MOR) could be significantly enhanced while using nickel phosphide (Ni2P) nanoparticles as co-catalyst. X-ray photoelectron spectroscopy revealed that the existence of Ni2P affected the particle size and electronic distribution of Pt obviously. Pt/CNTs catalyst, Pt/Ni2P/CNTs catalysts with different Ni2P amount were synthesized, among which Pt/6%Ni2P/CNTs catalyst exhibited the best MOR activity of 1400 mAmg-1Pt, which was almost 2.5 times of the commercial Pt/C-JM catalyst. Moreover, compared to other Pt-based catalysts, this novel Pt/Ni2P/CNTs catalyst also exhibited higher onset current density and better steady current density. The result of this work may provide positive guidance to the research on high efficiency and stability of Pt-based catalyst for direct methanol fuel cells.

Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

KAUST Repository

Atiqullah, Muhammad

2013-08-12

Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

KAUST Repository

Atiqullah, Muhammad; Anantawaraskul, Siripon; Emwas, Abdul-Hamid M.; Al-Harthi, Mamdouh Ahmed; Hussain, Ikram; Ul-Hamid, Anwar; Hossaen, Anwar

2013-01-01

Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

Aberration-corrected imaging of active sites on industrial catalyst nanoparticles

DEFF Research Database (Denmark)

Gontard, Lionel Cervera; Chang, L-Y; Hetherington, CJD

2007-01-01

Picture perfect: Information about the local topologies of active sites on commercial nanoparticles can be gained with atomic resolution through spherical-aberration-corrected transmission electron microscopy (TEM). A powder of Pt nanoparticles on carbon black was examined with two advanced TEM t...

Novel synthesis of highly durable and active Pt catalyst encapsulated in nitrogen containing carbon for polymer electrolyte membrane fuel cell

Science.gov (United States)

Lee, Hyunjoon; Sung, Yung-Eun; Choi, Insoo; Lim, Taeho; Kwon, Oh Joong

2017-09-01

Novel synthesis of a Pt catalyst encapsulated in a N-containing carbon layer for use in a polymer electrolyte membrane fuel cell is described in this study. A Pt-aniline complex, formed by mixing Pt precursor and aniline monomer, was used as the source of Pt, C, and N. Heat treatment of the Pt-aniline complex with carbon black yielded 5 nm Pt nanoparticles encapsulated by a N-containing carbon layer originating from aniline carbonization. The synthesized Pt catalyst exhibited higher mass specific activity to oxygen reduction reaction than that shown by conventional Pt/C catalyst because pyridinic N with graphitic carbon in the carbon layer provided active sites for oxygen reduction reaction in addition to those provided by Pt. In single cell testing, initial performance of the synthesized catalyst was limited because the thick catalyst layer increased resistance related to mass transfer. However, it was observed that the carbon layer successfully prevented Pt nanoparticles from growing via agglomeration and Ostwald ripening under fuel cell operation, thereby improving durability. Furthermore, a mass specific performance of the synthesized catalyst higher than that of a conventional Pt/C catalyst was achieved by modifying the synthesized catalyst's layer thickness.

New Method to Synthesize Highly Active and Durable Chemically Ordered fct-PtCo Cathode Catalyst for PEMFCs.

Science.gov (United States)

Jung, Won Suk; Popov, Branko N

2017-07-19

In the bottom-up synthesis strategy performed in this study, the Co-catalyzed pyrolysis of chelate-complex and activated carbon black at high temperatures triggers the graphitization reaction which introduces Co particles in the N-doped graphitic carbon matrix and immobilizes N-modified active sites for the oxygen reduction reaction (ORR) on the carbon surface. In this study, the Co particles encapsulated within the N-doped graphitic carbon shell diffuse up to the Pt surface under the polymer protective layer and forms a chemically ordered face-centered tetragonal (fct) Pt-Co catalyst PtCo/CCCS catalyst as evidenced by structural and compositional studies. The fct-structured PtCo/CCCS at low-Pt loading (0.1 mg Pt cm -2 ) shows 6% higher power density than that of the state-of-the-art commercial Pt/C catalyst. After the MEA durability test of 30 000 potential cycles, the performance loss of the catalyst is negligible. The electrochemical surface area loss is less than 40%, while that of commercial Pt/C is nearly 80%. After the accelerated stress test, the uniform catalyst distribution is retained and the mean particle size increases approximate 1 nm. The results obtained in this study indicated that highly stable compositional and structural properties of chemically ordered PtCo/CCCS catalyst contribute to its exceptional catalyst durability.

Fischer-Tropsch Cobalt Catalyst Activation and Handling Through Wax Enclosure Methods

Science.gov (United States)

Klettlinger, Jennifer L. S.; Yen, Chia H.; Nakley, Leah M.; Surgenor, Angela D.

2016-01-01

Fischer-Tropsch (F-T) synthesis is considered a gas to liquid process which converts syn-gas, a gaseous mixture of hydrogen and carbon monoxide, into liquids of various hydrocarbon chain length and product distributions. Cobalt based catalysts are used in F-T synthesis and are the focus of this paper. One key concern with handling cobalt based catalysts is that the active form of catalyst is in a reduced state, metallic cobalt, which oxidizes readily in air. In laboratory experiments, the precursor cobalt oxide catalyst is activated in a fixed bed at 350 ?C then transferred into a continuous stirred tank reactor (CSTR) with inert gas. NASA has developed a process which involves the enclosure of active cobalt catalyst in a wax mold to prevent oxidation during storage and handling. This improved method allows for precise catalyst loading and delivery into a CSTR. Preliminary results indicate similar activity levels in the F-T reaction in comparison to the direct injection method. The work in this paper was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

Syntheses, Characterization and Kinetics of Nickel-Tungsten Nitride Catalysts for Hydrotreating of Gas Oil

Science.gov (United States)

Botchwey, Christian

This thesis summarizes the methods and major findings of Ni-W(P)/gamma-Al 2O3 nitride catalyst synthesis, characterization, hydrotreating activity, kinetic analysis and correlation of the catalysts' activities to their synthesis parameters and properties. The range of parameters for catalyst synthesis were W (15-40 wt%), Ni (0-8 wt%), P (0-5 wt%) and nitriding temperature (TN) (500-900 °C). Characterization techniques used included: N2 sorption studies, chemisorption, elemental analysis, temperature programmed studies, x-ray diffraction, scanning electron microscopy, energy dispersive x-ray, infrared spectroscopy, transmission electron microscopy and x-ray absorption near edge structure. Hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) were performed at: temperature (340-380 °C), pressure (6.2-9.0 MPa), liquid hourly space velocity (1-3 h-1) and hydrogen to oil ratio (600 ml/ml, STP). The predominant species on the catalyst surface were Ni3N, W2N and bimetallic Ni2W3N. The bimetallic Ni-W nitride species was more active than the individual activities of the Ni3N and W2N. P increased weak acid sites while nitriding temperature decreased amount of strong acid sites. Low nitriding temperature enhanced dispersion of metal particles. P interacted with Al 2O3 which increased the dispersion of metal nitrides on the catalyst surface. HDN activity increased with Ni and P loading but decreased with increase in nitriding temperature (optimum conversion; 60 wt%). HDS and HDA activities went through a maximum with increase in the synthesis parameters (optimum conversions; 88. wt% for HDS and 47 wt% for HDA). Increase in W loading led to increase in catalyst activity. The catalysts were stable to deactivation and had the nitride structure conserved during hydrotreating in the presence of hydrogen sulfide. The results showed good correlation between hydrotreating activities (HDS and HDN) and the catalyst nitrogen content, number of exposed

Catalytic activity of zeolite-containing catalysts in cumene cracking

Energy Technology Data Exchange (ETDEWEB)

Koval' chuk, L V; Takhtarova, G N; Topchieva, K V [Moskovskij Gosudarstvennyj Univ. (USSR). Kafedra Fizicheskoj Khimii

1977-01-01

The catalytic properties are studied of decationized forms (Ca and La) of zeolite-containing catalysts in relation to the nature of the cation and the degree of exchange in the cumene cracking reaction. It has been established that the increase in the activity of Ca-decationized catalysts occurs at a degree of exchange from 22 to 40% and at a ratio of the cation and decationized areas from 0.4 to 1. For La-decationized catalysts the activity increases at a degree of exchange up to 60% and at a ratio between the cation and decationized areas exceeding 1.

Characterization of alumina supported molybdenum catalysts

Energy Technology Data Exchange (ETDEWEB)

Pastura, N M; Carmo, L M.P.M.; Sachett, C M.M.; Lam, Y L [Instituto Militar de Engenharia, Rio de Janeiro (Brazil). Secao de Quimica

1983-10-01

In order to optimize a bifunctional catalyst (acid and hydrogenating) of Mo/Al/sub 2/O/sub 3/, oxygen adsorption at 195 K and ethanol dehydration at 480-520 K were carried out using a series of these catalysts. The increase of Mo content increased the quantity of adsorbed oxygen, thus indicating that the number of hydrogenating sites also increased. The specific activity of ethanol dehydration varied slightly, indicating that the number of acid sites remains almost constant. On the other hand, the selectivity in ethylene (versus ether) increased markedly. This may be attributed to the increase in acid force of the acid sites.

Characterization of alumina supported molybdenum catalysts

International Nuclear Information System (INIS)

Pastura, N.M.; Carmo, L.M.P.M.; Sachett, C.M.M.; Lam, Y.L.

1983-01-01

In order to optimize a bifunctional catalyst (acid and hydrogenating) of Mo/Al 2 O 3 , oxygen adsorption at 195 K and ethanol dehydration at 480-520 K were carried out using a series of these catalysts. The increase of Mo content increased the quantity of adsorbed oxygen, thus indicating that the number of hydrogenating sites also increased. The specific activity of ethanol dehydration varied slightly, indicating that the number of acid sites remains almost constant. On the other hand, the selectivity in ethylene (versus ether) increased markedly. This may be attributed to the increase in acid force of the acid sites. (C.L.B.) [pt

Structure-activity relationship of surfactant for preparing DMFC anodic catalyst

International Nuclear Information System (INIS)

Su Yi; Xue Xinzhong; Xu Weilin; Liu Changpeng; Xing Wei; Zhou Xiaochun; Tian Tian; Lu Tianhong

2006-01-01

Three kinds of surfactants as stabilizer were applied to the preparation of electrocatalysts for direct methanol fuel cell (DMFC). The catalysts have been characterized by examining their catalytic activities, morphologies and particle sizes by means of cyclic voltammetry, chronoamperometry, X-ray diffraction and transmission electron microscopy (TEM). It is found that the surfactants with different structures have a significantly influence on the catalyst shape and activity. The catalysts prepared with non-ionic surfactants as the stabilizer show higher activity for direct oxidation of methanol. The structure-activity relationship (SAR) analysis has been explored and the effect of hydrophile-lipophile balance (HLB value) has also been discussed

Synthesis of Dicyclopentadiene Oligomer Over Nanoporous Al-MCM-41 Catalysts.

Science.gov (United States)

Park, Eunseo; Kim, Jinhan; Yim, Jin-Heong; Han, Jeongsik; Kwon, Tae Soo; Park, Y K; Jeon, Jong-Ki

2016-05-01

One step reaction composed of DCPD oligomerization and DCPD oligomer isomerization was investigated over nanoporous Al-MCM-41 catalysts. The effects of aluminum grafting over MCM-41 on the catalyst characteristics were studied with respect to the synthesis of TCPD isomer. Physical and chemical properties of the catalysts were analyzed by N2 adsorption, temperature-programmed desorption of ammonia, and infrared spectroscopy of adsorbed pyridine. The overall number of acid sites as well as the number of Lewis acid sites increased with increasing of aluminum content over MCM-41. When utilizing MCM-41 and Al-MCM-41 as the catalyst, DCPD oligomerization reaction activity greatly increased compared to the thermal reaction. The highest TCPD isomer selectivity over the Al-MCM-41 catalyst with the highest aluminum content could be ascribed to the largest amount of acid sites. This study showed an increased level of TCPD isomer selectivity by an increasing level of Lewis acid sites through aluminum addition over MCM-41.

Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis.

Science.gov (United States)

Wan, Gang; Yu, Pengfei; Chen, Hangrong; Wen, Jianguo; Sun, Cheng-Jun; Zhou, Hua; Zhang, Nian; Li, Qianru; Zhao, Wanpeng; Xie, Bing; Li, Tao; Shi, Jianlin

2018-04-01

The development of cost-effective catalysts to replace noble metal is attracting increasing interests in many fields of catalysis and energy, and intensive efforts are focused on the integration of transition-metal sites in carbon as noble-metal-free candidates. Recently, the discovery of single-atom dispersed catalyst (SAC) provides a new frontier in heterogeneous catalysis. However, the electrocatalytic application of SAC is still subject to several theoretical and experimental limitations. Further advances depend on a better design of SAC through optimizing its interaction with adsorbates during catalysis. Here, distinctive from previous studies, favorable 3d electronic occupation and enhanced metal-adsorbates interactions in single-atom centers via the construction of nonplanar coordination is achieved, which is confirmed by advanced X-ray spectroscopic and electrochemical studies. The as-designed atomically dispersed cobalt sites within nonplanar coordination show significantly improved catalytic activity and selectivity toward the oxygen reduction reaction, approaching the benchmark Pt-based catalysts. More importantly, the illustration of the active sites in SAC indicates metal-natured catalytic sites and a media-dependent catalytic pathway. Achieving structural and electronic engineering on SAC that promotes its catalytic performances provides a paradigm to bridge the gap between single-atom catalysts design and electrocatalytic applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid Nanomaterials with Single-Site Catalysts by Spatially Controllable Immobilization of Nickel Complexes via Photoclick Chemistry for Alkene Epoxidation.

Science.gov (United States)

Ghosh, Dwaipayan; Febriansyah, Benny; Gupta, Disha; Ng, Leonard Kia-Sheun; Xi, Shibo; Du, Yonghua; Baikie, Tom; Dong, ZhiLi; Soo, Han Sen

2018-05-22

Catalyst deactivation is a persistent problem not only for the scientific community but also in industry. Isolated single-site heterogeneous catalysts have shown great promise to overcome these problems. Here, a versatile anchoring strategy for molecular complex immobilization on a broad range of semiconducting or insulating metal oxide ( e. g., titanium dioxide, mesoporous silica, cerium oxide, and tungsten oxide) nanoparticles to synthesize isolated single-site catalysts has been studied systematically. An oxidatively stable anchoring group, maleimide, is shown to form covalent linkages with surface hydroxyl functionalities of metal oxide nanoparticles by photoclick chemistry. The nanocomposites have been thoroughly characterized by techniques including UV-visible diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy (XAS). The IR spectroscopic studies confirm the covalent linkages between the maleimide group and surface hydroxyl functionalities of the oxide nanoparticles. The hybrid nanomaterials function as highly efficient catalysts for essentially quantitative oxidations of terminal and internal alkenes and show molecular catalyst product selectivities even in more eco-friendly solvents. XAS studies verify the robustness of the catalysts after several catalytic cycles. We have applied the photoclick anchoring methodology to precisely control the deposition of a luminescent variant of our catalyst on the metal oxide nanoparticles. Overall, we demonstrate a general approach to use irradiation to anchor molecular complexes on oxide nanoparticles to create recyclable, hybrid, single-site catalysts that function with high selectivity in a broad range of solvents. We have achieved a facile, spatially and temporally controllable photoclick method that can potentially be extended to other ligands, catalysts, functional molecules, and surfaces.

Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

International Nuclear Information System (INIS)

Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

2015-01-01

Graphical abstract: Ligand-modified signal-site SBA-15 supported zirconium catalysts were synthesized by SOMC method and characterized by a variety of techniques. The zirconium surface complexes show high catalytic efficiency for cyanosilylation of benzaldehyde. - Highlights: • Some Zr active species have been anchored on the surface of SBA-15 by SOMC technique. • The structures of the Zr species have been characterized by a variety of techniques. • The anchored Zr species are single-sited surface complexes. • The Zr surface complexes are catalytic active for cyanosilylation of benzaldehyde. - Abstract: A successive anchoring of Zr(NMe 2 ) 4 , cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15 -500 ) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15 -500 supported zirconium complexes were characterized by in situ FT-IR, 13 C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands

Study of the catalytic activity of supported technetium catalysts

International Nuclear Information System (INIS)

Spitsyn, V.I.; Mikhailenko, I.E.; Pokorovskaya, O.V.

1985-01-01

The radioactive d metal 43 Tc 99 has catalytic properties in the synthesis of ammonia. For the purpose of reducing the quantity of the radioactive metal and of increasing the specific surface, the active component was applied to BaTiO 3 and gamma-Al 2 O 3 supports. This paper uses charcoal as a support and a table presents the catalytic activity of the samples during the synthesis of ammonia. X-ray diffractometric investigation of the catalysts was carried out with the use of Cu K /SUB alpha/ radiation. It is shown that the catalysts. The values of the specific rate constants of technetium in the catalysts. The values of the specific rate constants remain practically constant for all the catalyst samples studied, attesting to the absence of a specific metal-support interaction during the synthesis of ammonia

Immobilisation of homogeneous olefin polymerisation catalysts. Factors influencing activity and stability

NARCIS (Netherlands)

Severn, J.R.; Chadwick, J.C.

2013-01-01

The activity and stability of homogeneous olefin polymerisation catalysts, when immobilised on a support, are dependent on both chemical and physical effects. Chemical factors affecting catalyst activity include the ease of formation of the active species, which is strongly dependent on the

Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

Science.gov (United States)

Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

2018-06-26

It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

Soot oxidation over NOx storage catalysts. Activity and deactivation

International Nuclear Information System (INIS)

Krishna, K.; Makkee, M.

2006-01-01

Soot oxidation activity and deactivation of NO x storage and reduction (NSR) catalysts containing Pt, K, and Ba supported on Al 2 O 3 , are studied under a variety of reaction conditions. K-containing catalysts decrease soot oxidation temperature with O 2 alone and the presence of Pt further enhance the activity due to synergetic effect. The active species responsible for synergism on Pt/K-Al 2 O 3 are unstable and cannot be regenerated. Soot oxidation temperature decreases by about 150 o C with NO+O 2 exhaust feed gas and under lean conditions NSR system acts as catalysed soot filter (CSF). The reactions that are mainly responsible for decreasing soot oxidation temperature are: (1) soot oxidation with NO 2 followed by NO recycles to NO 2 , and (2) soot oxidation with O 2 assisted by NO 2 . Only a part of the stored NO x that is decomposed at high temperatures under lean conditions is found to be useful for soot oxidation. NO x storage capacity of NSR catalysts decreases upon ageing under soot oxidising conditions. This will lead to a decreased soot oxidation activity on stored nitrate decomposition. Pt/K-Al 2 O 3 catalyst is more active, but least stable compared with Pt/Ba-Al 2 O 3 . (author)

Combining Ru, Ni and Ni(OH){sub 2} active sites for improving catalytic performance in benzene hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Zhu, Lihua, E-mail: lihuazhu@stu.xmu.edu.cn [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Sun, Hanlei; Zheng, Jinbao [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Yu, Changlin, E-mail: yuchanglinjx@163.com [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Zhang, Nuowei [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Shu, Qing [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Chen, Bing H., E-mail: chenbh@xmu.edu.cn [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

2017-05-01

In this study, the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts were successfully prepared by the simple methods of hydrazine-reduction and galvanic replacement, where 0.04/0.96 and T represented the Ru/Ni atomic ratio and reducing temperature of the catalyst in N{sub 2}+10%H{sub 2}, respectively. The nanostructures of the Ru{sub 0.04}Ni{sub 0.96} nanoparticles in the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts were controlled by modulating their annealing temperature in N{sub 2}+10%H{sub 2} and characterized by an array of techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy energy dispersive X-ray spectroscopy (STEM-EDS) mapping and high-sensitivity low-energy ion scattering (HS-LEIS). The Ru{sub 0.04}Ni{sub 0.96}/C(30) catalyst, which was composed of Ru clusters or single atoms supported on Ni/Ni(OH){sub 2} nanoparticles, exhibited much better catalytic performance for benzene hydrogenation than the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts reduced at above 30 °C, such as Ru{sub 0.04}Ni{sub 0.96}/C(160) with the nanostructure of partial Ru{sub 0.04}Ni{sub 0.9} alloy and Ru{sub 0.04}Ni{sub 0.96}/C(280) with the nanostructure of complete Ru{sub 0.04}Ni{sub 0.9} alloy. The reason was that the synergistic effect of multiple active sites – Ru, Ni and Ni(OH){sub 2} sites was present in the Ru{sub 0.04}Ni{sub 0.96}/C(30) catalyst, where hydrogen was preferentially activated at Ru sites, benzene was probably activated at Ni(OH){sub 2} surface and Ni acted as a “bridge” for transferring activated H{sup ∗} species to activated benzene by hydrogen spillover effect, hydrogenating and forming product – cyclohexane. This study also provided a typical example to illustrate that the synergy effect of multiple active sites can largely improve the catalytic hydrogenation performance. - Highlights: • The Ru

Activities of Heterogeneous Acid-Base Catalysts for Fragrances Synthesis: A Review

Directory of Open Access Journals (Sweden)

Hartati Hartati

2013-06-01

Full Text Available This paper reviews various types of heterogeneous acid-base catalysts for fragrances preparation. Catalytic activities of various types of heterogeneous acid and base catalysts in fragrances preparation, i.e. non-zeolitic, zeolitic, and mesoporous molecular sieves have been reported. Generally, heterogeneous acid catalysts are commonly used in fragrance synthesis as compared to heterogeneous base catalysts. Heteropoly acids and hydrotalcites type catalysts are widely used as heterogeneous acid and base catalysts, respectively. © 2013 BCREC UNDIP. All rights reservedReceived: 20th January 2013; Revised: 31st March 2013; Accepted: 1st April 2013[How to Cite: Hartati, H., Santoso, M., Triwahyono, S., Prasetyoko, D. (2013. Activities of Heterogeneous Acid-Base Catalysts for Fragrances Synthesis: A Review. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1: 14-33. (doi:10.9767/bcrec.8.1.4394.14-33][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.1.4394.14-33] | View in  |

EXAFS characterization of supported metal catalysts in chemically dynamic environments

International Nuclear Information System (INIS)

Robota, H.J.

1991-01-01

Characterization of catalysts focuses on the identification of an active site responsible for accelerating desirable chemical reactions. The identification, characterization, and selective modification of such sites is fundamental to the development of structure-function relationships. Unfortunately, this goal is far from realized in nearly all catalysts, and particularly in catalysts comprised of small supported metal particles. X-ray absorption spectroscopy (XAS) has had a dramatic effect on our understanding of supported metal particles in their resting state. However, the performance of a catalyst can not be assessed from such simple resting state measurements. Among the factors which influence catalyst performance are the exact catalyst composition, including the support and any modifiers; particle size; catalyst finishing and pretreatment conditions; pressure, composition, and temperature of the operating environment; time. Gaining an understanding of how the structure of a catalytic site can change with such an array of variables requires that we begin to develop measurement methods which are effective under chemically dynamic conditions. Ideally, it should be possible to obtain a full X-ray absorption spectrum of each element thought to have a causal relationship with observed catalyst properties. From these spectra, we can optimally extract only a relatively limited amount of information which we must then piece together with information derived from other characterization methods and intuition to arrive at a hypothetical structure of the operating catalyst. Information about crystallinity, homogeneity, and general disorder can be obtained from the Debye-Waller factor. Finally, through analogy with known compounds, the electronic structure of the active atoms can be inferred from near edge absorption features

Basic study of catalyst aging in the H-coal process

Energy Technology Data Exchange (ETDEWEB)

Cable, T.L.; Massoth, F.E.; Thomas, M.G.

1985-04-01

Samples of CoMo/Al/sub 2/O/sub 3/ catalysts used in an H-coal process demonstration run were studied to determine causes of catalyst deactivation. Physical and surface properties of the aged and regenerated catalysts were examined. Model compounds were used to assess four catalyst activity functions, viz., hydrodesulfurization (HDS), hydrogenation, cracking and hydrodeoxygenation (HDO). Other tests were performed to study the effects of coke and metals separately on the four catalyst activity functions. Catalyst coke content and metal deposits first increased rapidly, then more gradually with exposure time in the process run. Surface area and pore volume markedly decreased with exposure time. Catalyst activities of aged catalysts showed a rapid decline with exposure time. One-day exposure to coal resulted in significant losses in HDS and hydrogenation activities and nearly complete loss in cracking and HDO activities. Although metal deposits caused some permanent catalyst deactivation, coke had a much greater effect. Regenerated catalysts showed less recovery of catalytic activity as processing time increased. These results agreed well with product inspections from the process run. Oxygen chemisorption on aged-regenerated catalysts decreased with catalyst exposure time, indicating a significant loss of active sites. However, ESCA results showed no evidence of extensive sintering of the active MoS/sub 2/ phase. Permanent deactivation of the longer-time exposed catalysts can be ascribed, at least partly, to lateral growth of the active molybdenum sulfide phase. In addition, some loss in cobalt promotion occurred early in the process, which may account for the rapid loss in HDS and HDO activity in regenerated catalysts. 24 references.

Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

Science.gov (United States)

Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

2015-12-01

The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites. Here we show for a bifunctional catalyst—comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder—that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts.

Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes.

Science.gov (United States)

Sun, Bo; Yoshino, Tatsuhiko; Kanai, Motomu; Matsunaga, Shigeki

2015-10-26

The synthesis of isoquinolines by site-selective C-H activation of O-acyl oximes with a Cp*Co(III) catalyst is described. In the presence of this catalyst, the C-H activation of various unsymmetrically substituted O-acyl oximes selectively occurred at the sterically less hindered site, and reactions with terminal as well as internal alkynes afforded the corresponding products in up to 98 % yield. Whereas the reactions catalyzed by the Cp*Co(III) system proceeded with high site selectivity (15:1 to 20:1), use of the corresponding Cp*Rh(III) catalysts led to low selectivities and/or yields when unsymmetrical O-acyl oximes and terminal alkynes were used. Deuterium labeling studies indicate a clear difference in the site selectivity of the C-H activation step under Cp*Co(III) and Cp*Rh(III) catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Step sites in syngas catalysis

DEFF Research Database (Denmark)

Rostrup-Nielsen, J.; Nørskov, Jens Kehlet

2006-01-01

Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative explanat......Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative...... explanation of the impact of step sites on catalyst activity and side reactions such as carbon formation. This leads to a discussion of principles for catalyst promotion....

Ethanolysis conversion of spent frying oils over aluminium, calcium-phosphate based bi-functional formulated catalysts. Catalytic activity assessment study

Energy Technology Data Exchange (ETDEWEB)

Al-Zaini, Essam O.; Chesterfield, Dean; Adesina, Adesoji A. [The Univ. of New South Wales, Sydney (Australia). Reactor Engineering and Technology Group; Olsen, John [The Univ. of New South Wales, Sydney (Australia). School of Mechanical and Manufacturing Engineering

2013-06-01

The current study compares the catalytic performance of two bi-functional solid catalysts for the transesterification of waste cooking vegetable oil in presence of bio-ethanol acyl-acceptor. The two catalysts were aluminum oxide and seashell-derived calcium oxide supported K{sub 3}PO{sub 4}. The catalytic activity of the produced catalyst samples were assessed and evaluated in terms of their textural and surface chemical properties. Evaluative runs showed that increased amounts of K{sub 3}PO{sub 4} have differently controlled the textural and surface chemical property of the finally synthesised catalyst samples. The behaviour revealed a strong correlation between the percentage yield of ethyl esters EEY% and acid-base site density and strength between the two types of catalysts. Possible leaching test of the catalysts was also used as a measure of performance and as a result, the optimum catalyst, on the basis of both ester yield and resistance to leaching was identified as the sample containing between 10 and 15wt% of K{sub 3}PO{sub 4} on AlO{sub 3} and CaO respectively. (orig.)

Metal Chlorides Supported Solid Catalysts for F-C Acylations of Arenes

Institute of Scientific and Technical Information of China (English)

李阳; 刘云龙; 穆曼曼; 陈立功

2015-01-01

A series of metal chlorides supported solid catalysts were prepared by simple wet impregnation method. Their catalytic performances for Friedel-Crafts acylation of toluene with benzoyl chloride were evaluated and the excellent results were obtained over FeCl3/SiO2. These catalysts were characterized by BET, NH3-TPD and FT-IR of pyridine adsorption to clarify the structure-activity relationship. It was found that FeCl3/SiO2 has larger pore size and pore volume than other catalysts, which increased the accessibility of the catalyst. In addition, FeCl3/SiO2 ex-hibited higher molar ratio of Lewis acid sites and Brφnsted acid sites, which might be another reason for the in-crease of toluene conversion. Furthermore, the reaction parameters, including temperature, time and molar ratio, were optimized. Under the optimized conditions, 91.2%, conversion and 82.0%, selectivity were obtained. Mean-while, the generality of the catalyst was demonstrated by the acylations of alkyl substituted aromatics. Finally, the catalyst was reused for four runs with slight loss in catalytic activity, which attributed to the drain of the active component.

Olefin polymerization from single site catalysts confined within porous media

Science.gov (United States)

Kasi, Rajeswari M.

Single Site Catalysts (SSCs) have been utilized for olefin polymerization. Altering the metal-ligand architecture in the SSCs, polyolefin properties can be enhanced in a rational manner. This influence of the ligands in the SSC on the property of polyolefins prepared can be referred to as the primary ligand influence. Extending this understanding and subsequent control of the metal-ligand framework to the interaction of SSCs within organic and inorganic supports is vital for the synthesis of polyolefins with tailored properties. The motivation behind this thesis was to explore the support influence on the reactivity of the SSC tethered to a support matrix during ethylene homo and copolymerization. In order to address this question of the support influence on the final polyolefin properties, synthetic routes to covalently bind SSCs on different matrices have been explored. Two distinct supported SSCs have been used to prepare branched polyethylenes. Branched polyethylenes can be prepared by either copolymerization (ethylene and alpha-olefin) or oligomerization/copolymerization processes (ethylene and in situ generated alpha-olefin). Synthetic routes to prepare precursor catalysts to Constrained Geometry Catalysts (CGCs) by silyl elimination chemistry have been developed (Chapter 2). Efficient synthetic protocols to assemble CGCs on aminomethylpolysytrene matrices (Chapter 3) and amine-functionalized mesoporous silica (Chapter 4) are also reported. These supported catalysts, with appropriate cocatalysts have been used to prepare ethylene homo and copolymers, the polymer thermal properties and microstructures were analyzed by various analytical techniques. Branched polyethylenes (LLDPE) can be prepared by copolymerization chemistry. It has been observed is that the influence of the support is seen in the production of lower crystalline forms of high density polyethylene (HDPE, 20--50% crystalline), while homogeneous polymerization of analogous soluble CGCs afford HDPE

Multifunctional magnetic core–shell dendritic mesoporous silica nanospheres decorated with tiny Ag nanoparticles as a highly active heterogeneous catalyst

International Nuclear Information System (INIS)

Sun, Zebin; Li, Haizhen; Cui, Guijia; Tian, Yaxi; Yan, Shiqiang

2016-01-01

Graphical abstract: - Highlights: • A multifunctional magnetic core–shell dendritic silica nanocatalyst was successfully fabricated by an oil–water biphase stratification coating strategy. • The magnetic core–shell dendritic silica nanomaterials Fe_3O_4@SiO_2@Dendritic-SiO_2 were chosen as the catalyst's support for the first time. • The as-synthesized nanocatalyst exhibited excellent catalytic activity and reusability due to easy accessibility of active sites and superparamagnetism. • The novel catalyst could be conveniently recovered by magnetic separation from the reaction system. - Abstract: In present work, a multifunctional magnetic core–shell dendritic silica nanocatalyst Fe_3O_4@SiO_2@Dendritic-SiO_2-NH_2-Ag with easy accessibility of active sites and convenient recovery was successfully fabricated by an oil–water biphase stratification coating strategy, and characterized by transmission electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, N_2 adsorption–desorption, Fourier transform infrared spectroscopy, and vibrating sample magnetometry. The as-synthesized nanocatalyst Fe_3O_4@SiO_2@Dendritic-SiO_2-NH_2-Ag displayed excellent catalytic activity for the catalytic reduction of 4-nitrophenol and 2-nitroaniline using sodium borohydride in aqueous solution at room temperature due to easy accessibility of active sites. Interestingly, the novel catalyst could be conveniently recovered by magnetic separation from the reaction system and recycled for at least five times without significant loss in activity. These results indicate that the above mentioned approach based on magnetic core–shell dendritic silica Fe_3O_4@SiO_2@Dendritic-SiO_2 provided a useful platform for the preparation of noble metal nanocatalysts with easy accessibility, excellent catalytic activity and convenient recovery.

Immunity of the Fe-N-C catalysts to electrolyte adsorption: phosphate but not perchloric anions

DEFF Research Database (Denmark)

Hu, Yang; Jensen, Jens Oluf; Pan, Chao

2018-01-01

often carried out, like for Pt-based catalysts, in dilute perchloric acid by assuming its non-adsorbing nature on the active sites. The assumption is however not true. In this work, a typical Fe-N-C catalyst was first synthesized by high-pressure pyrolysis in the presence of carbon support...... and thoroughly characterized in terms of morphology, structure and active site distribution. The subsequent electrochemical characterization of the catalyst shows strong adsorption and poisoning effect of, in addition to the known Cl-, perchloric anions on the oxygen reduction reaction (ORR) activity...

CATALYTIC PERFORMANCES OF Fe2O3/TS-1 CATALYST IN PHENOL HYDROXYLATION REACTION

Directory of Open Access Journals (Sweden)

Didik Prasetyoko

2010-07-01

Full Text Available Hydroxylation reaction of phenol into diphenol, such as hydroquinone and catechol, has a great role in many industrial applications. Phenol hydroxylation reaction can be carried out using Titanium Silicalite-1 (TS-1 as catalyst and H2O2 as an oxidant. TS-1 catalyst shows high activity and selectivity for phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O2 adsorption toward the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be low. Addition of metal oxide Fe2O3 enhanced hydrophilicity of TS-1 catalyst. Liquid phase catalytic phenol hydroxylation using hydrogen peroxide as oxidant was carried out over iron (III oxide-modified TS-1 catalyst (Fe2O3/TS-1, that were prepared by impregnation method using iron (III nitrate as precursor and characterized by X-ray diffraction, infrared spectroscopy, nitrogen adsorption, pyridine adsorption, and hydrophilicity techniques. Catalysts 1Fe2O3/TS-1 showed maximum catalytic activity of hydroquinone product. In this research, the increase of hydroquinone formation rate is due to the higher hydrophilicity of Fe2O3/TS-1 catalysts compare to the parent catalyst, TS-1.   Keywords: Fe2O3/TS-1, hydrophilic site, phenol hydroxylation

Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

Energy Technology Data Exchange (ETDEWEB)

Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang, E-mail: gfzhang@snnu.edu.cn; Gao, Ziwei, E-mail: zwgao@snnu.edu.cn

2015-01-15

Graphical abstract: Ligand-modified signal-site SBA-15 supported zirconium catalysts were synthesized by SOMC method and characterized by a variety of techniques. The zirconium surface complexes show high catalytic efficiency for cyanosilylation of benzaldehyde. - Highlights: • Some Zr active species have been anchored on the surface of SBA-15 by SOMC technique. • The structures of the Zr species have been characterized by a variety of techniques. • The anchored Zr species are single-sited surface complexes. • The Zr surface complexes are catalytic active for cyanosilylation of benzaldehyde. - Abstract: A successive anchoring of Zr(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15{sub -500}) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15{sub -500} supported zirconium complexes were characterized by in situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands.

More active and sulfur resistant bimetallic Pd-Ni catalysts

Energy Technology Data Exchange (ETDEWEB)

Betti, Carolina; Carrara, Nicolás; Badano, Juan; Lederhos, Cecilia; Vera, Carlos; Quiroga, Mónica, E-mail: mquiroga@fiq.unl.edu.ar [Instituto de Investigaciones en Catálisis y Petroquímica, INCAPE (FIQ-UNL, CONICET), Santa Fe (Argentina)

2018-02-15

The influence of the kind of metal precursor and the sequence of impregnation on the properties of Pd-Ni catalysts was evaluated during the test reaction of selective hydrogenation of styrene to ethylbenzene by means of physicochemical characterization. The focus was put on the final hydrogenating activity and the resistance to deactivation by sulfide compounds (thiophene). The used techniques of characterization were ICP, XPS, XDR, TPR, CO chemisorption and TEM. XPS results indicated the presence of different Pd species: Pd{sup δ-}, Pd{sup 0} and Pd{sup δ+}. In the case of the Ni containing catalysts, Ni{sup 0} and NiO species were also detected. These palladium and nickel species would be responsible of the variation of activity and sulfur resistance of the catalysts. NiClPd catalysts had a higher resistance to deactivation by sulfur poisoning. This was associated to a higher concentration of Pd{sup η+}Cl{sub x}O{sub y} species that would prevent the adsorption of thiophene by both steric and electronic effects. It could also be due to the lower concentration of Pd{sup 0} and Ni{sup 0} on these catalysts, as compared to those shown by the PdNiCl catalysts. Both the Pd{sup 0} and Ni{sup 0} species are more prone to poisoning because of their higher electronic availability. (author)

Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

Energy Technology Data Exchange (ETDEWEB)

Coan, Patrick D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Ellis, Lucas D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Griffin, Michael B. [National Bioenergy Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Schwartz, Daniel K. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Medlin, J. Will [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States

2018-03-01

Cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al2O3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivity for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al2O3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.

Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

Science.gov (United States)

Albayati, Talib M.; Doyle, Aidan M.

2015-02-01

Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

Energy Technology Data Exchange (ETDEWEB)

Albayati, Talib M., E-mail: talib-albyati@yahoo.com [University of Technology, Department of Chemical Engineering (Iraq); Doyle, Aidan M., E-mail: a.m.doyle@mmu.ac.uk [Manchester Metropolitan University, Division of Chemistry and Environmental Science (United Kingdom)

2015-02-15

Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption–desorption porosimetry (Brunauer–Emmett–Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96–99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

International Nuclear Information System (INIS)

Albayati, Talib M.; Doyle, Aidan M.

2015-01-01

Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption–desorption porosimetry (Brunauer–Emmett–Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96–99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction

Evaluation of photocatalytic activities of supported catalysts on NaX zeolite or activated charcoal

Energy Technology Data Exchange (ETDEWEB)

Brites-Nóbrega, Fernanda F. de [Chemical Engineering Department, Universidade Estadual de Maringá (UEM), Av. Colombo, 5790, CEP 87020-900 Maringá, PR (Brazil); Sanitary and Environmental Engineering Department, Universidade Federal de Minas Gerais (UFMG), Av. Antônio Carlos, 6627, Campus Pampulha, Belo Horizonte, MG (Brazil); Polo, Aldino N.B.; Benedetti, Angélica M. [Chemical Engineering Department, Universidade Estadual do Oeste do Paraná (UNIOESTE), Rua da Faculdade, 645, CEP 85903-000 Toledo, PR (Brazil); Leão, Mônica M.D. [Sanitary and Environmental Engineering Department, Universidade Federal de Minas Gerais (UFMG), Av. Antônio Carlos, 6627, Campus Pampulha, Belo Horizonte, MG (Brazil); Slusarski-Santana, Veronice, E-mail: veronice.santana@unioeste.br [Chemical Engineering Department, Universidade Estadual do Oeste do Paraná (UNIOESTE), Rua da Faculdade, 645, CEP 85903-000 Toledo, PR (Brazil); Fernandes-Machado, Nádia R.C. [Chemical Engineering Department, Universidade Estadual de Maringá (UEM), Av. Colombo, 5790, CEP 87020-900 Maringá, PR (Brazil)

2013-12-15

Highlights: • The synergic effect between ZnO and NaX was positive, which increased its activity. • The best results were obtained at pH 3 and 9 with ZnO/NaX and at pH 3 with Nb{sub 2}O{sub 5}/AC. • High degradation and considerable mineralization were attained with 10% ZnO/NaX. • ZnO and Nb{sub 2}O{sub 5} supported on NaX and AC are promising alternatives as photocatalysts. -- Abstract: This study aimed to evaluate the photocatalytic activity of ZnO and Nb{sub 2}O{sub 5} catalysts, both supported on NaX zeolite and activated charcoal (AC). The synergistic effect between oxide and support and the influence of solution pH (3, 7 and 9) on photocatalytic degradation of reactive blue 5G (C.I. 222) were analyzed. The catalysts Nb{sub 2}O{sub 5}/NaX, Nb{sub 2}O{sub 5}/AC and ZnO/NaX, ZnO/AC with 5 and 10% (wt%) were prepared by wet impregnation. The results showed that the catalysts exhibit quite different structural and textural properties. The synergic effect between ZnO and NaX support was higher than that with the activated charcoal, showing that these catalysts were more efficient. The most photoactive catalyst was 10% ZnO/NaX which showed 100% discoloration of the dye solution at pH 3, 7 and 9 after 0.5, 5 and 2 h of irradiation, respectively. The hydrolytic nature of zeolite favored the formation of surface hydroxyl radicals, which increased the activity of the photocatalyst. Thus, catalysts supported on NaX zeolite are promising for use in photocatalysis.

Activity enhancement of Ag/mordenite catalysts by addition of palladium for the removal of nitrogen oxides from diesel engine exhaust gas

Energy Technology Data Exchange (ETDEWEB)

Masuda, K.; Tsujimura, K. [New A.C.E. Institute Co., Ltd., Ibaraki (Japan); Shinoda, K.; Kato, T. [Mitsui Mining and Smelting Co., Ltd., Saitama (Japan)

1998-01-15

Various Ag-Pd/mordenite catalysts were prepared on washcoated honeycombs and tested in terms of NO{sub x} removal from diesel exhaust gas with (CH{sub 3}){sub 2}O as a reducing agent at a practical high level of space velocity. The activity was dependent upon the palladium loading. In terms of NO{sub x} removal, the order of catalytic activity was Ag(3)/Pd(0.01)/mordenite Ag(3)/Pd(0.1)/mordenite Ag(3)/mordenite catalyst Ag(3)/Pd(1.0)/mordenite. It was found that a relatively small loading of palladium on Ag/mordenite catalysts led to a significant improvement in catalytic activity over a wide range of temperatures. The properties of these catalysts were also investigated by the NH{sub 3} temperature programed desorption (TPD) and BET method. It was found that Ag(3)/Pd(0.01)/mordenite had a larger amount of acid sites. It was concluded that Ag/mordenite catalyst with a small amount of palladium can effectively remove NO{sub x} over a wide range of temperatures using (CH{sub 3}){sub 2}O as a reducing agent

Sustainable Applications of Magnetic Nano-catalysts and Graphitic Carbon Nitrides (presentation)

Science.gov (United States)

Homogeneous catalysts, known for chemo-, regio- and enantioselectivity, have better contact with the reactants but the catalyst separation creates barriers. Heterogeneous systems enable better separation although at the cost of reduction in the availability of active sites. Becau...

Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation.

Science.gov (United States)

Feng, Yue; Bin, Duan; Yan, Bo; Du, Yukou; Majima, Tetsuro; Zhou, Weiqiang

2017-05-01

Porous bimetallic PdNi catalysts were fabricated by a novel method, namely, reduction of Pd and Ni oxides prepared via calcining the complex chelate of PdNi-dimethylglyoxime (PdNi-dmg). The morphology and composition of the as-prepared PdNi were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Furthermore, the electrochemical properties of PdNi catalysts towards ethanol electrooxidation were also studied by electrochemical impedance spectrometry (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurement. In comparison with porous Pd and commercial Pd/C catalysts, porous structural PdNi catalysts showed higher electrocatalytic activity and durability for ethanol electrooxidation, which may be ascribed to Pd and Ni property, large electroactive surface area and high electron transfer property. The Ni exist in the catalyst in the form of the nickel hydroxides (Ni(OH) 2 and NiOOH) which have a high electron and proton conductivity enhances the catalytic activity of the catalysts. All results highlight the great potential application of the calcination-reduction method for synthesizing high active porous PdNi catalysts in direct ethanol fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Dehydration of alcohols using solid acid catalysts

OpenAIRE

Cholerton, Mary

2014-01-01

Solid acid catalysts were prepared through silicon substitution into aluminophosphate frameworks. Silicon incorporation was confirmed using solid state nuclear magnetic resonance spectroscopy. The nature of the acid sites generated was determined using Fourier Transform infrared spectroscopy. These materials were tested as catalysts for the dehydration of ethanol to ethylene at low operating temperatures. The materials were active for dehydration of ethanol to ethylene with significant differ...

The acidic properties of mixed tin and antimony oxide catalysts

Energy Technology Data Exchange (ETDEWEB)

Irving, E.A.; Taylor, D.

1978-01-01

The acidic properties of mixed tin + antimony oxide catalysts were studied in the isomerization of 3,3-dimethyl-1-butene, cyclopropane, 1-butene, and cis-2-butene and the dehydration of isopropanol over the mixed oxides outgassed at room temperature and 698/sup 0/K. Only the zero-order portions of the reaction were used for calculations. With catalysts outgassed at room temperature, weakly acidic sites were present, and all the reactions probably occurred by a carbonium ion mechanism with Broensted acid sites as a source of protons. The rates increased with increasing antimony content to a maximum at approx. 50 at. % and then decreased with further increase in the antimony content. Outgassing of the catalysts at 698/sup 0/K increased the isomerization rate of 3,3-dimethyl-1-butene, but decreased those for cyclopropane and isopropanol due to poisoning by the propylene produced. For 1-butene and cis-2-butene and catalysts outgassed at 698/sup 0/K, only catalysts with less than 50Vertical Bar3< antimony were active. The catalysts were poisoned by treatment with bases or with sodium acetate. A proposed correlation between rates and acidity led to the conclusion that the catalyst composition corresponding to maximum acidity differs from that for maximum selective oxidation activity. Graphs and 10 references.

Change in activity of catalysts for the oxidation of tritium during a fire event

International Nuclear Information System (INIS)

Iwai, Yasunori; Sato, Katsumi; Yamanishi, Toshihiko

2012-01-01

Highlights: ► We experimentally demonstrated the influence of produced gases from burned low-halogen cable on the activity of catalysts for tritium oxidation. ► At 423 K, no considerable decrease in catalytic activity was observed. ► At 293 K, considerable increase in catalytic activity was initially observed due to the effect of produced hydrogen. Then the temporary decrease was observed due mainly to the effect of produced moisture, however the activity was gradually recovered. - Abstract: The catalytic performance should be maintained in any off normal events. Fire accident is the typical off normal event. In the fusion plant, typical combustibles are evaluated to be polymeric low-halogen cables. Produced gases from burned low-halogen cable may affect the activity of catalysts for the oxidation of tritium. We experimentally demonstrated the influence of produced gases from burned low-halogen cable on the activity of catalyst using tritium gas. Our evaluation showed that ethylene, methane and benzene were major produced gases. The activity of catalysts for the oxidation of tritium during a fire event was evaluated using a commercial hydrophilic Pt/Al 2 O 3 catalyst and a commercial hydrophobic Pt-catalyst. The temperature of catalytic reactor was selected to be 423 and 293 K. At 423 K, no considerable decrease in catalytic activity was observed for both catalysts even in the presence of produced gases from burned low-halogen cable. At 293 K, considerable increase in catalytic activity was initially observed for both catalysts due to the effect of produced hydrogen. Then the temporary decrease was observed, however the catalytic activity was gradually recovered to be the original activity. Consequently, the irreversible decrease in activity of the catalysts during a fire event was not observed.

An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15.

Science.gov (United States)

Zhang, Lei; Abbenhuis, Hendrikus C L; Gerritsen, Gijsbert; Bhriain, Nollaig Ní; Magusin, Pieter C M M; Mezari, Brahim; Han, Wei; van Santen, Rutger A; Yang, Qihua; Li, Can

2007-01-01

A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active center, was immobilized successfully by in-situ copolymerization on a mesoporous SBA-15-supported polystyrene polymer. The resulting hybrid materials exhibit attractive textural properties (highly ordered mesostructure, large specific surface area (>380 m2 g-1) and pore volume (>or==0.46 cm3 g-1)), and high activity in the epoxidation of alkenes. In the epoxidation of cyclooctene with tert-butyl hydrogen peroxide (TBHP), the hybrid catalysts have rate constants comparable with that of their homogeneous counterpart, and can be recycled at least seven times. They can also catalyze the epoxidation of cyclooctene with aqueous H2O2 as the oxidant. In two-phase reaction media, the catalysts show much higher activity than their homogeneous counterpart due to the hydrophobic environment around the active centers. They behave as interfacial catalysts due to their multifunctionality, that is, the hydrophobicity of polystyrene and the polyhedral oligomeric silsesquioxanes (POSS), and the hydrophilicity of the silica and the mesoporous structure. Combination of the immobilization of homogeneous catalysts on two conventional supports, inorganic solid and organic polymer, is demonstrated to achieve novel heterogeneous catalytic ensembles with the merits of attractive textural properties, tunable surface properties, and optimized environments around the active sites.

Acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts for hydrodeoxygenation process

Science.gov (United States)

Lup, A. Ng K.; Abnisa, F.; Daud, W. M. A. W.; Aroua, M. K.

2018-03-01

Hydrodeoxygenation is an oxygen removal process that occurs in the presence of hydrogen and catalysts. This study has shown the importance of acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts in having high hydrodeoxygenation activity and selectivity. These properties are required to ensure the catalyst has high affinity for C-O or C=O bonds and the capability for the adsorption and activation of H2 and O-containing compounds. A theoretical framework of temperature programmed desorption technique was also discussed for the quantitative understanding of these properties. By using NH3-TPD, the nature and abundance of acid sites of catalyst can be determined. By using H2-TPD, the nature and abundance of metallic sites can also be determined. The desorption activation energy could also be determined based on the Redhead analysis of TPD spectra with different heating rates.

Activation of heterogenised rhodium carbonylation catalyst infrared spectroscopic study

Energy Technology Data Exchange (ETDEWEB)

Scurrell, M S

1977-01-01

In a study related to heterogeneous versions of homogeneous catalysts active in carbonylation of methanol to acetic acid, the catalyst consisted of 1Vertical Bar3< rhodium as rhodium trichloride supported on 13X zeolite and evacuated at 437/sup 0/K. Contacting the catalyst with carbon monoxide caused two bands, at 2025 and 2095 cm/sup -1/, to appear. Contact with a mixture of carbon monoxide and methyl iodide (the usual promoter) caused bands at 2085, 1710, 1440, and 1370 cm/sup -1/ to appear; the first two correspond to the bands at 2062 and 1711 cm/sup -1/ in homogeneous catalysts attributed to the formation of Rh(CH/sup 3/CO)(CO)X/sup 2/I/sup -/. Spectra.

Regeneration of Pt-catalysts deactivated in municipal waste flue gas with H2/N2 and the effect of regeneration step on the SCR catalyst

DEFF Research Database (Denmark)

Due-Hansen, Johannes; Rasmussen, Søren Brik; Kustov, Arkady

The deactivation performance of Pt-catalysts for CO oxidation has been studied in relation to use in sewage sludge municipal waste burners, where HMDS was found to poison the industrial catalyst in a similar way to the model Pt/TiO2 catalyst. A promising regeneration procedure was developed based...... on reduction with hydrogen. This procedure had negligible effect on the performance of the SCR catalyst. After treatment with 2% H2, 8% O2 in N2 for one hour, a slight better NO SCR activity was observed due to increase in the concentration V4+ sites. However, after exposure in normal NO SCR gases the activity...

Cobalt-embedded carbon nanofiber derived from a coordination polymer as a highly efficient heterogeneous catalyst for activating oxone in water.

Science.gov (United States)

Lin, Kun-Yi Andrew; Tong, Wai-Chi; Du, Yunchen

2018-03-01

Carbon fiber (CF) supported cobalt nanoparticles (NPs) are promising catalysts for activating Oxone because carbon is non-metal and earth-abundant, and CF-based catalysts exhibit a high aspect ratio, which affords more accessible and dense catalytic sites. Nevertheless, most of CF-supported catalysts are fabricated by post-synthetic methods, which involve complicated preparations. More importantly, metallic NPs are attached to the outer surface of CF rather than embedded within CF. However, there is still a great demand for developing Co-bearing carbon fibers for Oxone activation via simple and effective methods. Thus, this study proposes to develop a cobalt NP-embedded carbon nanofiber (CCNF) by a simple hydrothermal reaction of Co and nitrilotriacetic acid (NA), followed by one-step carbonization. Owing to the coordinative structure of CoNA, the derivative CCNF exhibits a fibrous carbon matrix embedded with evenly distributed and densely packed Co 3 O 4 and magnetic Co 0 nanoparticles. The fibrous structure, magnetism and embedded Co NPs enable CCNF to be a promising catalyst for Oxone activation. As degradation of Rhodamine B (RhB) is selected as a model reaction, CCNF not only rapidly activates Oxone to fully degrade RhB but also shows a much higher catalytic activity than the most common Oxone activator, Co 3 O 4 . CCNF also exhibits the lowest activation energy than any reported catalysts for Oxone activation to degrade RhB. In addition, CCNF could be re-used to activate Oxone for RhB degradation. These results indicate that CCNF is a conveniently prepared and highly effective fibrous Co/C hybrid material for activating Oxone to oxidize contaminants in water. Copyright © 2017. Published by Elsevier Ltd.

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

Science.gov (United States)

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

Coatings of active and heat-resistant cobalt-aluminium xerogel catalysts.

Science.gov (United States)

Schubert, Miriam; Schubert, Lennart; Thomé, Andreas; Kiewidt, Lars; Rosebrock, Christopher; Thöming, Jorg; Roessner, Frank; Bäumer, Marcus

2016-09-01

The application of catalytically coated metallic foams in catalytic processes has a high potential for exothermic catalytic reactions such as CO2 methanation or Fischer-Tropsch synthesis due to good heat conductivity, improved turbulent flow properties and high catalyst efficiencies. But the preparation of homogenous catalyst coats without pore blocking is challenging with conventional wash coating techniques. Here, we report on a stable and additive free colloidal CoAlOOH suspension (sol) for the preparation of catalytically active Co/Al2O3 xerogel catalysts and coatings. Powders with 18wt% Co3O4 prepared from this additive free synthesis route show a catalytic activity in Fischer-Tropsch synthesis and CO2 methanation which is similar to a catalyst prepared by incipient wetness impregnation (IWI) after activating the material under flowing hydrogen at 430°C. Yet, the xerogel catalyst exhibits a much higher thermal stability as compared to the IWI catalyst, as demonstrated in catalytic tests after different heat agings between 430°C and 580°C. It was also found that the addition of polyethylene glycol (PEG) to the sol influences the catalytic properties of the formed xerogels negatively. Only non-reducible cobalt spinels were formed from a CoAlOOH sol with 20wt% PEG. Metallic foams with pores sizes between 450 and 1200μm were coated with the additive free CoAlOOH sol, which resulted in homogenous xerogel layers. First catalytic tests of the coated metal foams (1200μm) showed good performance in CO2 methanation. Copyright © 2016 Elsevier Inc. All rights reserved.

Application of zeolite-based catalyst to hydrocracking of coal-derived liquids

Energy Technology Data Exchange (ETDEWEB)

Shimada, H.; Sato, T.; Yoshimura, Y.; Hinata, A.; Yoshitomi, S.; Castillo Mares, A.; Nishijima, A. (National Chemical Laboratory for Industry, Tsukuba (Japan))

1990-06-01

Y-zeolite supported catalysts were applied to the hydrocracking of coal-derived liquids. By the introduction of two-stage upgrading consisting of hydrotreating and hydrocracking, Wandoan coal-derived middle distillate was hydrocracked over Ni-Mo/Y-zeolite, producing a high gasoline fraction yield. Zeolite supported catalysts gave little hydrocracked compounds in the hydroprocessing of coal-derived heavy oils, even after hydrotreatment. The reaction inhibitors which seriously poison the active sites of zeolites were found to be small nitrogen-containing molecules. In the hydroprocessing of coal-derived heavy oils, zeolite supported catalysts were inferior to alumina supported catalysts. This is due to the high hydrocracking but low hydrogenation activity of zeolite supported catalysts. 22 refs., 5 figs., 11 tabs.

Interaction of water, alkyl hydroperoxide, and allylic alcohol with a single-site homogeneous Ti-Si epoxidation catalyst: A spectroscopic and computational study.

Science.gov (United States)

Urakawa, Atsushi; Bürgi, Thomas; Skrabal, Peter; Bangerter, Felix; Baiker, Alfons

2005-02-17

Tetrakis(trimethylsiloxy)titanium (TTMST, Ti(OSiMe3)4) possesses an isolated Ti center and is a highly active homogeneous catalyst in epoxidation of various olefins. The structure of TTMST resembles that of the active sites in some heterogeneous Ti-Si epoxidation catalysts, especially silylated titania-silica mixed oxides. Water cleaves the Ti-O-Si bond and deactivates the catalyst. An alkyl hydroperoxide, TBHP (tert-butyl hydroperoxide), does not cleave the Ti-O-Si bond, but interacts via weak hydrogen-bonding as supported by NMR, DOSY, IR, and computational studies. ATR-IR spectroscopy combined with computational investigations shows that more than one, that is, up to four, TBHP can undergo hydrogen-bonding with TTMST, leading to the activation of the O-O bond of TBHP. The greater the number of TBHP molecules that form hydrogen bonds to TTMST, the more electrophilic the O-O bond becomes, and the more active the complex is for epoxidation. An allylic alcohol, 2-cyclohexen-1-ol, does not interact strongly with TTMST, but the interaction is prominent when it interacts with the TTMST-TBHP complex. On the basis of the experimental and theoretical findings, a hydrogen-bond-assisted epoxidation mechanism of TTMST is suggested.

Direct NO decomposition over conventional and mesoporous Cu-ZSM-5 and Cu-ZSM-11 catalysts

DEFF Research Database (Denmark)

Kustova, Marina; Rasmussen, Søren Birk; Kustov, Arkadii

2006-01-01

Conventional Cu-ZSM-5 has for many years been recognized as a unique catalyst for direct NO decomposition. Zeolite-based catalysts have a crystallographically well-defined microporous structure. In such microporous catalysts, the creation and accessibility of the active sites is often influenced...... that ZSM-11 has only straight microporous channels, while ZSNI-5 has both straight and sinusoidal channels. Apparently, there is a preferential formation of active sites and/or improved accessibility in the straight channels compared to the sinusoidal channels, which make the ZSM-11 material a better...

Enhanced Activity and Selectivity of Carbon Nanofiber Supported Pd Catalysts for Nitrite Reduction

KAUST Repository

Shuai, Danmeng; Choe, Jong Kwon; Shapley, John R.; Werth, Charles J.

2012-01-01

Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment. © 2012 American Chemical Society.

Enhanced Activity and Selectivity of Carbon Nanofiber Supported Pd Catalysts for Nitrite Reduction

KAUST Repository

Shuai, Danmeng

2012-03-06

Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment. © 2012 American Chemical Society.

Activity and Stability of Nanoscale Oxygen Reduction Catalysts

Energy Technology Data Exchange (ETDEWEB)

Shao-Horn, Yang

2015-07-28

Design of highly active and stable nanoscale catalysts for electro-oxidation of small organic molecules is of great importance to the development of efficient fuel cells. The amount and instability of Pt-based catalysts in the cathode limits the cost, efficiency and lifetime of proton exchange membrane fuel cells. We developed a microscopic understanding of the factors governing activity and stability in Pt and PtM alloys. Experimental efforts were focused on probing the size and shape dependence of ORR activity of Pt-based nanoparticles supported on carbon nanotubes. A microscopic understanding of the activity was achieved by correlating voltammetry and rotating ring disk electrodes to surface atomic and electronic structures, which were elucidated predominantly by high-resolution transmission electron microscopy (HRTEM), Scanning transmission electron microscopy energy dispersive X-ray Spectroscopy (STEM-EDS) and synchrotron X-ray absorption spectroscopy (XAS).

Secondary promoters in alumina-supported nickel-molybdenum hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Lewis, J.M.

1992-01-01

Two secondary promoters, phosphorus and fluoride, have been investigated for their influences on the physicochemical properties of alumina-supported nickel-molybdenum hydroprocessing catalysts. Model compound reactions and infrared spectroscopy were used to probe the functionalities of the different catalysts, and the catalysts were tested in the hydroprocessing of a low-nitrogen and a high-nitrogen (quinoline-spiked) gas oil feed to assess the utility of the model compound reaction studies. Fluoride-promoted catalysts with high cumene hydrocracking activity and with comparable thiophene hydrodesulphurization (HDS) activity to Ni-Mo/Al[sub 2]O[sub 3] can be prepared by coimpregnation of the F, Ni and Mo additives. Fluoride promotes the hydrogenation (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of a low-nitrogen feed. Fluoride promotes the quinoline hydrodenitrogenation (HDN) activity of Ni-Mo/Al[sub 2]O[sub 3] catalysts. Impregnation of phosphorus prior to the metal additives results in catalysts which are more active in HDS. Phosphorus increases indirectly the Broensted acidity of the catalyst by increasing the activity of the MoS[sub 2]-associated acid sites. Phosphorus promotes the HDSW and HYD activities of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of the low-N feed. A promotional effect of phosphorus is seen in quinoline HDN. P- and F-promoted Ni-MO/Al[sub 2]O[sub 3] catalysts are very active in quinoline HDN and maintain good activity in HDS and HYD of the high-N feed. Thiophene HDS was a good reaction for probing the activity of catalysts in the HDS of sterically-unhindered molecules, but an inaccurate probe for the HDS of hindered compounds.

Surface science of single-site heterogeneous olefin polymerization catalysts

OpenAIRE

Kim, Seong H.; Somorjai, Gabor A.

2006-01-01

This article reviews the surface science of the heterogeneous olefin polymerization catalysts. The specific focus is on how to prepare and characterize stereochemically specific heterogeneous model catalysts for the Ziegler–Natta polymerization. Under clean, ultra-high vacuum conditions, low-energy electron irradiation during the chemical vapor deposition of model Ziegler–Natta catalysts can be used to create a “single-site” catalyst film with a surface structure that produces only isotactic ...

Relating FTS Catalyst Properties to Performance

Science.gov (United States)

Ma, Wenping; Ramana Rao Pendyala, Venkat; Gao, Pei; Jermwongratanachai, Thani; Jacobs, Gary; Davis, Burton H.

2016-01-01

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of ?-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature

Rational Catalyst Design of Titanium-Silica Materials Aided by Site-Specific Titration Tools

Science.gov (United States)

Eaton, Todd Robert

Silica-supported titanium materials are widely used for thermocatalytic applications such as hydroxylation of alkanes and aromatics, oxidation of alcohols and ethers, ammoximation of carbonyls, and sulfoxidations, while Ti-based materials are widely studied for photocatalytic applications such as photo-oxidation of organic substrates and photo-reduction of CO 2. However, the underlying phenomena of how to synthesize, identify, and control the active structures in these materials is not well understood because of the narrow scope of previous work. Studies of titanium-based catalysts typically focus on materials where the metal is present as either highly-dispersed Ti cations or in bulk crystalline TiO2 form, neglecting the numerous and potentially useful intermediate structures. Furthermore, these works typically focus on a single synthesis technique and rely upon bulk characterization techniques to understand the materials. Here rigorous titanium-silica synthesis-structure-function relationships are established by examining several different synthetic method and utilizing characterization techniques that enable an atomic-level understanding of the materials. The materials studied span the range from isolated Ti cations to clustered TiOx domains, polymeric TiO x domains, anatase-like 2D TiO2 domains, and 3D crystalline TiO2. Tools to quantify accessible TiO x and tetrahedral Ti sites are developed, utilizing the selective titration of titanium with phenylphosphonic acid (PPA). Catalytic properties are probed with the photocatalytic oxidation of benzyl alcohol and the thermocatalytic epoxidation of cis-cyclooctene with H2O2 . PPA titration data indicate that the rate of benzyl alcohol photo-oxidation is independent of titanium coordination, while the rate of alkene epoxidation with H2O2 is proportional to the number of tetrahedral titanium sites on the catalyst. PPA titration data also enables the estimation of TiO2 particle size and reveals an important distinction

Some physico-chemical properties and catalytic activity of sulfate ion supported on WO3/SnO2 catalyst

Directory of Open Access Journals (Sweden)

M.N. Alaya

2017-02-01

Full Text Available Solid acid catalyst 15 wt%WO3/SnO2 was synthesized and loaded with 15 wt%SO4. The obtained catalyst was calcined at 400, 500, 650 and 800 °C. The prepared catalysts were characterized by TG-DTA, XRD, FTIR and N2 adsorption at −196 °C. The surface acidity was measured by non aqueous potentiometric titration and FT-IR spectra of chemisorbed pyridine. The catalytic performance was evaluated on the esterification of propionic acid with n-butanol in liquid phase. The TG-DTA analysis shows that the decomposition of sulfate species occurred at >500 °C. XRD measurements showed that WO3 dispersed completely on the surface of SnO2 and that the sulfating of WO3/SnO2 tends to hinder the crystallization of SnO2. The specific surface area, total pore volume and micropore volume are increased with increasing thermal treatment up to 500 °C, and then decreased gradually with a further increase in calcination temperature. The prepared catalysts possess very strong acid sites and contain both Brønsted and Lewis acid sites. The total surface acidity decreased with raising of the calcination temperature. The highest conversion of propionic acid was for 400 °C product, and decreased with an increase in calcination temperature. The effect of the reaction parameters, i.e., time of reaction, reaction temperature, and reactant molar ratio and the weight of the catalyst were also studied. The reaction obeys the second order kinetic equation with respect to propionic acid concentration. Brønsted and Lewis acid sites appeared to be needed for catalytic activity in n-butyl propionate formation.

A Study of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry - Nanostructure - Performance

Science.gov (United States)

Workman, Michael J., Jr.

Fuel cells have the potential to be a pollution-free, low-cost, and energy efficient alternative to the internal combustion engine for transportation and small-scale stationary power applications. The current state of fuel cell technology has already achieved two of these three lofty goals. The remaining barrier to wide-scale deployment is the high cost, which is primarily caused by dependence on large amounts of platinum to catalyze the energy conversion reactions. To overcome this barrier and facilitate the integration of fuel cells into mainstream applications, research into a new class of catalyst materials that do not require platinum is needed. There has been a significant amount of research effort directed toward the development of platinum-group metal free (PGM-free) catalysts, yet there is a lack of consensus on both the engineering parameters necessary to improve the technology and the fundamental science that would facilitate rational design. I have engaged in research on PGM-free catalysts based on inexpensive and abundant reagents, specifically: nicarbazin and iron. Catalysts made from these precursors have previously proven to be among the best PGM-free catalysts, but their continued advancement suffered from the same lack of understanding that besets all catalysts in this class. The work I have performed address both engineering concerns and fundamental underlying principles. I present results demonstrating correlations between physical structure, chemical speciation, and synthesis parameters, as well as addressing active site chemistry and likely locations. My research presented herein introduces new morphology analysis techniques and elucidates several key structure-to-property characteristics of catalysts derived from iron and nicarbazin. I discuss the development and application of a new length-scale specific surface analysis technique that allows for analysis of well-defined size ranges from a few nm to several microns. The existing technique of

Pyrochlore-type catalysts for the reforming of hydrocarbon fuels

Science.gov (United States)

Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV; Haynes, Daniel [Morgantown, WV; Smith, Mark [Morgantown, WV; Spivey, James J [Baton Rouge, LA

2012-03-13

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A.sub.2-w-xA'.sub.wA''.sub.xB.sub.2-y-zB'.sub.yB''.sub.zO.sub.7-.DELTA.. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H.sub.2+CO) for fuel cells, among other uses.

TiO2 nanotubes supported NiW hydrodesulphurization catalysts: Characterization and activity

International Nuclear Information System (INIS)

Palcheva, R.; Dimitrov, L.; Tyuliev, G.; Spojakina, A.; Jiratova, K.

2013-01-01

Highlights: ► NiW catalysts supported on TiO 2 nanotubes, titania and alumina. ► The best results are obtained with NiW/TiO 2 nanotubes in hydrodesulfurization (HDS) of thiophene. ► Active phase is Ni-WO x S y . ► Electronic promotion of W by Ti. - Abstract: High surface area TiO 2 nanotubes (Ti-NT) synthesized by alkali hydrothermal method were used as a support for NiW hydrodesulphurization catalyst. Nickel salt of 12-tungstophosphoric acid – Ni 3/2 PW 12 O 40 was applied as oxide precursor of the active components. The catalyst was characterized by S BET , XRD, UV–vis DRS, Raman spectroscopy, XPS, TPR and HRTEM. The results obtained were compared with those for the NiW catalysts prepared over high surface area titania and alumina supports. A polytungstate phase evidenced by Raman spectroscopy was observed indicating the destruction of the initial heteropolyanion. The catalytic experiments revealed two times higher thiophene conversion on NiW catalyst supported on Ti-NT than those of catalysts supported on alumina and titania. Increased HDS activity of the NiW catalyst supported on Ti-NT could be related to a higher amount of W oxysulfide entities interacting with Ni sulfide particles as consequence of the electronic effects of the Ti-NT observed with XPS analysis.

Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution.

Science.gov (United States)

Hung, Chang-Mao

2009-07-30

Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h(-1).

Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution

International Nuclear Information System (INIS)

Hung, Chang-Mao

2009-01-01

Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h -1 .

The influence of calcination temperature on catalytic activities in a Co based catalyst for CO2 dry reforming

International Nuclear Information System (INIS)

Song, Sang-Hoon; Son, Ju-Hee; Budiman, Anatta Wahyu; Choi, Myoung-Jae; Chang, Tae-Sun; Shin, Chae-Ho

2014-01-01

The carbon dioxide dry reforming of methane (CDR) reaction could be thermodynamically favored in the range of 800 to 1,000 .deg. C. However, the catalyst in this reaction should be avoided at the calcination temperature over 800 .deg. C since strong metal support interaction (SMSI) in this temperature range can decrease activity due to loss of active sites. Therefore, we focused on optimizing the temperature of pretreatment and a comparison of surface characterization results for CDR. Results related to metal sintering over support, re-dispersion by changing of particle size of metal-support, and strong metal support interaction were observed and confirmed in this work. In our conclusion, optimum calcination temperature for a preparation of catalyst was proposed that 400 .deg. C showed a higher and more stable catalytic activity without changing of support characteristics

A surface science model for the Phillips ethylene polymerization catalyst : thermal activation and polymerization activity

NARCIS (Netherlands)

Kimmenade, van E.M.E.; Kuiper, A.E.T.; Tamminga, Y.; Thuene, P.C.; Niemantsverdriet, J.W.

2004-01-01

A series of CrOx/SiO2/Si(100) model catalysts were tested for ethylene polymerization activity, varying chromium loading, and calcination temperature. Chromium coverage of the model catalyst, quantified by Rutherford backscattering spectrometry, decreases with increasing calcination temperature as

Synthesis of MoVTeNb Oxide Catalysts with Tunable Particle Dimensions

DEFF Research Database (Denmark)

Kolenko, Yury V.; Zhang, Wei; d'Alnoncourt, Raoul Naumann

2011-01-01

Reliable procedures for the controlled synthesis of phase-pure MoVTeNb mixed oxides with M1 structure (ICSD 55097) and tunable crystal dimensions were developed to study the structure sensitivity of the selective oxidation of propane to acrylic acid. A series of powdered M1 catalysts...... catalysts were studied in the selective oxidation of propane to acrylic acid, revealing that active sites appear on the entire M1 surface and illustrating the high sensitivity of catalyst performance on the catalyst synthesis method....

Preparation, Characterization, and Catalytic Activity of MoCo/USY Catalyst on Hydrodeoxygenation Reaction of Anisole

Science.gov (United States)

Nugrahaningtyas, K. D.; Suharbiansah, R. S. R.; Rahmawati, F.

2018-03-01

This research aims to prepare, characterize, and study the catalytic activity of Molybdenum (Mo) and Cobalt (Co) metal with supporting material Ultra Stable Y-Zeolite (USY), to produce catalysts with activity in hydrotreatment reaction and in order to eliminate impurities compounds that containing unwanted groups heteroatoms. The bimetallic catalysts MoCo/USY were prepared by wet impregnation method with weight variation of Co metal 0%, 2%, 4%, 6%, 8%, and Mo metal 8% (w/w), respectively. Activation method of the catalyst included calcination, oxidation, reduction and the crystallinity was characterized using X-ray diffraction (XRD), the acidity of the catalyst was analyzed using Fourier Transform Infrared Spectroscopy (FT-IR) and gravimetry method, minerals present in the catalyst was analyzed using X-Ray Fluorescence (XRF), and surface of the catalyst was analyzed using Surface Area Analyzer (SAA). Catalytic activity test (benzene yield product) of MoCo/USY on hydrodeoxigenation reaction of anisole aimed to determine the effect of Mo-Co/USY for catalytic activity in the reaction hydrodeoxigenation (HDO) anisole. Based on characterization and test of catalytic activity, it is known that catalytic of MoCo/USY 2% (catalyst B) shows best activities with acidity of 10.209 mmol/g, specific area of catalyst of 426.295 m2/g, pore average of 14.135 Å, total pore volume 0.318 cc/g, and total yield of HDO products 6.06%.

Highly active and durable Ca-doped Ce-SBA-15 catalyst for biodiesel production

International Nuclear Information System (INIS)

Thitsartarn, Warintorn; Maneerung, Thawatchai; Kawi, Sibudjing

2015-01-01

In this work, Ca-doped Ce-incorporated SBA-15 (Ca/CeS) catalyst was successfully synthesized by using direct synthesis of Ce-incorporated SBA-15 followed by impregnation of CaO (calcium oxide). The maximum Si/Ce molar ratio that Ce atoms can be incorporated successfully into the mesoporous framework was found to be 5 (CeS-5). After the impregnation of 30 wt. % Ca, the obtained 30Ca/CeS-5 catalysts showed the superior catalytic performance for transesterification reaction of palm oil with methanol and also the higher catalytic activity as compared to other supported catalysts, i.e. CaO/CeO 2 and CaO–CeO 2 /SBA-15. This can be attributed to the well-dispersion of CaO on the CeS-5 support surface. Furthermore, it was found that the leaching of Si, Ce and Ca from the catalyst into biodiesel produced was negligible (i.e. <1 ppm after 7 cycles), indicating the strong interaction between CaO and CeS-5 support. As a result, the 30Ca/CeS-5 catalyst can be reused at least 15 cycles with insignificant decrease in catalytic activity, offering the efficient CaO-based catalyst for biodiesel production. - Highlights: • Mesoporous Ca-based catalyst was successfully developed for biodiesel production. • Catalyst exhibited high activity towards transesterification (FAME yield > 98%). • Catalyst can be effectively re-used at least 15 cycles. • Extremely low catalyst contaminant (<1 ppm) was presented

Catalyst dispersion and activity under conditions of temperature-staged liquefaction

Energy Technology Data Exchange (ETDEWEB)

Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

1993-02-01

This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275[degrees]C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

Effect of phosphorus addition on the hydrotreating activity of NiMo/Al{sub 2}O{sub 3} carbide catalyst

Energy Technology Data Exchange (ETDEWEB)

Sundaramurthy, V.; Dalai, A.K. [Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, SK S7N 5A9 (Canada); Adjaye, J. [Syncrude Edmonton Research Centre, Edmonton, AB T6N 1H4 (Canada)

2007-07-30

A series of phosphorus promoted {gamma}-Al{sub 2}O{sub 3} supported NiMo carbide catalysts with 0-4.5 wt.% P, 13 wt.% Mo and 2.5 wt.% Ni were synthesized and characterized by elemental analysis, pulsed CO chemisorption, BET surface area measurement, X-ray diffraction, near-edge X-ray absorption fine structure, DRIFT spectroscopy of CO adsorption and H{sub 2} temperature programmed reduction. X-ray diffraction patterns and CO uptake showed the P addition to NiMo/{gamma}-Al{sub 2}O{sub 3} carbide, increased the dispersion of {beta}-Mo{sub 2}C particles. DRIFT spectra of adsorbed CO revealed that P addition to NiMo/{gamma}-Al{sub 2}O{sub 3} carbide catalyst not only increases the dispersion of Ni-Mo carbide phase, but also changes the nature of surface active sites. The hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activities of these P promoted NiMo/{gamma}-Al{sub 2}O{sub 3} carbide catalysts were performed in trickle bed reactor using light gas oil (LGO) derived from Athabasca bitumen and model feed containing quinoline and dibenzothiophene at industrial conditions. The P added NiMo/{gamma}-Al{sub 2}O{sub 3} carbide catalysts showed enhanced HDN activity compared to the NiMo/{gamma}-Al{sub 2}O{sub 3} catalysts with both the feed stocks. The P had almost no influence on the HDS activity of NiMo/{gamma}-Al{sub 2}O{sub 3} carbide with LGO and dibenzothiophene. P addition to NiMo/{gamma}-Al{sub 2}O{sub 3} carbide accelerated C-N bond breaking and thus increased the HDN activity. (author)

Cationic Zn-Porphyrin Polymer Coated onto CNTs as a Cooperative Catalyst for the Synthesis of Cyclic Carbonates.

Science.gov (United States)

Jayakumar, Sanjeevi; Li, He; Chen, Jian; Yang, Qihua

2018-01-24

The development of solid catalysts containing multiple active sites that work cooperatively is very attractive for biomimetic catalysis. Herein, we report the synthesis of bifunctional catalysts by supporting cationic porphyrin-based polymers on carbon nanotubes (CNTs) using the direct reaction of 5,10,15,20-tetrakis(4-pyridyl)porphyrin zinc(II), di(1H-imidazol-1-yl)methane, and 1,4-bis(bromomethyl)benzene in the presence of CNTs. The bifunctional catalysts could efficiently catalyze the cycloaddition reaction of epoxides and CO 2 under solvent-free conditions with porphyrin zinc(II) as the Lewis acid site and a bromine anion as a nucleophilic agent working in a cooperative way. Furthermore, a relative amount of porphyrin zinc(II) and quaternary ammonium bromide could be facilely adjusted for facilitating cooperative behavior. The bifunctional catalyst with a TOF up to 2602 h -1 is much more active than the corresponding homogeneous counterpart and is one of the most active heterogeneous catalysts ever reported under cocatalyst-free conditions. The high activity is mainly attributed to the enhanced cooperation effect of the bifunctional catalyst. With a wide substrate scope, the bifunctional catalyst could be stably recycled. This work demonstrates a new approach for the generation of a cooperative activation effect for solid catalysts.

The activation mechanism of Fe-based olefin metathesis catalysts

KAUST Repository

Poater, Albert; Pump, Eva; Vummaleti, Sai V. C.; Cavallo, Luigi

2014-01-01

Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

The activation mechanism of Fe-based olefin metathesis catalysts

KAUST Repository

Poater, Albert

2014-08-01

Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

Hydrotreatment of heavy oil from coal liquefaction on Sulfide Ni - W Catalysts

International Nuclear Information System (INIS)

Zhi-ping Lei; Li-juan Gao; Heng-fu Shui; Shi-biao, Ren; Zhi-cai Wang; Kang-shi Gang

2011-01-01

Heavy oil (distillation temperature: 320-340 deg C) derived from the direct coal liquefaction process using Shengli coal were hydrotreated using sulfided Ni-Mo/Al 2 O 3 , Ni-W/Al 2 O 3 , and Ni-W/SiO 2 catalysts respectively. The sulfided catalysts were characterized by BET, XRD, H 2 -TPR and NH 3 -TPD respectively. The evaluations of the hydrodenitrogenation (HDN) and hydrodearomatization (HDA) properties of heavy oil on the three catalysts were carried out at 400 deg C and 5.0 MPa initial H2 pressure. The W-based catalysts displayed better performances than Mo-based catalysts for the HDN and HDA reactions. Al 2 O 3 supported catalysts were found to have higher catalytic activities than on SiO 2 supported ones. The activities of sulfided catalysts were associated mainly with the nature of active sites, acidity, metal sulfide crystallite size and the amount of the reducible sulfur species of metal sulfide. (author)

Single-Atom Mn Active Site in a Triol-Stabilized β-Anderson Manganohexamolybdate for Enhanced Catalytic Activity towards Adipic Acid Production

Directory of Open Access Journals (Sweden)

Jianhui Luo

2018-03-01

Full Text Available Adipic acid is an important raw chemical for the commercial production of polyamides and polyesters. The traditional industrial adipic acid production utilizes nitric acid to oxidize KA oil (mixtures of cyclohexanone and cyclohexanol, leading to the emission of N2O and thus causing ozone depletion, global warming, and acid rain. Herein, we reported an organically functionalized β-isomer of Anderson polyoxometalates (POMs nanocluster with single-atom Mn, β-{[H3NC(CH2O3]2MnMo6O18}− (1, as a highly active catalyst to selectively catalyze the oxidation of cyclohexanone, cyclohexanol, or KA oil with atom economy use of 30% H2O2 for the eco-friendly synthesis of adipic acid. The catalyst has been characterized by single crystal and powder XRD, XPS, ESI-MS, FT-IR, and NMR. A cyclohexanone (cyclohexanol conversion of >99.9% with an adipic acid selectivity of ~97.1% (~85.3% could be achieved over catalyst 1 with high turnover frequency of 2427.5 h−1 (2132.5 h−1. It has been demonstrated that the existence of Mn3+ atom active site in catalyst 1 and the special butterfly-shaped topology of POMs both play vital roles in the enhancement of catalytic activity.

Electrochemical dopamine sensor based on P-doped graphene: Highly active metal-free catalyst and metal catalyst support.

Science.gov (United States)

Chu, Ke; Wang, Fan; Zhao, Xiao-Lin; Wang, Xin-Wei; Tian, Ye

2017-12-01

Heteroatom doping is an effective strategy to enhance the catalytic activity of graphene and its hybrid materials. Despite a growing interest of P-doped graphene (P-G) in energy storage/generation applications, P-G has rarely been investigated for electrochemical sensing. Herein, we reported the employment of P-G as both metal-free catalyst and metal catalyst support for electrochemical detection of dopamine (DA). As a metal-free catalyst, P-G exhibited prominent DA sensing performances due to the important role of P doping in improving the electrocatalytic activity of graphene toward DA oxidation. Furthermore, P-G could be an efficient supporting material for loading Au nanoparticles, and resulting Au/P-G hybrid showed a dramatically enhanced electrocatalytic activity and extraordinary sensing performances with a wide linear range of 0.1-180μM and a low detection limit of 0.002μM. All these results demonstrated that P-G might be a very promising electrode material for electrochemical sensor applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms.

Science.gov (United States)

Koepke, Sara J; Light, Kenneth M; VanNatta, Peter E; Wiley, Keaton M; Kieber-Emmons, Matthew T

2017-06-28

Deployment of solar fuels derived from water requires robust oxygen-evolving catalysts made from earth abundant materials. Copper has recently received much attention in this regard. Mechanistic parallels between Cu and single-site Ru/Ir/Mn water oxidation catalysts, including intermediacy of terminal Cu oxo/oxyl species, are prevalent in the literature; however, intermediacy of late transition metal oxo species would be remarkable given the high d-electron count would fill antibonding orbitals, making these species high in energy. This may suggest alternate pathways are at work in copper-based water oxidation. This report characterizes a dinuclear copper water oxidation catalyst, {[(L)Cu(II)] 2 -(μ-OH) 2 }(OTf) 2 (L = Me 2 TMPA = bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine) in which water oxidation proceeds with high Faradaic efficiency (>90%) and moderate rates (33 s -1 at ∼1 V overpotential, pH 12.5). A large kinetic isotope effect (k H /k D = 20) suggests proton coupled electron transfer in the initial oxidation as the rate-determining step. This species partially dissociates in aqueous solution at pH 12.5 to generate a mononuclear {[(L)Cu(II)(OH)]} + adduct (K eq = 0.0041). Calculations that reproduce the experimental findings reveal that oxidation of either the mononuclear or dinuclear species results in a common dinuclear intermediate, {[LCu(III)] 2 -(μ-O) 2 } 2+ , which avoids formation of terminal Cu(IV)═O/Cu(III)-O • intermediates. Calculations further reveal that both intermolecular water nucleophilic attack and redox isomerization of {[LCu(III)] 2 -(μ-O) 2 } 2+ are energetically accessible pathways for O-O bond formation. The consequences of these findings are discussed in relation to differences in water oxidation pathways between Cu catalysts and catalysts based on Ru, Ir, and Mn.

Influence of zeolite structure on the activity and durability of Co-Pd-zeolite catalysts in the reduction of NOx with methane

International Nuclear Information System (INIS)

Pieterse, J.A.Z.; Van den Brink, R.W.; Booneveld, S.; De Bruijn, F.A.

2003-01-01

Selective catalytic reduction of NO with CH 4 was studied over ZSM-5, MOR, FER and BEA zeolite-based cobalt (Co) and palladium (Pd) catalysts in the presence of oxygen and water. As compared to other catalytic systems reported in literature for CH 4 -SCR in the presence of water, zeolite supported Co-Pd combination catalysts are very active and selective. The most active catalysts, based on MOR and ZSM-5, are characterised by well-dispersed Pd ions in the zeolite that activate methane. Wet ion exchange is a good method to achieve high dispersion of Pd provided that it is carried out in a competitive manner. The presence of cobalt (Co 3 O 4 , Co-oxo ions) boosts SCR activity by oxidising NO to NO 2 . The activity of the zeolite-based Co-Pd combination catalysts decreases with prolonged times on stream. The severity of the deactivation was found to be different for different zeolite topologies. The characterisation and evaluation of freshly calcined catalysts and spent catalysts show two things that occur during reaction: (1) zeolite solvated metal cations disappear in favour of (inactive) metal oxides and presumably larger metal entities, i.e. loss of dispersion; (2) loss of crystallinity affiliated with steam-dealumination and the concomitant formation of extra-framework aluminium (EFAL) in the presence of water. Both phenomena strongly depend on the (reaction) temperature. The deactivation of Co-Pd-zeolite resembles the deactivation of Pd-zeolite. Hence, future research could encompass the stabilisation of Pd (cations) in the zeolite pores by exploring additives other than cobalt. For this, detailed understanding on the siting of Pd in zeolites is important

Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts.

Science.gov (United States)

Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander; Scholten, Fabian; Bonifacio, Cecile S; Sinev, Ilya; Divins, Nuria J; Zegkinoglou, Ioannis; Jeon, Hyo Sang; Kisslinger, Kim; Stach, Eric A; Yang, Judith C; Rossmeisl, Jan; Roldan Cuenya, Beatriz

2017-09-11

Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulk of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

International Nuclear Information System (INIS)

Ma Liang; Liu Changpeng; Liao Jianhui; Lu Tianhong; Xing Wei; Zhang Jiujun

2009-01-01

A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH 4 ) 2 PtCl 6 and Ru(OH) 3 ) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru 0 ) and hydrous ruthenium oxides (RuO x H y ) species on the catalyst surface. However, RuO x H y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO 2 ) species on the catalyst surface was found to be less active.

Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution

Energy Technology Data Exchange (ETDEWEB)

Hung, Chang-Mao, E-mail: hungcm1031@gmail.com [Department of Industry Engineering and Management, Yung-Ta Institute of Technology and Commerce, 316 Chung-shan Road, Linlo, Pingtung 909, Taiwan (China)

2009-07-30

Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h{sup -1}.

Highly Durable Platinum Single-Atom Alloy Catalyst for Electrochemical Reactions

DEFF Research Database (Denmark)

Kim, Jiwhan; Roh, Chi-Woo; Sahoo, Suman Kalyan

2018-01-01

Single atomic Pt catalyst can offer efficient utilization of the expensive platinum and provide unique selectivity because it lacks ensemble sites. However, designing such a catalyst with high Pt loading and good durability is very challenging. Here, single atomic Pt catalyst supported on antimony...... functional theory calculations show that replacing Sb sites with Pt atoms in the bulk phase or at the surface of SbSn or ATO is energetically favorable. The Pt1/ATO shows superior activity and durability for formic acid oxidation reaction, compared to a commercial Pt/C catalyst. The single atomic Pt...... structure is retained even after a harsh durability test, which is performed by repeating cyclic voltammetry in the range of 0.05–1.4 V for 1800 cycles. A full cell is fabricated for direct formic acid fuel cell using the Pt1/ATO as an anode catalyst, and an order of magnitude higher cell power is obtained...

Effect of the dispersants on Pd species and catalytic activity of supported palladium catalyst

Energy Technology Data Exchange (ETDEWEB)

Hu, Yue [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Yang, Xiaojun, E-mail: 10100201@wit.edu.cn [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Cao, Shuo, E-mail: cao23@email.sc.edu [North America R& D Center, Clariant BU Catalysts, Louisville, 40209, KY (United States); Zhou, Jie [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Wu, Yuanxin [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Han, Jinyu [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Yan, Zhiguo [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Zheng, Mingming [Oil Crops Research Institute, Chinese Academy of Agricultural Sciences, Hubei Key Laboratory of Oilcrops Lipid Chemistry and Nutrition, Wuhan 430062 (China)

2017-04-01

Highlights: • Polyvinyl alcohol (PVA) inhibited the sintering and reduction of Pd nanoparticles. • Activity was improved for supported Pd catalysts with PVA modified method. • PVA modified method minimized the catalyst deactivation. • This work provides an insight of the regeneration strategies for Pd catalysts. - Abstract: A series of supported palladium catalysts has been prepared through the precipitation method and the reduction method, using polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) as dispersants. The effects of the dispersants on the properties of catalysts were evaluated and the catalytic performance of the new materials was investigated for the oxidative carbonylation of phenol to diphenyl carbonate (DPC). The catalysts as prepared were also characterized by the X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET) measurements and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the addition of the dispersants had no effect on the crystal phase of the catalysts. However, the dispersion of Pd particles was improved when the dispersants were used. Moreover, the particle sizes of Pd nanoparticles modified by PVA were smaller than those modified by PVP. The catalysts prepared using the dispersants gave better yields of DPC than the catalysts prepared without the dispersants. The highest yield of DPC was 17.9% with the PVA-Red catalyst. The characterization results for the used catalysts showed that the Pd species in the PVA-Red catalyst remained mostly divalent and the lattice oxygen species were consumed during the reaction, which could lead to the higher catalytic activity of the PVA-Red catalyst. The experimental results confirm that PVA effectively inhibited the sintering and reduction of active Pd species in the oxidative carbonylation of phenol.

Effects of Activated Carbon Surface Property on Structure and Activity of Ru/AC Catalysts

Science.gov (United States)

Xu, S. K.; Li, L. M.; Guo, N. N.

2018-05-01

The activated carbon (AC) was modified by supercritical (SC) methanol, HNO3 oxidation, or HNO3 oxidation plus SC methanol, respectively. Then, the original and the modified AC were used as supports for Ru/AC catalysts prepared via the impregnation method. The results showed that the SC methanol modification decreased the content of surface acidic groups of AC. While HNO3 oxidation displayed the opposite behavior. Furthermore, the dispersion of ruthenium and the activity of catalysts were highly dependent on the content of surface acidic groups, and the SC methanol modified sample exhibited the highest activity for hydrogenation of glucose.

Hydroformylation of 1-Hexene over Rh/Nano-Oxide Catalysts

Directory of Open Access Journals (Sweden)

Sari Suvanto

2013-03-01

Full Text Available The effect of nanostructured supports on the activity of Rh catalysts was studied by comparing the catalytic performance of nano- and bulk-oxide supported Rh/ZnO, Rh/SiO2 and Rh/TiO2 systems in 1-hexene hydroformylation. The highest activity with 100% total conversion and 96% yield of aldehydes was obtained with the Rh/nano-ZnO catalyst. The Rh/nano-ZnO catalyst was found to be more stable and active than the corresponding rhodium catalyst supported on bulk ZnO. The favorable morphology of Rh/nano-ZnO particles led to an increased metal content and an increased number of weak acid sites compared to the bulk ZnO supported catalysts. Both these factors favored the improved catalytic performance. Improvements of catalytic properties were obtained also with the nano-SiO2 and nano-TiO2 supports in comparison with the bulk supports. All of the catalysts were characterized by scanning electron microscope (SEM, inductively coupled plasma mass spectrometry (ICP-MS, BET, powder X-ray diffraction (PXRD and NH3- temperature-programmed desorption (TPD.

Support effects on hydrotreating activity of NiMo catalysts

International Nuclear Information System (INIS)

Dominguez-Crespo, M.A.; Arce-Estrada, E.M.; Torres-Huerta, A.M.; Diaz-Garcia, L.; Cortez de la Paz, M.T.

2007-01-01

The effect of the gamma alumina particle size on the catalytic activity of NiMoS x catalysts prepared by precipitation method of aluminum acetate at pH = 10 was studied. The structural characterization of the supports was measured by using XRD, pyridine FTIR-TPD and nitrogen physisorption. NiMo catalysts were characterized during the preparation steps (annealing and sulfidation) using transmission electron microscopy (TEM). Hydrogen TPR studies of the NiMo catalysts were also carried out in order to correlate their hydrogenating properties and their catalytic functionality. Catalytic tests were carried out in a pilot plant at 613, 633 and 653 K temperatures. The results showed that the rate constants of hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatizing (HDA) at 613-653 K decreased in the following order: A > B > C corresponding to the increase of NiMoS particle size associated to these catalysts

Activity and selectivity control through periodic composition forcing over Fischer-Tropsch catalysts

Energy Technology Data Exchange (ETDEWEB)

Silveston, P L; Hudgins, R R; Adesina, A A; Ross, G S; Feimer, J L

1986-01-01

Data collected under steady-state and periodic composition forcing of the Fischer-Tropsch synthesis over three commonly used catalysts demonstrate that both activity and selectivity can be changed by the latter operating mode. Synthesis of hydrocarbons up to C/sub 7/are favored at the expense of the higher carbon numbers for the Co catalyst, while for the Ru catalyst, only the C/sub 3/ and lower species are favored. Only methane production is stimulated with the Fe catalyst. Fe and Ru catalysts shift production from alkenes to alkanes. Transient data is interpreted in the paper.

Hydroprocessing catalysts utilization and regeneration schemes

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.

The catalyst reactor inventory represents an important part of the cost of hydroprocessing operation. The selection of a suitable catalyst and reactor is influenced by feedstock properties. Processes ensuring an uninterrupted operation during catalyst addition and withdrawal are preferred for processing high asphaltene and metal content feedstocks. The spent catalyst can be regenerated and returned to the operation if the extent of its deactivation is not high. The regeneration may be performed either in-situ or off-site. The former is suitable for fixed bed reactors whereas the catalyst from ebullated bed reactors must be regenerated off-site. The regeneration of spent catalysts heavily loaded with metals such as V, Ni and Fe may not be economic. Such catalysts may be suitable for metal reclamation. An environmentally safe method for catalyst disposal must be found if neither regeneration nor metal reclamation from spent catalysts can be performed.

Magnetic properties of iron-based catalysts activated by various CO{sub 2} concentrations

Energy Technology Data Exchange (ETDEWEB)

Lim, Jung Tae; Kim, Chul Sung [Kookmin University, Seoul (Korea, Republic of); Chun, Dong Hyun; Park, Ji Chan [Korea Institute of Energy Research, Daejeon (Korea, Republic of)

2014-12-15

Fresh catalyst samples of 100Fe/5.26Cu/4.76K/18.2SiO{sub 2} in part per weight were synthesized by using a combination of a co-precipitation technique and spray-drying method and were activated in situ by using syngas (H{sub 2}/CO/xCO{sub 2}) with different amounts of CO{sub 2} (x = 0.0, 0.5, 1.0, and 2.0). All activated catalyst samples showed similar XRD patterns, a combination of ferrihydrite, magnetite, χ-carbide, and ε'-carbide, regardless of the CO{sub 2} contents. From the Moessbauer spectra, we also observed a combination of ferrihydrite, magnetite, χ-carbide, and ε'-carbide in all activated catalyst samples. The main compound of the activated catalyst sample activated by using CO{sub 2}-free syngas (H{sub 2}/CO) was magnetic χ-carbide, and the main compound changed from χ-carbide to ferrihydrite with increasing CO{sub 2} concentration, confirmed by both, Moessbauer spectra and XRD pattern.

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.

A recyclable Au(I) catalyst for selective homocoupling of arylboronic acids: significant enhancement of nano-surface binding for stability and catalytic activity.

Science.gov (United States)

Zhang, Xin; Zhao, Haitao; Wang, Jianhui

2010-08-01

Au nanoparticles stabilized by polystyrene-co-polymethacrylic acid microspheres (PS-co-PMAA) were prepared and characterized via X-ray diffraction (XRD), and transmission electron microscope (TEM). The Au nanoparticles supported on the microspheres showed highly selective catalytic activity for homo-coupling reactions of arylboronic acids in a system of aryl-halides and arylboronic acids. X-ray photoelectron spectroscopy (XPS) spectra of the catalyst shows large amounts of Au(I) complexes band to the surface of the Au nanoparticles, which contributes to the selective homocoupling of the arylboronic acids. More importantly, this supported Au complex is a highly recyclable catalyst. The supported Au catalyst can be recycled and reused at least 6 times for a phenylboronic acid reactant, whereas the parent complex shows very low catalytic activity for this compound. The high catalytic activity of this material is attributed to: (1) the high surface to volume ratio which leads to more active sites being exposed to reactants; (2) the strong surface binding of the Au nanoparticle to the Au(I) complexes, which enhances both the stability and the catalytic activity of these complexes.

Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network

Science.gov (United States)

Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren; Zhao, Dan; Liu, Di-Jia

2015-01-01

Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report here a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A⋅cm−3 at 0.9 V or 450 A⋅cm−3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed. PMID:26261338

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

Science.gov (United States)

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

Design of Embedded Metal Catalysts via Reverser Micro-Emulsion System: a Way to Suppress Catalyst Deactivation by Metal Sintering

KAUST Repository

Al Mana, Noor

2016-01-01

are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between

The nanosize catalysts role in the modern hydroprocesses

International Nuclear Information System (INIS)

Irisova, K N; Smirnov, V K; Talisman, E L

2011-01-01

Introduction of the modern technological procedures operating the catalytic systems with different nanosized characteristics is the only way to fabricate components of commercial oils that meet the current requirements. Specifications to the individual catalysts, which form a catalytic system, differ both in nanostructural features of the support porosity and in distribution of nanosized active site. These specifications are related to the purpose of the process and the role of the catalyst in the process.

Determination of catalyst residues in hydrocarbon fuels by instrumental neutron activation analysis

International Nuclear Information System (INIS)

Burgess, D.D.

1982-01-01

A procedure has been developed for the determination of entrained catalytic cracking catalyst in hydrocarbon fuels. Aluminium is measured by instrumental neutron activation analysis and the amount of catalyst present is calculated from the amount of aluminium found and the known composition of the catalyst. Entrained catalyst may be determined at levels above 3 ppm with a precision of +-2%-25% according to sample composition. Only simple procedures are required. Vanadium may reduce sensitivity by dead time and pulse pile-up. No other interferences were observed. (author)

Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

Science.gov (United States)

Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo

2016-02-05

As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium nanoparticles encapsulated in core-shell silica: A structured hydrogenation catalyst with enhanced activity for reduction of oxyanion water pollutants

KAUST Repository

Wang, Yin; Liu, Jinyong; Wang, Peng; Werth, Charles; Strathmann, Timothy J.

2014-01-01

Noble metal nanoparticles have been applied to mediate catalytic removal of toxic oxyanions and halogenated hydrocarbons in contaminated water using H2 as a clean and sustainable reductant. However, activity loss by nanoparticle aggregation and difficulty of nanoparticle recovery are two major challenges to widespread technology adoption. Herein, we report the synthesis of a core-shell-structured catalyst with encapsulated Pd nanoparticles and its enhanced catalytic activity in reduction of bromate (BrO3-), a regulated carcinogenic oxyanion produced during drinking water disinfection process, using 1 atm H2 at room temperature. The catalyst material consists of a nonporous silica core decorated with preformed octahedral Pd nanoparticles that were further encapsulated within an ordered mesoporous silica shell (i.e., SiO2@Pd@mSiO2). Well-defined mesopores (2.3 nm) provide a physical barrier to prevent Pd nanoparticle (6 nm) movement, aggregation, and detachment from the support into water. Compared to freely suspended Pd nanoparticles and SiO2@Pd, encapsulation in the mesoporous silica shell significantly enhanced Pd catalytic activity (by a factor of 10) under circumneutral pH conditions that are most relevant to water purification applications. Mechanistic investigation of material surface properties combined with Langmuir-Hinshelwood modeling of kinetic data suggest that mesoporous silica shell enhances activity by promoting BrO3- adsorption near the Pd active sites. The dual function of the mesoporous shell, enhancing Pd catalyst activity and preventing aggregation of active nanoparticles, suggests a promising general strategy of using metal nanoparticle catalysts for water purification and related aqueous-phase applications.

Palladium nanoparticles encapsulated in core-shell silica: A structured hydrogenation catalyst with enhanced activity for reduction of oxyanion water pollutants

KAUST Repository

Wang, Yin

2014-10-03

Noble metal nanoparticles have been applied to mediate catalytic removal of toxic oxyanions and halogenated hydrocarbons in contaminated water using H2 as a clean and sustainable reductant. However, activity loss by nanoparticle aggregation and difficulty of nanoparticle recovery are two major challenges to widespread technology adoption. Herein, we report the synthesis of a core-shell-structured catalyst with encapsulated Pd nanoparticles and its enhanced catalytic activity in reduction of bromate (BrO3-), a regulated carcinogenic oxyanion produced during drinking water disinfection process, using 1 atm H2 at room temperature. The catalyst material consists of a nonporous silica core decorated with preformed octahedral Pd nanoparticles that were further encapsulated within an ordered mesoporous silica shell (i.e., SiO2@Pd@mSiO2). Well-defined mesopores (2.3 nm) provide a physical barrier to prevent Pd nanoparticle (6 nm) movement, aggregation, and detachment from the support into water. Compared to freely suspended Pd nanoparticles and SiO2@Pd, encapsulation in the mesoporous silica shell significantly enhanced Pd catalytic activity (by a factor of 10) under circumneutral pH conditions that are most relevant to water purification applications. Mechanistic investigation of material surface properties combined with Langmuir-Hinshelwood modeling of kinetic data suggest that mesoporous silica shell enhances activity by promoting BrO3- adsorption near the Pd active sites. The dual function of the mesoporous shell, enhancing Pd catalyst activity and preventing aggregation of active nanoparticles, suggests a promising general strategy of using metal nanoparticle catalysts for water purification and related aqueous-phase applications.

Pt Single Atoms Embedded in the Surface of Ni Nanocrystals as Highly Active Catalysts for Selective Hydrogenation of Nitro Compounds.

Science.gov (United States)

Peng, Yuhan; Geng, Zhigang; Zhao, Songtao; Wang, Liangbing; Li, Hongliang; Wang, Xu; Zheng, Xusheng; Zhu, Junfa; Li, Zhenyu; Si, Rui; Zeng, Jie

2018-06-13

Single-atom catalysts exhibit high selectivity in hydrogenation due to their isolated active sites, which ensure uniform adsorption configurations of substrate molecules. Compared with the achievement in catalytic selectivity, there is still a long way to go in exploiting the catalytic activity of single-atom catalysts. Herein, we developed highly active and selective catalysts in selective hydrogenation by embedding Pt single atoms in the surface of Ni nanocrystals (denoted as Pt 1 /Ni nanocrystals). During the hydrogenation of 3-nitrostyrene, the TOF numbers based on surface Pt atoms of Pt 1 /Ni nanocrystals reached ∼1800 h -1 under 3 atm of H 2 at 40 °C, much higher than that of Pt single atoms supported on active carbon, TiO 2 , SiO 2 , and ZSM-5. Mechanistic studies reveal that the remarkable activity of Pt 1 /Ni nanocrystals derived from sufficient hydrogen supply because of spontaneous dissociation of H 2 on both Pt and Ni atoms as well as facile diffusion of H atoms on Pt 1 /Ni nanocrystals. Moreover, the ensemble composed of the Pt single atom and nearby Ni atoms in Pt 1 /Ni nanocrystals leads to the adsorption configuration of 3-nitrostyrene favorable for the activation of nitro groups, accounting for the high selectivity for 3-vinylaniline.

Recent development of active nanoparticle catalysts for fuel cell reactions

Energy Technology Data Exchange (ETDEWEB)

Mazumder, Vismadeb; Lee, Youngmin; Sun, Shouheng [Department of Chemistry Brown University Providence, RI (United States)

2010-04-23

This review focuses on the recent advances in the synthesis of nanoparticle (NP) catalysts of Pt-, Pd- and Au-based NPs as well as composite NPs. First, new developments in the synthesis of single-component Pt, Pd and Au NPs are summarized. Then the chemistry used to make alloy and composite NP catalysts aiming to enhance their activity and durability for fuel cell reactions is outlined. The review next introduces the exciting new research push in developing CoN/C and FeN/C as non-Pt catalysts. Examples of size-, shape- and composition-dependent catalyses for oxygen reduction at cathode and formic acid oxidation at anode are highlighted to illustrate the potentials of the newly developed NP catalysts for fuel cell applications. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Edge termination of MoS2 and CoMoS catalyst particles

DEFF Research Database (Denmark)

Byskov, Line Sjolte; Nørskov, Jens Kehlet; Clausen, B. S.

2000-01-01

The edge termination of MoS2 and CoMoS catalyst particles is studied by density functional calculations. We show that for structures without vacancies Mo-terminated edges have the lowest edge energies. Creation of vacancies, which are believed to be active sites in these catalyst systems, leads...

Hydrotreatment of heavy oil from coal liquefaction on Sulfide Ni - W Catalysts

Energy Technology Data Exchange (ETDEWEB)

Zhi-ping Lei; Li-juan Gao; Heng-fu Shui; Shi-biao, Ren; Zhi-cai Wang; Kang-shi Gang, E-mail: shhf@ahut.edu.c [Anhui University of Technology, Maanshan (China). School of Chemistry and Chemical Engineering. Anhui Key Lab. of Coal Clean Conversion and Utilization

2011-07-01

Heavy oil (distillation temperature: 320-340 deg C) derived from the direct coal liquefaction process using Shengli coal were hydrotreated using sulfided Ni-Mo/Al{sub 2}O{sub 3}, Ni-W/Al{sub 2}O{sub 3}, and Ni-W/SiO{sub 2} catalysts respectively. The sulfided catalysts were characterized by BET, XRD, H{sub 2}-TPR and NH{sub 3}-TPD respectively. The evaluations of the hydrodenitrogenation (HDN) and hydrodearomatization (HDA) properties of heavy oil on the three catalysts were carried out at 400 deg C and 5.0 MPa initial H2 pressure. The W-based catalysts displayed better performances than Mo-based catalysts for the HDN and HDA reactions. Al{sub 2}O{sub 3} supported catalysts were found to have higher catalytic activities than on SiO{sub 2} supported ones. The activities of sulfided catalysts were associated mainly with the nature of active sites, acidity, metal sulfide crystallite size and the amount of the reducible sulfur species of metal sulfide. (author)

A NEW TYPE OF HIGHLY-ACTIVE POLYMER-BOUND RHODIUM HYDROFORMYLATION CATALYST

NARCIS (Netherlands)

JONGSMA, T; KIMKES, P; CHALLA, G; VANLEEUWEN, PWNM

1992-01-01

A new route of attaching phosphites to a (co)polymer chain is described. These copolymers are used for the preparation of a rhodium phosphite hydroformylation catalyst. The catalytic activity of this polymer-bound system is identical to that of the low molecular weight analogue. The catalysts show a

Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

International Nuclear Information System (INIS)

Zhou, Juan; Chen, Huan; Chen, Quanyuan; Huang, Zhaolu

2016-01-01

Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N 2 adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H 2 chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d 5/2 shifted to higher positions while that of Au 4f 7/2 had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest catalytic activity

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

Energy Technology Data Exchange (ETDEWEB)

Mikolajczuk-Zychora, A., E-mail: amikolajczuk@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Mazurkiewicz-Pawlicka, M. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Stobinski, L. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw (Poland); Ciecierska, E. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Zimoch, A.; Opałło, M. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland)

2016-12-01

Highlights: • Palladium catalyst used on the cathode DFAFC is comparable to commercial platinum catalyst. • The treatment of carbon supports in nitric acid(V) increases the electrochemically available metal surface area and the catalytic activity in oxygen reduction reaction of catalysts. - Abstract: One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

An Active Alkali-Exchanged Faujasite Catalyst for p-Xylene Production via the One-Pot Diels-Alder Cycloaddition/Dehydration Reaction of 2,5-Dimethylfuran with Ethylene.

Science.gov (United States)

Rohling, Roderigh Y; Uslamin, Evgeny; Zijlstra, Bart; Tranca, Ionut C; Filot, Ivo A W; Hensen, Emiel J M; Pidko, Evgeny A

2018-02-02

The one-pot Diels-Alder cycloaddition (DAC)/dehydration (D) tandem reaction between 2,5-dimethylfuran and ethylene is a potent pathway toward biomass-derived p -xylene. In this work, we present a cheap and active low-silica potassium-exchanged faujasite (KY, Si/Al = 2.6) catalyst. Catalyst optimization was guided by a computational study of the DAC/D reaction mechanism over different alkali-exchanged faujasites using periodic density functional theory calculations complemented by microkinetic modeling. Two types of faujasite models were compared, i.e., a high-silica alkali-exchanged faujasite model representing isolated active cation sites and a low-silica alkali-exchanged faujasite in which the reaction involves several cations in the proximity. The mechanistic study points to a significant synergetic cooperative effect of the ensemble of cations in the faujasite supercage on the DAC/D reaction. Alignment of the reactants by their interactions with the cationic sites and stabilization of reaction intermediates contribute to the high catalytic performance. Experiments confirmed the prediction that KY is the most active catalyst among low-silica alkali-exchanged faujasites. This work is an example of how the catalytic reactivity of zeolites depends on multiple interactions between the zeolite and reagents.

Effect of preparation method on catalytic activity of Ni/ γ-Al2O3 catalysts

International Nuclear Information System (INIS)

Miranda Morales, Barbara

2017-01-01

The performance of catalysts was shown to be strongly dependent on their methods of preparation. A study to examine the relationship between catalyst preparation procedures and the structure, dispersion, activity, and selectivity of the finished catalyst is reported. 10 wt.%Ni/γ-Al 2 O 3 catalysts were prepared by incipient wetness impregnation and by wet impregnation. The catalysts were used in the conversion of glycerol in gas phase and atmospheric pressure. The selectivity and activity of the catalysts were affected by the preparation method employed. The catalysts were characterized by thermogravimetric analysis (TGA), temperature-programmed reduction (TPR), N 2 -physorption, H 2 -chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR) and temperature-programmed oxidation (TPO). The Ni particle size and dispersion of the catalysts affected the selectivity to hydrogenolysis and dehydration routes, and the formation of carbon deposits was also affected. (author) [es

Exploiting nanospace for asymmetric catalysis: confinement of immobilized, single-site chiral catalysts enhances enantioselectivity.

Science.gov (United States)

Thomas, John Meurig; Raja, Robert

2008-06-01

In the mid-1990s, it became possible to prepare high-area silicas having pore diameters controllably adjustable in the range ca. 20-200 Å. Moreover, the inner walls of these nanoporous solids could be functionalized to yield single-site, chiral, catalytically active organometallic centers, the precise structures of which could be determined using in situ X-ray absorption and FTIR and multinuclear magic angle spinning (MAS) NMR spectroscopy. This approach opened up the prospect of performing heterogeneous enantioselective conversions in a novel manner, under the spatial restrictions imposed by the nanocavities within which the reactions occur. In particular, it suggested an alternative method for preparing pharmaceutically and agrochemically useful asymmetric products by capitalizing on the notion, initially tentatively perceived, that spatial confinement of prochiral reactants (and transition states formed at the chiral active center) would provide an altogether new method of boosting the enantioselectivity of the anchored chiral catalyst. Initially, we anchored chiral single-site heterogeneous catalysts to nanopores covalently via a ligand attached to Pd(II) or Rh(I) centers. Later, we employed a more convenient and cheaper electrostatic method, relying in part on strong hydrogen bonding. This Account provides many examples of these processes, encompassing hydrogenations, oxidations, and aminations. Of particular note is the facile synthesis from methyl benzoylformate of methyl mandelate, which is a precursor in the synthesis of pemoline, a stimulant of the central nervous system; our procedure offers several viable methods for reducing ketocarboxylic acids. In addition to relying on earlier (synchrotron-based) in situ techniques for characterizing catalysts, we have constructed experimental procedures involving robotically controlled catalytic reactors that allow the kinetics of conversion and enantioselectivity to be monitored continually, and we have access to

An introduction to catalyst

International Nuclear Information System (INIS)

Jeon, Hak Je

1988-11-01

This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

In situ characterization of cofacial Co(IV) centers in Co4O4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts.

Science.gov (United States)

Brodsky, Casey N; Hadt, Ryan G; Hayes, Dugan; Reinhart, Benjamin J; Li, Nancy; Chen, Lin X; Nocera, Daniel G

2017-04-11

The Co 4 O 4 cubane is a representative structural model of oxidic cobalt oxygen-evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all-Co(III) resting state. This doubly oxidized Co(IV) 2 state may be captured in a Co(III) 2 (IV) 2 cubane. We demonstrate that the Co(III) 2 (IV) 2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge-transfer (IVCT) bands in the near-IR are observed for the Co(III) 2 (IV) 2 cubane, and spectroscopic analysis together with electrochemical kinetics measurements reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV) 2 dimer. The exchange coupling in the cofacial Co(IV) 2 site allows for parallels to be drawn between the electronic structure of the Co 4 O 4 cubane model system and the high-valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV) 2 center on O-O bond formation.

An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

Science.gov (United States)

Almeida, T. S.; Palma, L. M.; Leonello, P. H.; Morais, C.; Kokoh, K. B.; De Andrade, A. R.

2012-10-01

The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved.

Study on supported binary sulfide catalysts for secondary hydrogenation of coal-derived liquids; Sekitan ekikayu niji suisoka shokubai no kenkyu

Energy Technology Data Exchange (ETDEWEB)

Shimada, H.; Matsubayashi, N.; Sato, T.; Imamura, M.; Yoshimura, Y.; Nishijima, A. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

1995-07-28

To utilize the high performance of supported catalysts in coal liquefaction processes, one of the promising ways is to apply hydroprocessing sulfide catalysts to the secondary hydrogenation of coal-derived liquids which have undergone the solid separation unit. However, when the product yield from the first-stage liquefaction is maximized, the feed stocks in the secondary hydrogenation contain large amounts of residual fractions with preasphaltenes and metallic components. In this case, the development of a long-life catalyst is essential to establish the two-stage process as a practical one. From this viewpoint, the authors have investigated the deactivation causes of supported Ni-Mo sulfide catalysts through the analysis of the used catalysts in the secondary hydrogenation of coal-derived liquids for long periods. The major cause of the catalyst deactivation has been found to be metallic and carbonaceous deposition on the catalyst, which results thin layer which covers the catalyst particles. The catalysts located at the reactor inlet are more rapidly deactivated than those at the rector exit because of larger amounts of metallic foul ants and the above described shell-like layer. Hydrocracking active sites are much heavily deactivated compared with hydrogenation active sites. It is inferred that the basic or polar compounds contained in coal liquids are permanency adsorbed on the hydrocracking active sites. Spectroscopic analysis of the used catalysts clarified the destruction of the active phase of the binary sulfides, through the segregation and crystal growth. The structural changes of the catalysts are very likely caused by heteroatom compounds in the preasphaltenes. Thus, the primary cause of the catalyst deactivation is the preasphaltenes in the coal liquids. Hydroaromatic compounds in the coal liquids suppress the change of the deposited carbonaceous materials into inert coke which permanently deactivate the catalyst.

Design of heterogeneous catalysts

DEFF Research Database (Denmark)

Frey, Anne Mette

was inspired by a computational screening, suggesting that alloys such as Ni-Fe, Co-Ni, and Co-Fe should show superior activity to the industrially used nickel catalyst. Especially the Ni-Fe system was considered to be interesting, since such alloy catalysts should be both more active and cheaper than the Ni...... catalyst. The results from the screening were experimentally verified for CO hydrogenation, CO2 hydrogenation, and simultaneous CO and CO2 hydrogenation by bimetallic Ni-Fe catalysts. These catalysts were found to be highly active and selective. The Co-Ni and Co-Fe systems were investigated for CO...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

OpenAIRE

Khalid Khazzal Hummadi; Karim H. Hassan; Phillip C.H. Mitchell

2009-01-01

The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK), 10 atm (1013 kPa), with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III) molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a c...

NANOSTRUCTURED METAL OXIDE CATALYSTS VIA BUILDING BLOCK SYNTHESES

Energy Technology Data Exchange (ETDEWEB)

Craig E. Barnes

2013-03-05

A broadly applicable methodology has been developed to prepare new single site catalysts on silica supports. This methodology requires of three critical components: a rigid building block that will be the main structural and compositional component of the support matrix; a family of linking reagents that will be used to insert active metals into the matrix as well as cross link building blocks into a three dimensional matrix; and a clean coupling reaction that will connect building blocks and linking agents together in a controlled fashion. The final piece of conceptual strategy at the center of this methodology involves dosing the building block with known amounts of linking agents so that the targeted connectivity of a linking center to surrounding building blocks is obtained. Achieving targeted connectivities around catalytically active metals in these building block matrices is a critical element of the strategy by which single site catalysts are obtained. This methodology has been demonstrated with a model system involving only silicon and then with two metal-containing systems (titanium and vanadium). The effect that connectivity has on the reactivity of atomically dispersed titanium sites in silica building block matrices has been investigated in the selective oxidation of phenols to benezoquinones. 2-connected titanium sites are found to be five times as active (i.e. initial turnover frequencies) than 4-connected titanium sites (i.e. framework titanium sites).

Catalyst-free activation of peroxides under visible LED light irradiation through photoexcitation pathway

Energy Technology Data Exchange (ETDEWEB)

Gao, Yaowen [Department of Environmental Engineering, Wuhan University, Wuhan, 430079 (China); Shenzhen Research Institute of Wuhan University, Shenzhen, 518057 (China); Li, Yixi; Yao, Linyu; Li, Simiao; Liu, Jin [Department of Environmental Engineering, Wuhan University, Wuhan, 430079 (China); Zhang, Hui, E-mail: eeng@whu.edu.cn [Department of Environmental Engineering, Wuhan University, Wuhan, 430079 (China); Shenzhen Research Institute of Wuhan University, Shenzhen, 518057 (China)

2017-05-05

Highlights: • Persulfate could decolorize Rhodamine B (RhB) directly via non-radical reactions. • LED lamps emitting white light were utilized as the visible light source. • Dyes could activate peroxides through photoexcitation pathway. • Decolorization of dyes and production of radicals were achieved simultaneously. • The catalyst-free peroxide/dye/Vis process was effective in a broad pH range. - Abstract: Catalysts are known to activate peroxides to generate active radicals (i.e., hydroxyl radical (·OH) and sulfate radical (SO{sub 4}·{sup −})) under certain conditions, but the activation of peroxides in the absence of catalysts under visible light irradiation has been rarely reported. This work demonstrates a catalyst-free activation of peroxides for the generation of ·OH and/or SO{sub 4}·{sup −} through photoexcited electron transfer from organic dyes to peroxides under visible LED light irradiation, where Rhodamine B (RhB) and Eosin Y (EY) were selected as model dyes. The formation of ·OH and/or SO{sub 4}·{sup −} in the reactions and the electron transfer from the excited dyes to peroxides were validated via electron paramagnetic resonance (EPR), photoluminescence (PL) spectra and cyclic voltammetry (CV). The performance of the peroxide/dye/Vis process was demonstrated to be altered depending on the target substrate. Meanwhile, the peroxide/dye/Vis process was effective for simultaneous decolorization of dyes and production of active radicals under neutral even or basic conditions. The findings of this study clarified a novel photoexcitation pathway for catalyst-free activation of peroxides under visible light irradiation, which could avoid the secondary metal ion (dissolved or leached) pollution from the metal-based catalysts and expand the application range of the peroxide-based catalytic process.

Catalytic hydroprocessing of simulated coal tars. 2. Effect of acid catalysts on the hydroconversion of model compounds on a sulphided Ni-Mo/Al/sub 2/O/sub 3/ catalyst

Energy Technology Data Exchange (ETDEWEB)

Lemberton, J.L.; Touzeyidio, M.; Guisnet, M. (Laboratoire de Catalyse en Chimie Organique CNRS, Poitiers (France))

1989-09-15

Acid catalysts were added to sulphided Ni-Mo/Al/sub 2/O/sub 3/ catalyst in order to obtain a higher hydrocracking activity. The hydroconversion of phenanthrene, alone or in the presence of carbazole and/or 1-naphthol, was chosen as a model reaction. The presence of acid catalysts greatly increases the conversion of phenanthrene and allows significant amounts of light products to be obtained. In the presence of carbazole or of 1-naphthol, acid catalysts create a small increase in phenanthrene conversion, but light products are no longer obtained as the acid sites are poisoned either by adsorption of ammonia from carbazole decomposition, or by extensive coke deposition generated from 1-naphthol. In the presence of carbazole and 1-naphthol, there is no longer any effect of the acid catalysts on the hydroconversion of phenanthrene, owing to complete inhibition of the acid sites. 12 refs., 5 tabs.

Research advances in the catalysts for the selective oxidation of ethane to aldehydes

Institute of Scientific and Technical Information of China (English)

ZHANG Zhe; ZHAO Zhen; XU Chunming

2005-01-01

Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

Performance of (CoPC)n catalyst in active lithium-thionyl chloride cells

Science.gov (United States)

Shah, Pinakin M.

1990-01-01

An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.

In-situ Electrodeposition of Highly Active Silver Catalyst on Carbon Fiber Papers as Binder Free Cathodes for Aluminum-air Battery.

Science.gov (United States)

Hong, Qingshui; Lu, Huimin

2017-06-13

Carbon fiber papers supported Ag catalysts (Ag/CFP) with different coverage of electro-active site are prepared by electrochemical deposition and used as binder free cathodes in primary aluminum-air (Al-air) battery. Scanning Electron Microscopy and X-ray Diffraction studies are carried out to characterize the as-prepared Ag/CFP air cathodes. Oxygen reduction reaction (ORR) activities on these air cathodes in alkaline solutions are systematic studied. A newly designed aluminum-air cell is used to further determine the cathodes performance under real operation condition and during the test, the Ag/CFP electrodes show outstanding catalytic activity for ORR in concentrated alkaline electrolyte, and no obvious activity degradation is observed after long-time discharge. The electrochemical test results display the dependence of coverage of the electro-active Ag on the catalytic performance of the air cathodes. The resulting primary Al-air battery made from the best-performing cathode shows an impressive discharge peak power density, outperforming that of using commercial nano-manganese catalyst air electrodes.

Stable amorphous georgeite as a precursor to a high-activity catalyst

Science.gov (United States)

Kondrat, Simon A.; Smith, Paul J.; Wells, Peter P.; Chater, Philip A.; Carter, James H.; Morgan, David J.; Fiordaliso, Elisabetta M.; Wagner, Jakob B.; Davies, Thomas E.; Lu, Li; Bartley, Jonathan K.; Taylor, Stuart H.; Spencer, Michael S.; Kiely, Christopher J.; Kelly, Gordon J.; Park, Colin W.; Rosseinsky, Matthew J.; Hutchings, Graham J.

2016-03-01

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable—and hence little known and largely ignored—georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions—a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

Catalytic performance of activated carbon supported cobalt catalyst for CO2 reforming of CH4.

Science.gov (United States)

Zhang, Guojie; Su, Aiting; Du, Yannian; Qu, Jiangwen; Xu, Ying

2014-11-01

Syngas production by CO2 reforming of CH4 in a fixed bed reactor was investigated over a series of activated carbon (AC) supported Co catalysts as a function of Co loading (between 15 and 30wt.%) and calcination temperature (Tc=300, 400 or 500°C). The catalytic performance was assessed through CH4 and CO2 conversions and long-term stability. XRD and SEM were used to characterize the catalysts. It was found that the stability of Co/AC catalysts was strongly dependent on the Co loading and calcination temperature. For the loadings (25wt.% for Tc=300°C), stable activities have been achieved. The loading of excess Co (>wt.% 25) causes negative effects not only on the performance of the catalysts but also on the support surface properties. In addition, the experiment showed that ultrasound can enhance and promote dispersion of the active metal on the carrier, thus improving the catalytic performance of the catalyst. The catalyst activity can be long-term stably maintained, and no obvious deactivation has been observed in the first 2700min. After analyzing the characteristics, a reaction mechanism for CO2 reforming of CH4 over Co/AC catalyst was proposed. Copyright © 2014 Elsevier Inc. All rights reserved.

Mitigation of hydrogen by oxidation using nitrous oxide and noble metal catalysts

International Nuclear Information System (INIS)

Britton, M.D.

1995-01-01

This test studied the ability of a blend of nuclear-grade, noble-metal catalysts to catalyze a hydrogen/nitrous oxide reaction in an effort to mitigate a potential hydrogen (H 2 ) gas buildup in the Hanford Site Grout Disposal Facility. For gases having H 2 and a stoichiometric excess of either nitrous oxide or oxygen, the catalyst blend can effectively catalyze the H 2 oxidation reaction at a rate exceeding 380 μmoles of H 2 per hour per gram of catalyst (μmol/h/g) and leave the gas with less than a 0.15 residual H 2 Concentration. This holds true in gases with up to 2.25% water vapor and 0.1% methane. This should also hold true for gases with up to 0.1% carbon monoxide (CO) but only until the catalyst is exposed to enough CO to block the catalytic sites and stop the reaction. Gases with ammonia up to 1% may be slightly inhibited but can have reaction rates greater than 250 μmol/h/g with less than a 0.20% residual H 2 concentration. The mechanism for CO poisoning of the catalyst is the chemisorption of CO to the active catalyst sites. The CO sorption capacity (SC) of the catalyst is the total amount of CO that the catalyst will chemisorb. The average SC for virgin catalyst was determined to be 19.3 ± 2.0 μmoles of CO chemisorbed to each gram of catalyst (μmol/g). The average SC for catalyst regenerated with air was 17.3 ± 1.9 μmol/g

Catalytic Activity and Deactivation of SO2 Oxidation Catalysts in Simulated Power Plant Flue Gases

DEFF Research Database (Denmark)

Masters, Stephen G.; Chrissanthopoulos, Asthanassios; Eriksen, Kim Michael

1997-01-01

The catalyst deactivation and the simultaneious formation of compounds in commercial SO2 oxidation catalysts have been studied by combined activity measurements and in situ EPR spectroscopy in the temperature range 350-480 C in wet and dry simulated power plant flue gas.......The catalyst deactivation and the simultaneious formation of compounds in commercial SO2 oxidation catalysts have been studied by combined activity measurements and in situ EPR spectroscopy in the temperature range 350-480 C in wet and dry simulated power plant flue gas....

Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst

Directory of Open Access Journals (Sweden)

Istadi Istadi

2011-11-01

Full Text Available Major problem in CO2 reforming of methane (CORM process is coke formation which is a carbonaceous residue that can physically cover active sites of a catalyst surface and leads to catalyst deactivation. A key to develop a more coke-resistant catalyst lies in a better understanding of the methane reforming mechanism at a molecular level. Therefore, this paper is aimed to simulate a micro-kinetic approach in order to calculate coking rate in CORM reaction. Rates of encapsulating and filamentous carbon formation are also included. The simulation results show that the studied catalyst has a high activity, and the rate of carbon formation is relatively low. This micro-kinetic modeling approach can be used as a tool to better understand the catalyst deactivation phenomena in reaction via carbon deposition. Copyright © 2011 BCREC UNDIP. All rights reserved.(Received: 10th May 2011; Revised: 16th August 2011; Accepted: 27th August 2011[How to Cite: I. Istadi, D.D. Anggoro, N.A.S. Amin, and D.H.W. Ling. (2011. Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 129-136. doi:10.9767/bcrec.6.2.1213.129-136][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.2.1213.129-136 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/1213 ] | View in  |  

Achieving high-powered Zn/air fuel cell through N and S co-doped hierarchically porous carbons with tunable active-sites as oxygen electrocatalysts

Science.gov (United States)

Tang, Qiaowei; Wang, Luming; Wu, Mingjie; Xu, Nengneng; Jiang, Lei; Qiao, Jinli

2017-10-01

Electrochemical reduction of oxygen is the heart of the next-generation energy technologies to fuel cells and metal-air batteries, of which the reference catalysts suffer from two critical bottlenecks lying in their insufficient electroactivities and unclear active site structures. Herein, we introduce the effectively hierarchically porous carbons (HPCs) as the active-sites enriched platform for oxygen electroreduction. Three quaternized copolymers (PUB, PAADDA and PICP) with different chemical structures are used to pursue Fe/N/S-tailored ORR electrocatalysts. The most efficient one prepared by PAADDA gives the onset potential of 0.94 V and a half-wave potential of 0.85 V in basic solution, as well as superb electroactivities of low H2O2% and high electron transfer number in both alkaline and acidic medium. Surprisingly, they all display high discharge power density as applied to Zn-air fuel cells, and the HPCs-PAADDA catalyst thrillingly reaches 516.3 mW cm-2 when catalyst loading is optimized to 5.0 mg cm-2. The results elucidate that the polymer with long aliphatic chain is propitious to trap metals to create active sites and enwrap silica template to construct uniform pore structure. Only two kinds of nitrogen configuration (pyridinic-N and graphitic-N) are found with distinct structure in these HPCs, which happens to be active sites.

Novel, high-activity hydroprocessing catalysts: Iron group phosphides

Science.gov (United States)

Wang, Xianqin

A series of iron, cobalt and nickel transition metal phosphides was synthesized by means of temperature-programmed reduction (TPR) of the corresponding phosphates. The same materials, Fe2P, CoP and NO, were also prepared on a silica (SiO2) support. The phase purity of these catalysts was established by x-ray diffraction (XRD), and the surface properties were determined by N2 BET specific surface area (Sg) measurements and CO chemisorption. The activities of the silica-supported catalysts were tested in a three-phase trickle bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene using a model liquid feed at realistic conditions (30 atm, 370°C). The reactivity studies showed that the nickel phosphide (Ni2P/SiO2) was the most active of the catalysts. Compared with a commercial Ni-Mo-S/gamma-Al 2O3 catalyst at the same conditions, Ni2P/silica had a substantially higher HDS activity (100% vs. 76%) and HDN activity (82% vs. 38%). Because of their good hydrotreating activity, an extensive study of the preparation of silica supported nickel phosphides, Ni2P/SiO 2, was carried out. The parameters investigated were the phosphorus content and the weight loading of the active phase. The most active composition was found to have a starting synthesis Ni/P ratio close to 1/2, and the best loading of this sample on silica was observed to be 18 wt.%. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES) measurements were employed to determine the structures of the supported samples. The main phase before and after reaction was found to be Ni2P, but some sulfur was found to be retained after reaction. A comprehensive scrutiny of the HDN reaction mechanism was also made over the Ni2P/SiO2 sample (Ni/P = 1/2) by comparing the HDN activity of a series of piperidine derivatives of different structure. It was found that piperidine adsorption involved an alpha-H activation

Competing reaction processes on a lattice as a paradigm for catalyst deactivation

Science.gov (United States)

Abad, E.; Kozak, J. J.

2015-02-01

We mobilize both a generating function approach and the theory of finite Markov processes to compute the probability of irreversible absorption of a randomly diffusing species on a lattice with competing reaction centers. We consider an N-site lattice populated by a single deep trap, and N -1 partially absorbing traps (absorption probability 0 characteristic Ω =0 and Ω =2 . The results obtained allow a characterization of catalyst deactivation processes on planar surfaces and on catalyst pellets where only a single catalytic site remains fully active (deep trap), the other sites being only partially active as a result of surface poisoning. The central result of our study is that the predicted dependence of the reaction efficiency on system size N and on s is in qualitative accord with previously reported experimental results, notably catalysts exhibiting selective poisoning due to surface sites that have different affinities for chemisorption of the poisoning agent (e.g., acid zeolite catalysts). Deviations from the efficiency of a catalyst with identical sites are quantified, and we find that such deviations display a significant dependence on the topological details of the surface (for fixed values of N and s we find markedly different results for, say, a planar surface and for the polyhedral surface of a catalyst pellet). Our results highlight the importance of surface topology for the efficiency of catalytic conversion processes on inhomogeneous substrates, and in particular for those aimed at industrial applications. From our exact analysis we extract results for the two limiting cases s ≈1 and s ≈0 , corresponding respectively to weak and strong catalyst poisoning (decreasing s leads to a monotonic decrease in the efficiency of catalytic conversion). The results for the s ≈0 case are relevant for the dual problem of light-energy conversion via trapping of excitations in the chlorophyll antenna network. Here, decreasing the probability of excitation

Enzyme active site mimics based on TriAzaCyclophane (TAC)-scaffolded peptides and amino acid residues

NARCIS (Netherlands)

Albada, H.B.

2009-01-01

This thesis describes the scope and limitations of the application of TriAzaCyclophane (TAC)-scaffolded peptides or amino acid residues as enzyme active site mimics, as ligands in asymmetric catalysis and as hydrolysis catalysts attached to vancomycin. For the mimicry of functional group enzymes, of

Characterization and Regeneration of Pt-Catalysts Deactivated in Municipal Waste Flue Gas

DEFF Research Database (Denmark)

Rasmussen, Søren Birk; Kustov, Arkadii; Due-Hansen, Johannes

2006-01-01

Severe deactivation was observed for industrially aged catalysts used in waste incineration plants and tested in lab-scale. Possible compounds that cause deactivation of these Pt-based CO oxidation catalysts have been studied. Kinetic observations of industrial and model catalysts showed...... that siloxanes were the most severe catalyst poisons, although acidic sulfur compounds also caused deactivation. Furthermore, a method for on-site regeneration without shutdown of the catalytic flue gas cleaning system has been developed, i.e. an addition of H-2/N-2 gas to the off-gas can completely restore...... the activity of the deactivated catalysts. (c) 2006 Elsevier B.V. All rights reserved....

La-doped Al2O3 supported Au nanoparticles: highly active and selective catalysts for PROX under PEMFC operation conditions.

Science.gov (United States)

Lin, Qingquan; Qiao, Botao; Huang, Yanqiang; Li, Lin; Lin, Jian; Liu, Xiao Yan; Wang, Aiqin; Li, Wen-Cui; Zhang, Tao

2014-03-14

La-doped γ-Al2O3 supported Au catalysts show high activity and selectivity for the PROX reaction under PEMFC operation conditions. The superior performance is attributed to the formation of LaAlO3, which suppresses H2 oxidation and strengthens CO adsorption on Au sites, thereby improving competitive oxidation of CO at elevated temperature.

Activity of ruthenium, rhodium, iridium-ruthenium and iridium-rhodium adsorbed catalysts in dehydrogenation of formic acid

Energy Technology Data Exchange (ETDEWEB)

Mikhailov, V A; Zubovich, I A [Yaroslavskij Politekhnicheskij Inst. (USSR)

1977-04-01

The activity of Ru-, Rh- (Ir+nRu)- and (Ir+nRn) catalysts on sugar carbon and silicon dioxide in decomposition of HCOOH was studied. The catalyst activity increases in the series Iractivity is displayed by (Ir+nRh) catalysts on silicon dioxide. The results obtained point to activity of single centres (Ru)/sub 1/ and (Rh)/sub 1/ in the reaction of dehydration of HCOOH. It is shown that in the course of preparation of (Ir+nRh)- and (Ir+nRu)-catalysts the Ir atoms interact with Ru(Rh), and variable-composition structures are formed.

Liquefaction of kraft lignin by hydrocracking with simultaneous use of a novel dual acid-base catalyst and a hydrogenation catalyst.

Science.gov (United States)

Wang, Jindong; Li, Wenzhi; Wang, Huizhen; Ma, Qiaozhi; Li, Song; Chang, Hou-Min; Jameel, Hasan

2017-11-01

In this study, a novel catalyst, S 2 O 8 2- -KNO 3 /TiO 2 , which has active acidic and basic sites, was prepared and used in lignin hydrocracking with a co-catalyst, Ru/C. Ru/C is an efficient hydrogenation catalyst and S 2 O 8 2- -KNO 3 /TiO 2 is a dual catalyst, which could efficiently degrade lignin. This catalytic hydrogenation system can reduce solid products to less than 1%, while giving a high liquid product yield of 93%. Catalytic hydrocracking of kraft lignin at 320°C for 6h gave 93% liquid product with 0.5% solid product. Most of this liquid product was soluble in petroleum ether (60% of 93%), which is a clear liquid and comprises mainly of monomeric and dimeric degradation products. These results demonstrated that the combination of the two catalysts is an efficient catalyst for liquefaction of lignin, with little char formation (∼1%). This concept has the potential to produce valuable chemicals and fuels from lignin under moderate conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

The deuterium-exchange reaction between water and hydrogen with the thin-film hydrophobic catalyst

International Nuclear Information System (INIS)

Yamashita, Hisao; Mizumoto, Mamoru; Matsuda, Shimpei

1985-01-01

The deuterium-exchange reaction between water and hydrogen with a hydrophobic catalyst was studied. The hydrophobic catalyst was composed of platinum as an active component and porous poly(tetrafluoroethylene) (PTFE) as a support. The PTFE support was in two forms, i.e., (a) a pellet and (b) a thin-film with the thickness of 50 μm. The primary purpose of the thin film hydrophobic catalyst was to reduce the platinum usage in the reactor. The activity of the catalyst was measured in a trickle bed reactor at atmospheric pressure and temperature of 20 ∼ 70 deg C. It has been found that the employment of the thin-film catalyst reduced the platinum usage to 1/5 of the reactor in the case of using a conventional catalyst. Platinum particles on the thin-film catalyst work efficiently because the reactants were easily diffused to the active sites. It has also been found that the isotopic exchange rate with the thin-film catalyst increased with the increase in the ratio of liquid/gas and increased with the rise of the reaction temperature. It was found from an endurance test that the activity of the thin-film catalyst decreased gradually due to the condensation of water vapor in the catalyst, but was regenarated by heating the catalyst to remove the condensed water. (author)

Effects of impregnation methods and drying conditions on quinoline hydrodenitrogenation over Ni-W based catalysts

Energy Technology Data Exchange (ETDEWEB)

Guo, Fang; Qiu, Zegang; Zhao, Liangfu; Xiang, Hongwei [Institute of Coal Chemistry, Chinese Academy of Sciences (China); Guo, Shaoqing [Taiyuan University of Science and Technology (China)

2014-04-15

The effects of impregnation methods (co-impregnation and sequential impregnation) and drying conditions (air and vacuum) on the structure and catalytic behavior of MCM-41 supported Ni-W catalysts were investigated. The catalysts were characterized by powder X-ray diffraction (XRD) analysis, Fourier-transform infrared spectroscopy (FT-IR), diffuse reflectance UV-Vis absorbance spectroscopy (DRS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and pyridine adsorbed infrared spectroscopy (Py-IR) techniques. They were tested for hydrodenitrogenation (HDN) of quinoline at temperatures of 300-400 deg C. The HDN results showed that the catalysts prepared by co-impregnation were more active than the catalysts prepared by sequential impregnation and the catalysts prepared by drying under vacuum were more active than the catalysts dried in air. Characterization revealed that the co-impregnation method and drying under vacuum promoted the dispersion of W, the formation of the active phases, and the formation of acidic sites on the catalysts. (author)

Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

Energy Technology Data Exchange (ETDEWEB)

Zhou, Juan [School of the Environment, Donghua University, Shanghai 201620 (China); Chen, Huan, E-mail: hchen404@njust.edu.cn [Key Laboratory of Jiangsu Province for Chemical Pollution Control and Resources Reuse, School of Environmental & Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Chen, Quanyuan; Huang, Zhaolu [School of the Environment, Donghua University, Shanghai 201620 (China)

2016-11-30

Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N{sub 2} adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H{sub 2} chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d{sub 5/2} shifted to higher positions while that of Au 4f{sub 7/2} had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest

Effect of Solvent, Catalyst Type and Catalyst Activation on the Microwave Transformation of 2-Tert-butylphenol

Czech Academy of Sciences Publication Activity Database

Radoiu, M.; Hájek, Milan

2002-01-01

Roč. 186, 1-2 (2002), s. 121-126 ISSN 1381-1169 Institutional research plan: CEZ:AV0Z4072921 Keywords : microwaves * tert-butylphenols * catalyst activation Subject RIV: CC - Organic Chemistry Impact factor: 1.729, year: 2002

Part I: A Comparative Thermal Aging Study on the Regenerability of Rh/Al2O3 and Rh/CexOy-ZrO2 as Model Catalysts for Automotive Three Way Catalysts

Directory of Open Access Journals (Sweden)

Qinghe Zheng

2015-10-01

Full Text Available The rhodium (Rh component in automotive three way catalysts (TWC experiences severe thermal deactivation during fuel shutoff, an engine mode (e.g., at downhill coasting used for enhancing fuel economy. In a subsequent switch to a slightly fuel rich condition, in situ catalyst regeneration is accomplished by reduction with H2 generated through steam reforming catalyzed by Rh0 sites. The present work reports the effects of the two processes on the activity and properties of 0.5% Rh/Al2O3 and 0.5% Rh/CexOy-ZrO2 (CZO as model catalysts for Rh-TWC. A very brief introduction of three way catalysts and system considerations is also given. During simulated fuel shutoff, catalyst deactivation is accelerated with increasing aging temperature from 800 °C to 1050 °C. Rh on a CZO support experiences less deactivation and faster regeneration than Rh on Al2O3. Catalyst characterization techniques including BET surface area, CO chemisorption, TPR, and XPS measurements were applied to examine the roles of metal-support interactions in each catalyst system. For Rh/Al2O3, strong metal-support interactions with the formation of stable rhodium aluminate (Rh(AlO2y complex dominates in fuel shutoff, leading to more difficult catalyst regeneration. For Rh/CZO, Rh sites were partially oxidized to Rh2O3 and were relatively easy to be reduced to active Rh0 during regeneration.

Study on the correlation between the surface active species of Pd/cordierite monolithic catalyst and its catalytic activity

International Nuclear Information System (INIS)

Liao, Hengcheng; Zuo, Peiyuan; Liu, Miaomiao

2016-01-01

Two Pd-loading routes and three Pd-precursor matters were adopted to prepare Pd/(Ce,Y)O_2/γ-Al_2O_3/cordierite monolithic catalyst. The surface active species on the catalyst were characterized by XPS, and its catalytic activity for methane combustion was tested, and the dynamics of the catalytic combustion reaction was also discussed. Pd-loading route and Pd-precursor mass have a significant influence on the catalytic activity and surface active species. The sol dipping method is more advanced than the aqueous solution impregnating method. PN-sol catalyst, by sol dipping combined with Pd(NO_3)_2-precursor, has the best catalytic activity. The physical reason is the unique active Pd phase coexisting with active PdO phase on the surface, and thus the Pd3d_5_/_2 binding energy of surface species and apparent activation energy of combustion reaction are considerably decreased. The catalytic activity index, Pd3d_5_/_2 binding energy and apparent activation energy are highly tied each other with exponential relations.

Immobilization of isolated FI catalyst on polyhedral oligomeric silsesquioxane-functionalized silica for the synthesis of weakly entangled polyethylene.

Science.gov (United States)

Li, Wei; Yang, Huaqin; Zhang, Jingjing; Mu, Jingshan; Gong, Dirong; Wang, Xiaodong

2016-09-25

Polyhedral oligomeric silsesquioxanes (POSSs) were adsorbed on methylaluminoxane-activated silica for the immobilization of fluorinated bis(phenoxyimine)Ti complexes (FI catalyst). These POSSs have been characterized as horizontal spacers isolating the active sites and hindering the chain overlap in polymerization. The heterogeneous catalyst exhibits considerable activity in the synthesis of weakly entangled polyethylene.

Activity Tests of Macro-Meso Porous Catalysts over Metal Foam Plate for Steam Reforming of Bio-Ethanol.

Science.gov (United States)

Park, No-Kuk; Jeong, Yong Han; Kang, Misook; Lee, Tae Jin

2018-09-01

The catalytic activity of a macro-mesoporous catalyst coated on a metal foam plate in the reforming of bio-ethanol to synthesis gas was investigated. The catalysts were prepared by coating a support with a noble metal and transition metal. The catalytic activity for the production of synthetic gas by the reforming of bio-ethanol was compared according to the support material, reaction temperature, and steam/carbon ratio. The catalysts coated on the metal foams were prepared using a template method, in which macro-pores and meso-pores were formed by mixing polymer beads. In particular, the thermodynamic equilibrium composition of bio-ethanol reforming with the reaction temperature and steam/carbon ratio to produce synthetic gas was examined using the HSC (Enthalpy-Entropy-Heat capacity) chemistry program in this study. The composition of hydrogen and carbon monoxide in the reformate gas produced by steam reforming over the Rh/Ni-Ce-Zr/Al2O3-based pellet type catalysts and metal foam catalysts that had been coated with the Rh/Al-Ce-Zr-based catalysts was investigated by experimental activity tests. The activity of the metal foam catalyst was higher than that of the pellet type catalyst.

Oxygen reduction activities compared in rotating-disk electrode and proton exchange membrane fuel cells for highly active Fe-N-C catalysts

International Nuclear Information System (INIS)

Jaouen, F.; Goellner, V.; Lefèvre, M.; Herranz, J.; Proietti, E.; Dodelet, J.P.

2013-01-01

In the past three years, two novel synthesis methods for non-precious metal catalysts resulting in a breakthrough of their activity and performance at the cathode of the proton-exchange membrane fuel cell (PEMFC) have been reported by the group of Prof. Dodelet. While the activity of these novel Fe-based catalysts for the oxygen reduction reaction is very high in PEMFC, our preliminary activity measurements with the rotating disk electrode (RDE) technique on one of them showed an activity being a factor 30–100 lower than the one measured in PEMFC at 80 °C. The present work explains to a large extent this huge difference. Two Fe-N-C catalysts synthesized via our novel approaches and one Fe-N-C catalyst synthesized via our classical approach were investigated in RDE and PEMFC. In both systems, the effect of the ink formulation (Nafion-to-catalyst ratio) was investigated. Optimization of the RDE ink formulation explains a factor between 5 and 10 in the two-decade gap mentioned above. Then, the effect of temperature in the RDE system was investigated. An increase from 20 to 80 °C was found to result in a theoretical maximum twofold increase in activity. However, in practice, decreased O 2 solubility with increased temperature cancels this effect. After taking into account these two parameters, a difference in ORR activity between RDE and PEMFC of ca a factor five still remained for one of the two novel Fe-N-C catalysts investigated here. The lower initial activity measured in RDE for this catalyst is shown to be due to the fast adsorption of anions (HSO 4 − ) from the liquid H 2 SO 4 electrolyte on protonated nitrogen atoms (NH + ) found on its surface. The phenomenon of anion adsorption and associated decreased ORR activity also applies to the other novel Fe-N-C catalyst, but is slower and does not immediately occur in RDE.

Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Dumesic, James A. [Univ. of Wisconsin, Madison, WI (United States)

2016-01-04

The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

Biopolymer-stabilized Pt nanoparticles colloid: a highly active and recyclable catalyst for biphasic catalysis

Energy Technology Data Exchange (ETDEWEB)

Wang, Yujia; Shen, Yueyue; Qiu, Yunfei; Zhang, Ting; Liao, Yang; Zhao, Shilin; Ma, Jun, E-mail: 1044208419@qq.com; Mao, Hui, E-mail: rejoice222@163.com [Sichuan Normal University, College of Chemistry and Materials Science (China)

2016-10-15

Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85–2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous–organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al{sub 2}O{sub 3} catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

Biopolymer-stabilized Pt nanoparticles colloid: a highly active and recyclable catalyst for biphasic catalysis

International Nuclear Information System (INIS)

Wang, Yujia; Shen, Yueyue; Qiu, Yunfei; Zhang, Ting; Liao, Yang; Zhao, Shilin; Ma, Jun; Mao, Hui

2016-01-01

Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85–2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous–organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al 2 O 3 catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

Application in industry and energy production of active carbon/cobalt catalyst for nitrogen oxide neutralization

International Nuclear Information System (INIS)

Mekhandzhiev, D.; Nikolov, R.; Lyutskanov, L.; Dushanov, D.; Lakov, L.

1997-01-01

A new material for neutralization of nitrogen oxides is presented. Two or three metals containing catalysts with a good activity and selectivity towards NO x have been obtained. Preparation of carbon catalysts by deposition of the active phase precursor on the initial carbon material prior to activation is considered as the most promising method. An active carbon-based catalyst (AC/Co) has been synthesized Apricot shells preliminary impregnated with a water-alcohol solution of Co nitrate have been used as initial carbon material. after drying they have been subjected to one-phase steam pyrolysis using a fix-bed reactor. The catalyst thus obtained has a specific surface area (BET) of 53 m 2 g -1 , a favorable mesopore volume/total volume ratio (about 0.85) determined by nitrogen adsorption, a suitable mesopore distribution, about 70% of the mesopores being characterized by r p larger than 25 A and a high dispersion of the Co oxide phase. In addition the catalyst possesses the necessary mechanical resistance. The catalyst has exhibited a high activity with respect to NO x reduction with CO at low temperatures (at 150-250 o C which are the temperatures of industrial flue gases, nO conversion up to 60-95% occurs) and a high selectivity. No presence of H 2 O has been established over the whole temperature range (100-300 o C). An additional advantage of the catalyst is the fact that the amount of CO above 150 o C is lower than the stoichiometric which indicates parallel participation in the process of both the active phase and the support (active carbon) It is also important that the presented catalyst has a low price due to the use of waste products from agriculture and the elimination of special thermal treatment of the supported Co nitrate. There are possibilities of using of other organic wastes from agriculture as well as wastes obtained during flotation of coal. (author)

Enhanced oxidation of naphthalene using plasma activation of TiO2/diatomite catalyst.

Science.gov (United States)

Wu, Zuliang; Zhu, Zhoubin; Hao, Xiaodong; Zhou, Weili; Han, Jingyi; Tang, Xiujuan; Yao, Shuiliang; Zhang, Xuming

2018-04-05

Non-thermal plasma technology has great potential in reducing polycyclic aromatic hydrocarbons (PAHs) emission. But in plasma-alone process, various undesired by-products are produced, which causes secondary pollutions. Here, a dielectric barrier discharge (DBD) reactor has been developed for the oxidation of naphthalene over a TiO 2 /diatomite catalyst at low temperature. In comparison to plasma-alone process, the combination of plasma and TiO 2 /diatomite catalyst significantly enhanced naphthalene conversion (up to 40%) and CO x selectivity (up to 92%), and substantially reduced the formation of aerosol (up to 90%) and secondary volatile organic compounds (up to near 100%). The mechanistic study suggested that the presence of the TiO 2 /diatomite catalyst intensified the electron energy in the DBD. Meantime, the energized electrons generated in the discharge activated TiO 2 , while the presence of ozone enhanced the activity of the TiO 2 /diatomite catalyst. This plasma-catalyst interaction led to the synergetic effect resulting from the combination of plasma and TiO 2 /diatomite catalyst, consequently enhanced the oxidation of naphthalene. Importantly, we have demonstrated the effectiveness of plasma to activate the photocatalyst for the deep oxidation of PAH without external heating, which is potentially valuable in the development of cost-effective gas cleaning process for the removal of PAHs in vehicle applications during cold start conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

Science.gov (United States)

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-01-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

Effect of Au Precursor and Support on the Catalytic Activity of the Nano-Au-Catalysts for Propane Complete Oxidation

Directory of Open Access Journals (Sweden)

Arshid M. Ali

2015-01-01

Full Text Available Catalytic activity of nano-Au-catalyst(s for the complete propane oxidation was investigated. The results showed that the nature of both Au precursor and support strongly influences catalytic activity of the Au-catalyst(s for the propane oxidation. Oxidation state, size, and dispersion of Au nanoparticles in the Au-catalysts, surface area, crystallinity, phase structure, and redox property of the support are the key aspects for the complete propane oxidation. Among the studied Au-catalysts, the AuHAuCl4-Ce catalyst is found to be the most active catalyst.

Highly active Ni/Y-doped ZrO{sub 2} catalysts for CO{sub 2} methanation

Energy Technology Data Exchange (ETDEWEB)

Takano, H., E-mail: takano_hi@hitachizosen.co.jp [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Kirihata, Y.; Izumiya, K.; Kumagai, N. [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Habazaki, H., E-mail: habazaki@eng.hokudai.ac.jp [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Division of Applied Chemistry & Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Hashimoto, K. [Tohoku Institute of Technology, Sendai, 277-8515 (Japan)

2016-12-01

Highlights: • The Ni/Y-doped ZrO{sub 2} catalysts show highly catalytic activity for CO{sub 2} methanation. • Bidentate carbonate is a major adsorption spice on the Ni/Y-doped ZrO{sub 2} catalysts. • The oxide support of t-ZrO{sub 2} and/or c-ZrO{sub 2} with oxygen vacancies plays a key role. - Abstract: The catalytic methanation of CO{sub 2} was carried out on Ni catalysts supported on Y-doped ZrO{sub 2} with various Y{sup 3+} concentrations and Ni/(Zr + Y) molar ratio = 1. The catalysts were characterized by X-ray diffraction, scanning transmission electron microscopy, specific surface area, temperature-programmed desorption of CO{sub 2}, and temperature-programmed reaction. In addition, operando diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFT) was used to identify the adsorbed reaction intermediate. Catalysts supported on Y-doped ZrO{sub 2} show higher catalytic activity than the catalyst on Y-free ZrO{sub 2} with a monoclinic ZrO{sub 2} phase. The catalytic activity is also dependent upon the Y{sup 3+} concentration, and the highest activity was obtained for the catalyst with a Y/(Zr + Y) molar ratio of 0.333, which consists mainly of fcc Ni and cubic ZrO{sub 2} phase. Y{sup 3+} doping into ZrO{sub 2} introduces oxygen vacancies, which play an important role in enhancing the catalytic activity. The operando DRIFT study reveals that a CO adsorption intermediate is absent, and bidentate carbonate is an important intermediate for CH{sub 4} formation.

TiO2-Containing Carbon Derived from a Metal-Organic Framework Composite: A Highly Active Catalyst for Oxidative Desulfurization.

Science.gov (United States)

Bhadra, Biswa Nath; Song, Ji Yoon; Khan, Nazmul Abedin; Jhung, Sung Hwa

2017-09-13

A new metal-organic framework (MOF) composite consisting of Ti- and Zn-based MOFs (ZIF-8(x)@H 2 N-MIL-125; in brief, ZIF(x)@MOF) was designed and synthesized. The pristine MOF [H 2 N-MIL-125 (MOF)]- and an MOF-composite [ZIF(30)@MOF]-derived mesoporous carbons consisting of TiO 2 nanoparticles were prepared by pyrolysis (named MDC-P and MDC-C, respectively). MDC-C showed a higher surface area, larger pore sizes, and larger mesopore volumes than MDC-P. In addition, the TiO 2 nanoparticles on MDC-C have more uniform shapes and sizes and are smaller than those of MDC-P. The obtained MDC-C and MDC-P [together with MOF, ZIF(30)@MOF, pure/nanocrystalline TiO 2 , and activated carbon] were applied in the oxidative desulfurization reaction of dibenzothiophene in a model fuel. The MDC-C, even with a lower TiO 2 content than that of MDC-P, showed an outstanding catalytic performance, especially with a very low catalyst dose (i.e., a very high quantity of dibenzothiophene was converted per unit weight of the catalyst), fast kinetics (∼3 times faster than that for MDC-P), and a low activation energy (lower than that for any reported catalyst) for the oxidation of dibenzothiophene. The large mesopores of MDC-C and the well-dispersed/small TiO 2 might be the dominant factors for the superior catalytic conversions. The oxidative desulfurization of other sulfur-containing organic compounds with various electron densities was also studied with MDC-C to understand the mechanism of catalysis. Moreover, the MDC-C catalyst can be reused many times in the oxidative desulfurization reaction after a simple washing with acetone. Finally, composing MOFs and subsequent pyrolysis is suggested as an effective way to prepare a catalyst with well-dispersed active sites, large pores, and high mesoporosity.

Catalyst dispersion and activity under conditions of temperature-staged liquefaction. Final report

Energy Technology Data Exchange (ETDEWEB)

Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

1993-02-01

This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275{degrees}C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

Phosphorene Co-catalyst Advancing Highly Efficient Visible-Light Photocatalytic Hydrogen Production.

Science.gov (United States)

Ran, Jingrun; Zhu, Bicheng; Qiao, Shi-Zhang

2017-08-21

Transitional metals are widely used as co-catalysts boosting photocatalytic H 2 production. However, metal-based co-catalysts suffer from high cost, limited abundance and detrimental environment impact. To date, metal-free co-catalyst is rarely reported. Here we for the first time utilized density functional calculations to guide the application of phosphorene as a high-efficiency metal-free co-catalyst for CdS, Zn 0.8 Cd 0.2 S or ZnS. Particularly, phosphorene modified CdS shows a high apparent quantum yield of 34.7 % at 420 nm. This outstanding activity arises from the strong electronic coupling between phosphorene and CdS, as well as the favorable band structure, high charge mobility and massive active sites of phosphorene, supported by computations and advanced characterizations, for example, synchrotron-based X-ray absorption near edge spectroscopy. This work brings new opportunities to prepare highly-active, cheap and green photocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

In-situ Electrodeposition of Highly Active Silver Catalyst on Carbon Fiber Papers as Binder Free Cathodes for Aluminum-air Battery

OpenAIRE

Hong, Qingshui; Lu, Huimin

2017-01-01

Carbon fiber papers supported Ag catalysts (Ag/CFP) with different coverage of electro-active site are prepared by electrochemical deposition and used as binder free cathodes in primary aluminum-air (Al-air) battery. Scanning Electron Microscopy and X-ray Diffraction studies are carried out to characterize the as-prepared Ag/CFP air cathodes. Oxygen reduction reaction (ORR) activities on these air cathodes in alkaline solutions are systematic studied. A newly designed aluminum-air cell is use...

Electron beam application for regeneration of catalysts used in refinery cracking units

International Nuclear Information System (INIS)

Kondo, Fernando Mantovani; Duarte, Celina Lopes; Sato, Ivone Mulako; Salvador, Vera Lucia Ribeiro; Calvo, Wilson Aparecido Parejo

2013-01-01

A catalyst is a substance that alters the rate of a reaction. The process of catalysis is essential to the modern day manufacturing industry, mainly in Fluid Catalytic Cracking Process (FCC) units. However, long-term exploitation of oil and gas processing catalysts leads to formation of carbon-and sulfur-containing structures of coke and dense products on the catalyst surface. They block reactive catalyst sites and reduce the catalytic activity. The main advantage of radiation processing by electron beam (EB) and gamma rays is chain cracking reaction in crude oil. Otherwise, under exposure to ionic radiation, considerable structure modification of equilibrium silica-alumina catalyst from FCC process may occur, in addition to the removal of impurities. The conditions applied in the irradiation range (20-150 kGy) of gamma rays and electron beam were not sufficient to alter the structure of the catalyst, whether for removal of the contaminant nickel, a major contaminant of the FCC catalyst, either to rupture of the crystalline structure either for the future reutilization of chemical elements. Attenuated Total Reflectance - Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Energy Dispersive X-Ray Fluorescence Spectrometry (EDXRFS) analysis were used to characterize and evaluate effects of radiation processing on equilibrium catalysts purification. To evaluate and comprehend the reactive catalyst sites, Scanning Electron Microscopy (SEM) and particle size distribution analyses were carried out. (author)

Spectroscopic identification of the active site for CO oxidation on Rh/Al{sub 2}O{sub 3} by concentration modulation in situ DRIFTS

Energy Technology Data Exchange (ETDEWEB)

Cavers, M.; Davidson, J.M.; Harkness, I.R.; Rees, L.V.C.; McDougall, G.S.

1999-12-10

Diffuse reflectance infrared spectroscopy experiments are described in which the concentrations of the reactant gases passing over a solid catalyst are modulated. This simple modification to the normal in situ experiment enables direct correlation of specific surface species with the production of gaseous products. Spectra of solely the active surface intermediates with no contribution from so called spectator species are generated. For CO oxidation over a Rh/alumina catalyst at 576 K, the active CO species is identified as linearly adsorbed CO on oxidized Rh sites ({nu}{sub CO} = 2,100 cm{sup {minus}1}) on a catalyst surface apparently otherwise dominated by CO adsorbed as unreactive geminal dicarbonyl.

Improved ethanol electrooxidation performance by shortening Pd-Ni active site distance in Pd-Ni-P nanocatalysts

Science.gov (United States)

Chen, Lin; Lu, Lilin; Zhu, Hengli; Chen, Yueguang; Huang, Yu; Li, Yadong; Wang, Leyu

2017-01-01

Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (~5 nm) Pd-Ni-P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mgPd, which is 6.88 times higher than commercial Pd/C (0.72 A per mgPd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni-P heterodimers into Pd-Ni-P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH3CO radicals on adjacent Pd active sites.

Process intensification by combination of activated carbon supported catalysts and alternative energy sources

OpenAIRE

Calvino Casilda, Vanesa; Pérez-Mayoral, E.

2014-01-01

[EN] Activated carbons are well known for their catalytic properties and for being used as a catalyst support in heterogeneous catalysis. Activated carbons possess most of the desired properties of a catalyst support; inertness towards unwanted reactions, stability under regeneration and reaction conditions, suitable mechanical properties, tunable surface area, porosity, and the possibility of being manufactured in different size and shape. On the other hand, the in...

Synthesis and comparison of the activities of a catalyst supported on two silicate materials

Energy Technology Data Exchange (ETDEWEB)

Vieira, Eduardo G., E-mail: eduardogv5007@gmail.com [Departamento de Física e Química, Unesp-Univ Estadual Paulista, Av. Brasil, 56-Centro, Caixa Postal 31, CEP 15385-000, Ilha Solteira, São Paulo (Brazil); Silva, Rafael O.; Carmo, Devaney R. do [Departamento de Física e Química, Unesp-Univ Estadual Paulista, Av. Brasil, 56-Centro, Caixa Postal 31, CEP 15385-000, Ilha Solteira, São Paulo (Brazil); Junior, Enes F. [Departamento de Fitotecnia, Tecnologia de Alimentos e Sócio Economia, Faculdade de Engenharia de Ilha Solteira, Universidade Estadual Paulista, Ilha Solteira, São Paulo (Brazil); Dias Filho, Newton L., E-mail: nldias@unesc.net [Departamento de Física e Química, Unesp-Univ Estadual Paulista, Av. Brasil, 56-Centro, Caixa Postal 31, CEP 15385-000, Ilha Solteira, São Paulo (Brazil); Universidade do Extremo Sul Catarinense, Av. Universitaria, 1105, CP 3167, CEP 88806-000, Criciúma, SC (Brazil)

2017-04-15

The focus of this work is inspecting the synthesis and comparison of the activities of a catalyst supported on two silicate materials in the epoxidation of 1-octene. The two new catalyst materials were characterized by infrared spectroscopy, elemental analysis, solid-state {sup 29}Si and {sup 13}C nuclear magnetic resonance, scanning electronic microscope (SEM) and analysis of nitrogen. Lastly, the two new catalysts, Silsesq-TCA-[(W(CO){sub 3}I{sub 2}){sub 3}] and Silica-TCA-[W(CO){sub 3}I{sub 2}] were tested as catalysts in reactions of epoxidation of 1-octene and compared with their analogue not supported [W(CO){sub 3}I{sub 2}(thiocarbamide)]. After an extensive literature search, we verified that our work is the first that has reported the immobilization process of [W(CO){sub 3}I{sub 2}(NCCH{sub 3}){sub 2}] on silsesquioxane and silica gel functionalized with propyl-thiocarbamide groups and their applications as catalysts of reactions of catalytic epoxidation of 1-octene. - Highlights: • Immobilization of [W(CO){sub 3}I{sub 2}(NCCH{sub 3}){sub 2}] complex onto mesoporous supports. • Synthesis and characterization of new mesoporous catalysts. • The new catalysts exhibit great catalytic activity in the epoxidation of 1-octene. • Recyclable catalysts with excellent reusability and stability.

Catalytic Oxidation of NO over MnOx–CeO2 and MnOx–TiO2 Catalysts

Directory of Open Access Journals (Sweden)

Xiaolan Zeng

2016-11-01

Full Text Available A series of MnOx–CeO2 and MnOx–TiO2 catalysts were prepared by a homogeneous precipitation method and their catalytic activities for the NO oxidation in the absence or presence of SO2 were evaluated. Results show that the optimal molar ratio of Mn/Ce and Mn/Ti are 0.7 and 0.5, respectively. The MnOx–CeO2 catalyst exhibits higher catalytic activity and better resistance to SO2 poisoning than the MnOx–TiO2 catalyst. On the basis of Brunauer–Emmett–Teller (BET, X-ray diffraction (XRD, and scanning transmission electron microscope with mapping (STEM-mapping analyses, it is seen that the MnOx–CeO2 catalyst possesses higher BET surface area and better dispersion of MnOx over the catalyst than MnOx–TiO2 catalyst. X-ray photoelectron spectroscopy (XPS measurements reveal that MnOx–CeO2 catalyst provides the abundance of Mn3+ and more surface adsorbed oxygen, and SO2 might be preferentially adsorbed to the surface of CeO2 to form sulfate species, which provides a protection of MnOx active sites from being poisoned. In contrast, MnOx active sites over the MnOx–TiO2 catalyst are easily and quickly sulfated, leading to rapid deactivation of the catalyst for NO oxidation. Furthermore, temperature programmed desorption with NO and O2 (NO + O2-TPD and in situ diffuse reflectance infrared transform spectroscopy (in situ DRIFTS characterizations results show that the MnOx–CeO2 catalyst displays much stronger ability to adsorb NOx than the MnOx–TiO2 catalyst, especially after SO2 poisoning.

Isobutane alkylation over solid catalysts

Energy Technology Data Exchange (ETDEWEB)

Kozorezov, Y.I.; Lisin, V.I.

1979-05-01

Commercial alumina modified with 6Vertical Bar3< by wt boron trifluoride was active in isobutane alkylation with ethylene in a flow reactor at 5:1 isobutane-ethylene and 5-20 min reaction time. The reaction rate was first-order in ethylene and increased with increasing temperature (20/sup 0/-80/sup 0/C) and ethylene pressure (0.2-3 atm). The calculated activation energy was 8.4 kj. Kinetic data and the activity of tert.-butyl chloride, but not ethyl chloride as alkylating agents in place of ethylene suggested a carbonium-ion chain mechanism involving both surface and gas-phase reactions. The ethylene-based yield of the alkylate decreased from 132 to 41Vertical Bar3< by wt after nine hours on stream, and its bromine number increased from 0.2 to 1 g Br/sub 2//100 ml. This inhibition was attributed to adsorption on the active acidic sites of the reaction products, particularly C/sub 10//sup +/ olefins. Catalyst stabilization could probably be achieved by selecting an appropriate solvent that would continuously desorb the inhibiting products from the catalyst surface.

Molecular Active Sites in Heterogeneous Ir-La/C-Catalyzed Carbonylation of Methanol to Acetates.

Science.gov (United States)

Kwak, Ja Hun; Dagle, Robert; Tustin, Gerald C; Zoeller, Joseph R; Allard, Lawrence F; Wang, Yong

2014-02-06

We report that when Ir and La halides are deposited on carbon, exposure to CO spontaneously generates a discrete molecular heterobimetallic structure, containing an Ir-La covalent bond that acts as a highly active, selective, and stable heterogeneous catalyst for the carbonylation of methanol to produce acetic acid. This catalyst exhibits a very high productivity of ∼1.5 mol acetyl/mol Ir·s with >99% selectivity to acetyl (acetic acid and methyl acetate) without detectable loss in activity or selectivity for more than 1 month of continuous operation. The enhanced activity can be mechanistically rationalized by the presence of La within the ligand sphere of the discrete molecular Ir-La heterobimetallic structure, which acts as a Lewis acid to accelerate the normally rate-limiting CO insertion in Ir-catalyzed carbonylation. Similar approaches may provide opportunities for attaining molecular (single site) behavior similar to homogeneous catalysis on heterogeneous surfaces for other industrial applications.

Synthesis, characterization and catalytic activity of CoFe{sub 2}O{sub 4}-APTES-Pd magnetic recyclable catalyst

Energy Technology Data Exchange (ETDEWEB)

Demirelli, M. [Department of Chemistry, Faculty of Arts and Sciences, Yıldız Teknik University Davutpaşa Campus, Esenler, İstanbul (Turkey); Department of Chemistry, Faculty of Arts and Sciences, Fatih University, B. Cekmece, İstanbul 34500 (Turkey); Karaoğlu, E., E-mail: ebubekirkaraoglu@gmail.com [Department of Chemistry, Faculty of Arts and Sciences, Fatih University, B. Cekmece, İstanbul 34500 (Turkey); Department of Medical Biochemistry, Faculty of Medicine, Sakarya University, Korucuk, Sakarya (Turkey); Baykal, A. [Department of Chemistry, Faculty of Arts and Sciences, Fatih University, B. Cekmece, İstanbul 34500 (Turkey); Sözeri, H.; Uysal, E. [TUBITAK-UME, National Metrology Institute, PO Box 54, 41470 Gebze, Kocaeli (Turkey)

2014-01-05

Highlights: • CoFe{sub 2}O{sub 4}-APTES-Pd (0) nanocomposite, as effective catalysts for reduction reactions. • It could be reused several times without significant loss in hydrogenation reaction. • So far, CoFe{sub 2}O{sub 4}-APTES-Pd (0) nanocomposite have not been synthesized. • CoFe{sub 2}O{sub 4}-APTES-Pd (0) nanocomposite was confirmed by XRD, FT-IR. • Pd containing nanoparticles embedded in organic surfactant observed by TEM. -- Abstract: A new magnetically recyclable catalyst, CoFe{sub 2}O{sub 4}-APTES-Pd(0) nanocomposite, as highly effective catalysts for reduction reactions in liquid phase was fabricated and characterized. The reduction of Pd{sup 2+} was accomplished with sodium borohydride (NaBH{sub 4}). The chemical characterization of the product was done with X-ray diffractometry, infrared spectroscopy, transmission electron microscopy, UV–Vis spectroscopy and inductively coupled plasma. It was found that the combination of CoFe{sub 2}O{sub 4} and 3-aminopropyltriethoxysilane (APTES) could give rise to structurally stable catalytic sites. Furthermore, the high magnetization CoFe{sub 2}O{sub 4}-APTES-Pd(0) catalyst can be recovered by magnet and reused for ten runs for hydrogenation reaction of 4-nitro aniline, 1,3 dinitro and cyclohexanone. The catalyst was easily isolated from the reaction mixture by a magnetic bar and reused at least 10 times without significant degradation in the activity which shows the indicative of a potential applications of these catalysts in industry.

Polymer Catalysts Imprinted with Metal Ions as Biomimics of Metalloenzymes

Directory of Open Access Journals (Sweden)

Joanna Czulak

2013-01-01

Full Text Available This work presents the preparation and properties of molecularly imprinted polymers (MIPs with catalytic centers that mimic the active sites of metalloenzymes. The MIP synthesis was based on suspension polymerization of functional monomers (4-vinylpyridine and acrylonitrile with trimethylolpropane trimethacrylate as a crosslinker in the presence of transition metal ions and 4-methoxybenzyl alcohol as a template. Four metal ions have been chosen for imprinting from among the microelements that are the most essential in the native enzymes: Cu2+, Co2+, Mn2+, and Zn2+. To prepare catalysts, the required loading of metal ions was obtained during sorption process. The catalysts imprinted with Cu2+, Co2+, and Zn2+ were successfully used for hydroquinone oxidation in the presence of hydrogen peroxide. The Mn2+-imprinted catalyst showed no activity due to the insufficient metal loading. Cu2+ MIP showed the highest efficiency. In case of Cu- and Co-MIP catalysts, their activity was additionally increased by the use of surface imprinting technique.

Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

Energy Technology Data Exchange (ETDEWEB)

Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

2016-01-01

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

Hydrous titanium oxide-supported catalysts

International Nuclear Information System (INIS)

Dosch, R.G.; Stohl, F.V.; Richardson, J.T.

1990-01-01

Catalysts were prepared on hydrous titanium oxide (HTO) supports by ion exchange of an active metal for Na + ions incorporated in the HTO support during preparation by reaction with the parent Ti alkoxide. Strong active metal-HTO interactions as a result of the ion exchange reaction can require significantly different conditions for activation as compared to catalysts prepared by more widely used incipient wetness methods. The latter catalysts typically involve conversion or while the HTO catalysts require the alteration of electrostatic bonds between the metal and support with subsequent alteration of the support itself. In this paper, the authors discuss the activation, via sulfidation or reduction, of catalysts consisting of Co, Mo, or Ni-Mo dispersed on HTO supports by ion exchange. Correlations between the activation process and the hydrogenation, hydrodeoxygenation, and hydrodesulfurization activities of the catalysts are presented

Tunable, Chemo- and Site-Selective Nitrene Transfer Reactions through the Rational Design of Silver(I) Catalysts.

Science.gov (United States)

Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

2017-09-19

Carbon-nitrogen (C-N) bonds are ubiquitous in pharmaceuticals, agrochemicals, diverse bioactive natural products, and ligands for transition metal catalysts. An effective strategy for introducing a new C-N bond into a molecule is through transition metal-catalyzed nitrene transfer chemistry. In these reactions, a metal-supported nitrene can either add across a C═C bond to form an aziridine or insert into a C-H bond to furnish the corresponding amine. Typical catalysts for nitrene transfer include Rh 2 L n and Ru 2 L n complexes supported by bridging carboxylate and related ligands, as well as complexes based on Cu, Co, Ir, Fe, and Mn supported by porphyrins and related ligands. A limitation of metal-catalyzed nitrene transfer is the ability to predictably select which specific site will undergo amination in the presence of multiple reactive groups; thus, many reactions rely primarily on substrate control. Achieving true catalyst-control over nitrene transfer would open up exciting possibilities for flexible installation of new C-N bonds into hydrocarbons, natural product-inspired scaffolds, existing pharmaceuticals or biorenewable building blocks. Silver-catalyzed nitrene transfer enables flexible control over the position at which a new C-N bond is introduced. Ag(I) supported by simple N-donor ligands accommodates a diverse range of coordination geometries, from linear to tetrahedral to seesaw, enabling the electronic and steric parameters of the catalyst to be tuned independently. In addition, the ligand, Ag salt counteranion, Ag/ligand ratio and the solvent all influence the fluxional and dynamic behavior of Ag(I) complexes in solution. Understanding the interplay of these parameters to manipulate the behavior of Ag-nitrenes in a predictable manner is a key design feature of our work. In this Account, we describe successful applications of a variety of design principles to tunable, Ag-catalyzed aminations, including (1) changing Ag/ligand ratios to influence

Local Environment and Nature of Cu Active Sites in Zeolite-Based Catalysts for the Selective Catalytic Reduction of NOx

NARCIS (Netherlands)

Deka, U.|info:eu-repo/dai/nl/325811202; Lezcano-Gonzalez, I.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Beale, A.M.|info:eu-repo/dai/nl/325802068

2013-01-01

Cu-exchanged zeolites have demonstrated widespread use as catalyst materials in the abatement of NOx, especially from mobile sources. Recent studies focusing on Cu-exchanged zeolites with the CHA structure have demonstrated them to be excellent catalysts in the ammonia-assisted selective catalytic

SCR activity of conformed CuOx/ZrO2-SO4 catalysts

DEFF Research Database (Denmark)

Rasmussen, Søren Birk; Yates, Malcolm; Due-Hansen, Johannes

2010-01-01

CuOX/ZrO2-SO4 catalysts have been synthesised as conformed materials with the use of sepiolite as agglomerant and the performance in the NH3-SCR reaction with relation to biomass fired boiler units have been studied. The optimal Cu-loading of the catalysts is 3 wt.% CuO, both in terms of activity...

Fe3C-based oxygen reduction catalysts: synthesis, hollow spherical structures and applications in fuel cells

DEFF Research Database (Denmark)

Hu, Yang; Jensen, Jens Oluf; Zhang, Wei

2015-01-01

We present a detailed study of a novel Fe3C-based spherical catalyst with respect to synthetic parameters, nanostructure formation, ORR active sites and fuel cell demonstration. The catalyst is synthesized by high temperature autoclave pyrolysis using decomposing precursors. Below 500 °C, melamine...

Sulfated zirconia modified SBA-15 catalysts for cellobiose hydrolysis

NARCIS (Netherlands)

Degirmenci, V.; Uner, D.; Cinlar, B.; Shanks, B.H.; Yilmaz, A.; Santen, van R.A.; Hensen, E.J.M.

2011-01-01

Zirconia modified SBA-15 becomes a very active catalyst for the selective hydrolysis of cellobiose to glucose after sulfation. Spectroscopic investigations indicate the presence of Brønsted acid sites with similar properties to those present in conventional sulfated zirconia. Indications are found

Highly active Pd–In/mesoporous alumina catalyst for nitrate reduction

Energy Technology Data Exchange (ETDEWEB)

Gao, Zhenwei; Zhang, Yonggang; Li, Deyi [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Werth, Charles J. [Civil, Architectural and Environmental Engineering, University of Texas at Austin, 301 East Dean Keeton St., Stop C1786, Austin, TX 78712 (United States); Zhang, Yalei, E-mail: zhangyalei2003@163.com [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Zhou, Xuefei, E-mail: zhouxuefei@tongji.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China)

2015-04-09

Highlights: • Pd–In nanoparticles (6–7 nm) uniformly form in the mesopores of alumina (4 nm). • Pd–In nanoparticles aggregation is prevented during the synthesis process. • The reduction rate of nitrate is efficient by using the obtained catalyst. • The selectivity toward N{sub 2} is ideal by using the obtained catalyst. - Abstract: The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd–In/Al{sub 2}O{sub 3} with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO{sub 2}-buffered water and under continuous H{sub 2} as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd–In ratio of 4, with a first-order rate constant (k{sub obs} = 0.241 L min{sup −1} g{sub cata}{sup −1}) that was 1.3× higher than that of conventional Pd–In/Al{sub 2}O{sub 3} (5 wt% Pd; 0.19 L min{sup −1} g{sub cata}{sup −1}). The Pd–In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate.

Microwave-activated Ni/carbon catalysts for highly selective hydrogenation of nitrobenzene to cyclohexylamine.

Science.gov (United States)

Lu, Xinhuan; He, Jie; Jing, Run; Tao, Peipei; Nie, Renfeng; Zhou, Dan; Xia, Qinghua

2017-06-01

Biocarbon supported Ni catalysts have been prepared by facile impregnation of Ni species by microwave-heating and used for selective hydrogenation of nitrobenzene to cyclohexylamine. These catalysts were characterized by X-ray diffraction, Raman spectra, N2 sorption measurement, X-ray photoelectron spectroscopy, temperature programmed reduction of H2 and H2 temperature-programmed desorption. The morphology and particle size of catalysts were imaged by scanning electron microscope and transmission electron microscope. For the hydrogenation of nitrobenzene to cyclohexylamine, 10%Ni/CSC-II(b) exhibits the best catalytic activity to achieve 100 mol% conversion of nitrobenzene and 96.7% selectivity of cyclohexylamine under reaction conditions of 2.0 MPa H2 and 200 °C, ascribed to high dispersion of Ni species and formation of nanosized Ni particles on the support aided by microwave-heating. Thus-prepared Ni/CSC catalyst is greatly activated, in which the addition of precious metal like Rh is totally avoided.

Development of Molecular Catalysts to Bridge the Gap between Heterogeneous and Homogeneous Catalysts

Science.gov (United States)

Ye, Rong

Catalysts, heterogeneous, homogeneous, and enzymatic, are comprised of nanometer-sized inorganic and/or organic components. They share molecular factors including charge, coordination, interatomic distance, bonding, and orientation of catalytically active atoms. By controlling the governing catalytic components and molecular factors, catalytic processes of a multichannel and multiproduct nature could be run in all three catalytic platforms to create unique end-products. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis. Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles - some without homogeneous analogues - for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence and structural uniformity, dendrimers have proven to

Cobalt doped CuMnOx catalysts for the preferential oxidation of carbon monoxide

Science.gov (United States)

Dey, Subhashish; Dhal, Ganesh Chandra; Mohan, Devendra; Prasad, Ram; Gupta, Rajeev Nayan

2018-05-01

Carbon monoxide (CO) is a poisonous gas, recognized as a silent killer for the 21st century. It is produced from the partial oxidation of carbon containing compounds. The catalytic oxidation of CO receives a huge attention due to its applications in different fields. In the present work, hopcalite (CuMnOx) catalysts were synthesized using a co-precipitation method for CO oxidation purposes. Also, it was doped with the cobalt by varying concentration from 1 to 5wt%. It was observed that the addition of cobalt into the CuMnOx catalyst (by the deposition-precipitation method) improved the catalytic performance for the low-temperature CO oxidation. CuMnOx catalyst doped with 3wt% of cobalt exhibited most active performance and showed the highest activity than other cobalt concentrations. Different analytical tools (i.e. XRD, FTIR, BET, XPS and SEM-EDX) were used to characterize the as-synthesized catalysts. It was expected that the introduction of cobalt will introduce new active sites into the CuMnOx catalyst that are associated with the cobalt nano-particles. The order of calcination strategies based on the activity for cobalt doped CuMnOx catalysts was observed as: Reactive calcinations (RC) > flowing air > stagnant air. Therefore, RC (4.5% CO in air) route can be recommended for the synthesis of highly active catalysts. The catalytic activity of doped CuMnOx catalysts toward CO oxidation shows a correlation among average oxidation number of Mn and the position and the nature of the doped cobalt cation.

Effect of support on the activity of MoVCeZr catalyst for propane ammoxidation reaction

International Nuclear Information System (INIS)

Anita Ramli; Farinaa Md Jamil; Ishak Ahmad

2010-01-01

Mixed metal oxide catalysts based on Mo-V have been known as the most active and selective in the ammoxidation of propane to ACN. A series of MoVCeZr (5 % wt/ wt) supported with MOR, TiO 2 and MgO have been prepared by incipient wetness impregnation method for propane ammoxidation reaction to ACN. The catalyst was calcined in a two step calcination process in static air between 350 - 600 degree Celsius for 10 hour. The surface area and pore size of these catalysts were measured using physical adsorption of nitrogen following Brunauer, Emmet and Teller (BET) equation. The textural and morphological of these catalysts were determined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). The activities of all catalysts were tested using a fixed-bed reactor with online gas chromatography (GC) at 420 degree Celsius and atmospheric pressure in the presence of 0.5 ml catalyst with composition consisting of 5.8:7:17.4 (propane: ammonia: air) and helium as carrier to give a total flow of 120 ml. Result shows that MoVCeZr support gives a better conversion due to the surface area and pore size characteristic of the catalyst. (author)

Diels-Alder reactions in confined spaces: the influence of catalyst structure and the nature of active sites for the retro-Diels-Alder reaction.

Science.gov (United States)

Cantín, Ángel; Gomez, M Victoria; de la Hoz, Antonio

2016-01-01

Diels-Alder cycloaddition between cyclopentadiene and p -benzoquinone has been studied in the confined space of a pure silica zeolite Beta and the impact on reaction rate due to the concentration effect within the pore and diffusion limitations are discussed. Introduction of Lewis or Brønsted acid sites on the walls of the zeolite strongly increases the reaction rate. However, contrary to what occurs with mesoporous molecular sieves (MCM-41), Beta zeolite does not catalyse the retro-Diels-Alder reaction, resulting in a highly selective catalyst for the cycloaddition reaction.

Hydroprocessing catalyst development

Energy Technology Data Exchange (ETDEWEB)

Boorman, P.M.; Kydd, R.A.; Sorensen, T.S.; Chong, K.; Lewis, J.

1992-08-01

Co-Mo and Ni-Mo hydroprocessing catalysts were examined for their activity in removal of sulfur from thiophene in model compounds, and in the cracking and hydrocracking of cumene. Three types of support materials were examined: carbon, modified carbon, and carbon covered alumina. The objective of the study was to examine the correlation between catalyst activity in the hydrodenitrogenation of model compounds, and the resistance of the catalyst to nitrogen poisoning during use in the hydroprocessing of gas oils. The use of model compound testing provided information on the individual catalytic reactions promoted by those materials. Infrared spectroscopy was used to study surface species on the catalysts and to explain many of the trends in activity observed, revealing the role of fluoride and phosphorus as a secondary promoter. Testing of the catalysts in hydrotreating of gas oils allowed comparison of model compound results with those from a real feedstock. The gas oil was also spiked with a model nitrogen compound and the results from catalytic hydrotreating of this material were compared with those from unspiked material. A key finding was that the carbon supported catalysts were the most effective in treating high-nitrogen feeds. The very favorable deactivation properties of carbon and carbon-covered alumina supported catalysts make these promising from an industrial point of view where catalyst deactivation is a limiting factor. 171 refs., 25 figs., 43 tabs.

One-step flame synthesis of an active Pt/TiO2 catalyst for SO2 oxidation

DEFF Research Database (Denmark)

Johannessen, Tue; Koutsopoulos, Sotiris

2002-01-01

Flame synthesis as a route for production of composite metal oxides has been employed for the one-step synthesis of a supported noble metal catalyst, i.e. a Pt/TiO2 catalyst, by simultaneous combustion of Ti-isopropoxide and platinum acetylacetonate in a quench-cooled flame reactor. The average...... size of the platinum particles supported on aggregated nano-particles of TiO2 is approximately 2 nm. The high SO2-oxidation activity of the catalyst proves that platinum is not hidden in the titania matrix. The flame-produced catalyst showed catalytic activity similar to samples prepared by wet...

Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability.

Science.gov (United States)

Jackson, Ariel; Strickler, Alaina; Higgins, Drew; Jaramillo, Thomas Francisco

2018-01-12

Improving the performance of oxygen reduction reaction (ORR) electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs). Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C) prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mg Pt -1 at 0.9 V versus the reversible hydrogen electrode (RHE), which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing) are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mg Pt -1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s -1 ), maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS) analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.

SABER: a computational method for identifying active sites for new reactions.

Science.gov (United States)

Nosrati, Geoffrey R; Houk, K N

2012-05-01

A software suite, SABER (Selection of Active/Binding sites for Enzyme Redesign), has been developed for the analysis of atomic geometries in protein structures, using a geometric hashing algorithm (Barker and Thornton, Bioinformatics 2003;19:1644-1649). SABER is used to explore the Protein Data Bank (PDB) to locate proteins with a specific 3D arrangement of catalytic groups to identify active sites that might be redesigned to catalyze new reactions. As a proof-of-principle test, SABER was used to identify enzymes that have the same catalytic group arrangement present in o-succinyl benzoate synthase (OSBS). Among the highest-scoring scaffolds identified by the SABER search for enzymes with the same catalytic group arrangement as OSBS were L-Ala D/L-Glu epimerase (AEE) and muconate lactonizing enzyme II (MLE), both of which have been redesigned to become effective OSBS catalysts, demonstrated by experiments. Next, we used SABER to search for naturally existing active sites in the PDB with catalytic groups similar to those present in the designed Kemp elimination enzyme KE07. From over 2000 geometric matches to the KE07 active site, SABER identified 23 matches that corresponded to residues from known active sites. The best of these matches, with a 0.28 Å catalytic atom RMSD to KE07, was then redesigned to be compatible with the Kemp elimination using RosettaDesign. We also used SABER to search for potential Kemp eliminases using a theozyme predicted to provide a greater rate acceleration than the active site of KE07, and used Rosetta to create a design based on the proteins identified. Copyright © 2012 The Protein Society.

Location of adsorbed species in NO-reduction catalysts by high resolution neutron powder diffraction

International Nuclear Information System (INIS)

Fowkes, A.J.; Rosseinsky, M.J.

1999-01-01

Complete text of publication follows. Catalysts containing copper ion exchanged into zeolites are attracting considerable attention due to their efficiency for both NO decomposition and the selective catalytic reduction of NO x in so-called lean-burn conditions in automotive exhausts. This presentation will describe the application of in-situ high resolution neutron powder diffraction to study active sites in a Cu-zeolite Y catalyst active for NO decomposition. The study under NO pressure reveals the location of two distinct copper sites for sorption. The influence of copper oxidation state on the structure of both the pristine and NO-loaded zeolites will be discussed. (author)

Effects of precursor and sulfation on OMS-2 catalyst for oxidation of ethanol and acetaldehyde at low temperatures.

Science.gov (United States)

Wang, Renhu; Li, Junhua

2010-06-01

Volatile organic compounds (VOCs) emitted from many industrial processes and transportation activities are major organic pollutants in the atmosphere and toxic to human health. Octahedral molecular sieve (OMS-2) catalysts with different precursors and sulfate-acidified OMS-2 catalysts were synthesized using refluxing methods. The catalysts were investigated on complete oxidation of ethanol and acetaldehyde, and both demonstrated good reactivity. However, acidification resulted in a decrease in activity. OMS-2 catalyst using MnSO(4) as precursor exhibited the best catalytic performance and, thus, was selected for catalyst deactivation by sulfur dioxide. The results of this study suggested that the Mn-O bond of OMS-2 catalysts was the main determinant of the catalytic activity toward oxygenated VOC oxidation and weaker acid sites benefited higher acetaldehyde selectivity. Catalyst deactivation resulted from a strong but slow chemical interaction between the Mn-O bond and sulfur dioxide, probably forming manganese sulfate.

Catalytic Activity Studies of Vanadia/Silica–Titania Catalysts in SVOC Partial Oxidation to Formaldehyde: Focus on the Catalyst Composition

Directory of Open Access Journals (Sweden)

Niina Koivikko

2018-02-01

Full Text Available In this work, silica–titania supported catalysts were prepared by a sol–gel method with various compositions. Vanadia was impregnated on SiO2-TiO2 with different loadings, and materials were investigated in the partial oxidation of methanol and methyl mercaptan to formaldehyde. The materials were characterized by using N2 physisorption, X-ray diffraction (XRD, X-ray fluorescence spectroscopy (XRF, X-ray photoelectron spectroscopy (XPS, Scanning transmission electron microscope (STEM, NH3-TPD, and Raman techniques. The activity results show the high importance of an optimized SiO2-TiO2 ratio to reach a high reactant conversion and formaldehyde yield. The characteristics of mixed oxides ensure a better dispersion of the active phase on the support and in this way increase the activity of the catalysts. The addition of vanadium pentoxide on the support lowered the optimal temperature of the reaction significantly. Increasing the vanadia loading from 1.5% to 2.5% did not result in higher formaldehyde concentration. Over the 1.5%V2O5/SiO2 + 30%TiO2 catalyst, the optimal selectivity was reached at 415 °C when the maximum formaldehyde concentration was ~1000 ppm.

Production of Biodiesel by Esterification of Free Fatty Acid over Solid Catalyst from Biomass Waste

Science.gov (United States)

Mukti, N. I. F.; Sutrisno, B.; Hidayat, A.

2018-05-01

Recently, low cost feedstocks have been utilized to replace vegetable oils in order to improve the economic feasibility of biodiesel. The esterification of free fatty acid (FFA) on Palm Fatty Acid Distillate (PFAD) with methanol using solid catalyst generated from bagasse fly ash is a promising method to convert FFA into biodiesel. In this research, the esterification of FFA on PFAD using the sulfonated bagasse fly ash catalyst was studied. The performances of the catalysts were evaluated in terms of the reaction temperatures, the molar ratios of methanol to PFAD, and the catalyst loading. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimum conditions were methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%wt. of PFAD, and reaction temperature of 6°C. The reusability of the solid acid carbon catalysts was also studied in this work. The catalytic activity decreased up to 38% after third cycle. The significant decline in catalyst esterification activity was due to acid site leaching. The physico-characteristics and acid site densities were analyzed by Nitrogen gas adsorption, surface functional groups by Fourier transform infrared spectroscopy (FT-IR), elemental analysis using X-ray fluorescent (XRF), and acid-base back titration methods for determination of acid density.

Regeneration of Pt-catalysts deactivated in municipal waste flue gas with H2/N2 and the effect of regeneration step on the SCR catalyst

DEFF Research Database (Denmark)

Due-Hansen, Johannes; Rasmussen, Søren Birk; Kustov, Arkadii

Municipal waste flue gas was previously found to deactivate the Pt-based CO oxidation catalyst severely. In the specific case studied, siloxanes were found to cause the deactivation. An on-site method for complete regeneration of the catalyst activity was found without shutdown of the flue gas...... stream, i.e. by in situ treatment of the Pt-catalyst by reductive H2-gas. However, introduction of H2 gas in the gas stream could also affect other units in the tail pipe gas cleaning system. Of special interest here, is the effect of hydrogen gas on the performance of the deNOx + SCR catalytic process...

Anti-bacteria activity of carbon nanotubes grown on trimetallic catalyst

Science.gov (United States)

Ibrahim, S. O.; Abdulkareem, A. S.; Isah, K. U.; Ahmadu, U.; Bankole, M. T.; Kariim, I.

2018-06-01

Trimetallic catalyst was prepared using wet impregnation method to produce carbon nanotubes (CNTs) through the method of catalytic chemical vapor deposition (CCVD). Characterization of the developed catalyst and CNTs were carried out using thermogravimetric analysis (TGA), x-ray diffraction (XRD), specific surface area Brunauer-Emmett-Teller (BET), Fourier-transform infrared spectroscopy (FTIR), high-resolution scanning electron microscopy (HRSEM)/energy dispersive x-ray spectroscopy (EDS) and high-resolution transmission electron microscopy (HRTEM)/selected area electron diffraction (SAED). The BET and TGA analysis indicated that the catalyst has a high surface area and is thermally stable. The FTIR of the developed catalyst shows notable functional group with presence of unbound water. The HRSEM of the catalyst revealed agglomerated, homogeneous and porous particles while the HRSEM/HRTEM of the produced CNTs gave the formation of long strand of multiwalled carbon nanotubes (MWCNTs), and homogeneous crystalline fringe like structure with irregular diameter. EDS revealed the dominance of carbon in the elemental composition. XRD/SAED patterns of the catalyst suggest high dispersion of the metallic particles in the catalyst mixture while that of the CNTs confirmed that the produced MWCNTs were highly graphitized and crystalline in nature with little structural defects. The anti-bacteria activity of the produced MWCNTs on Klebsiella pneumoneae, Escherichia coli, and Pseudomonas aeruginosa was also carried out. It was observed that the produced MWCNTs have an inhibitory property on bacteria; Escherichia coli and Klebsiella pneumoneae from zero day ( and ) through to twelfth day (Nil count) respectively. It has no effect on Pseudomonas aeruginosa with too numerous to count at zero-sixth day, but a breakdown in its growth at ninth-twelfth day (). This study implied that MWCNTs with varying diameter and well-ordered nano-structure can be produced from catalyst via CCVD

Effect of Mo-Doped Mesoporous Al-SSP Catalysts for the Catalytic Dehydration of Ethanol to Ethylene

Directory of Open Access Journals (Sweden)

Titinan Chanchuey

2016-01-01

Full Text Available The catalytic dehydration of ethanol to ethylene over the mesoporous Al-SSP and Mo-doped Al-SSP catalysts was investigated. The Al-SSP catalyst was first synthesized by the modified sol-gel method and then doped with Mo by impregnation to obtain 1% Mo/Al-SSP and 5% Mo/Al-SSP catalysts (1 and 5 wt% of Mo. The final catalysts were characterized using various techniques such as XRD, N2 physisorption, SEM/EDX, TEM, and NH3-TPD. The catalytic activity for all catalysts in gas-phase ethanol dehydration reaction was determined at temperature range of 200°C to 400°C. It was found that the most crucial factor influencing the catalytic activities appears to be the acidity. The acid property of catalysts depended on the amount of Mo loading. Increased Mo loading in Al-SSP resulted in increased weak acid sites, which enhanced the catalytic activity. Besides acidity, the high concentration of Al at surface of catalyst is also essential to obtain high activity. Based on the results, the most suitable catalyst in this study is 1% Mo/Al-SSP catalyst, which can produce ethylene yield of ca. 90% at 300°C with slight amounts of diethyl ether (DEE and acetaldehyde.

Activation of Mg-Al hydrotalcite catalysts for transesterification of rape oil

Energy Technology Data Exchange (ETDEWEB)

Hong-yan Zeng; Zhen Feng; Xin Deng; Yu-qin Li [University of Xiangtan, Hunan (China). Institute of Biotechnology

2008-10-15

Mg-Al hydrotalcites with different Mg/Al molar ratios were prepared and characterized by powder X-ray diffraction (XRD), Fourier-transform infrared spectra (FTIR), thermogravimetric apparatus and differential thermal analysis (TGA-DTA) and scanning electron micrograph (SEM). It was confirmed by XRD that the materials had hydrotalcite structure. The hydrotalcite catalyst calcined at 773 K with Mg/Al molar ratio of 3.0 exhibited the highest catalytic activity in the transesterification. In addition, a study for optimizing the transesterification reaction conditions such as molar ratio of the methanol to oil, the reaction temperature, the reaction time, the stirring speed and the amount of catalyst, was performed. The optimized parameters, 6:1 methanol/oil molar ratio with 1.5% catalyst (w/w of oil) reacted under stirring speed 300 rpm at 65{sup o}C for 4 h reaction, gave a maximum ester conversion of 90.5%. Moreover, the solid catalyst could be easily separated and possibly reused. 33 refs., 5 figs., 1 tab.

High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst

KAUST Repository

Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi Zhang

2016-01-01

Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst.

Science.gov (United States)

Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi-Zhang

2016-12-14

Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst

KAUST Repository

Zheng, Yao

2016-11-28

Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas

2017-09-25

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas; Le Qué mé ner, Fré dé ric; Barman, Samir; Samantaray, Manoja; Szeto, Kai C.; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

2017-01-01

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

Recent density functional studies of hydrodesulfurization catalysts: insight into structure and mechanism

International Nuclear Information System (INIS)

Hinnemann, Berit; Moses, Poul Georg; Noerskov, Jens K

2008-01-01

The present article will highlight some recent density functional theory (DFT) studies of hydrodesulfurization (HDS) catalysts. It will be summarized how DFT in combination with experimental studies can give a detailed picture of the structure of the active phase. Furthermore, we have used DFT to investigate the reaction pathway for thiophene HDS, and we find that the reaction entails a complex interplay of different active sites, depending on reaction conditions. An investigation of pyridine inhibition confirmed some of these results. These fundamental insights constitute a basis for rational improvement of HDS catalysts, as they have provided important structure-activity relationships

The atomistic origin of the extraordinary oxygen reduction activity of Pt3Ni7 fuel cell catalysts.

Science.gov (United States)

Fortunelli, Alessandro; Goddard Iii, William A; Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Jaramillo-Botero, Andrés

2015-07-01

Recently Debe et al. reported that Pt 3 Ni 7 leads to extraordinary Oxygen Reduction Reaction (ORR) activity. However, several reports show that hardly any Ni remains in the layers of the catalysts close to the surface ("Pt-skin effect"). This paradox that Ni is essential to the high catalytic activity with the peak ORR activity at Pt 3 Ni 7 while little or no Ni remains close to the surface is explained here using large-scale first-principles-based simulations. We make the radical assumption that processing Pt-Ni catalysts under ORR conditions would leach out all Ni accessible to the solvent. To simulate this process we use the ReaxFF reactive force field, starting with random alloy particles ranging from 50% Ni to 90% Ni and containing up to ∼300 000 atoms, deleting the Ni atoms, and equilibrating the resulting structures. We find that the Pt 3 Ni 7 case and a final particle radius around 7.5 nm lead to internal voids in communication with the exterior, doubling the external surface footprint, in fair agreement with experiment. Then we examine the surface character of these nanoporous systems and find that a prominent feature in the surface of the de-alloyed particles is a rhombic structure involving 4 surface atoms which is crystalline-like but under-coordinated. Using density-functional theory, we calculate the energy barriers of ORR steps on Pt nanoporous catalysts, focusing on the O ad -hydration reaction (O ad + H 2 O ad → OH ad + OH ad ) but including the barriers of O 2 dissociation (O 2ad → O ad + O ad ) and water formation (OH ad + H ad → H 2 O ad ). We find that the reaction barrier for the O ad -hydration rate-determining-step is reduced significantly on the de-alloyed surface sites compared to Pt(111). Moreover we find that these active sites are prevalent on the surface of particles de-alloyed from a Pt-Ni 30 : 70 initial composition. These simulations explain the peak in surface reactivity at Pt 3 Ni 7 , and provide a rational guide to

Catalytic activity of cobalt and cerium catalysts supported on calcium hydroxyapatite in ethanol steam reforming

Directory of Open Access Journals (Sweden)

Dobosz Justyna

2016-09-01

Full Text Available In this paper, Co,Ce/Ca10(PO46(OH2 catalysts with various cobalt loadings for steam reforming of ethanol (SRE were prepared by microwave-assisted hydrothermal and sol-gel methods, and characterized by XRD, TEM, TPR-H2, N2 adsorption-desorption measurements and cyclohexanol (CHOL decomposition tests. High ethanol conversion (close to 100% was obtained for the catalysts prepared by both methods but these ones prepared under hydrothermal conditions (HAp-H ensured higher hydrogen yield (3.49 mol H2/mol C2H5OH as well as higher amount of hydrogen formed (up to 70% under reaction conditions. The superior performance of 5Co,10Ce/HAp-H catalyst is thought to be due to a combination of factors, including increased reducibility and oxygen mobility, higher density of basic sites on its surface, and improved textural properties. The results also show a significant effect of cobalt loading on catalysts efficiency in hydrogen production: the higher H2 yield exhibit catalysts with lower cobalt content, regardless of the used synthesis method.

C-C Coupling on Single-Atom-Based Heterogeneous Catalyst.

Science.gov (United States)

Zhang, Xiaoyan; Sun, Zaicheng; Wang, Bin; Tang, Yu; Nguyen, Luan; Li, Yuting; Tao, Franklin Feng

2018-01-24

Compared to homogeneous catalysis, heterogeneous catalysis allows for ready separation of products from the catalyst and thus reuse of the catalyst. C-C coupling is typically performed on a molecular catalyst which is mixed with reactants in liquid phase during catalysis. This homogeneous mixing at a molecular level in the same phase makes separation of the molecular catalyst extremely challenging and costly. Here we demonstrated that a TiO 2 -based nanoparticle catalyst anchoring singly dispersed Pd atoms (Pd 1 /TiO 2 ) is selective and highly active for more than 10 Sonogashira C-C coupling reactions (R≡CH + R'X → R≡R'; X = Br, I; R' = aryl or vinyl). The coupling between iodobenzene and phenylacetylene on Pd 1 /TiO 2 exhibits a turnover rate of 51.0 diphenylacetylene molecules per anchored Pd atom per minute at 60 °C, with a low apparent activation barrier of 28.9 kJ/mol and no cost of catalyst separation. DFT calculations suggest that the single Pd atom bonded to surface lattice oxygen atoms of TiO 2 acts as a site to dissociatively chemisorb iodobenzene to generate an intermediate phenyl, which then couples with phenylacetylenyl bound to a surface oxygen atom. This coupling of phenyl adsorbed on Pd 1 and phenylacetylenyl bound to O ad of TiO 2 forms the product molecule, diphenylacetylene.

Solid Catalyst Nanoparticles derived from Oil-Palm Empty Fruit Bunches (OP-EFB) as a Renewable Catalyst for Biodiesel Production

Science.gov (United States)

Husin, H.; Asnawi, T. M.; Firdaus, A.; Husaini, H.; Ibrahim, I.; Hasfita, F.

2018-05-01

Solid nanocatalyst derived from oil-palm empty fruit bunches (OP-EFB) fiber was successfully synthesized and its application for biodiesel production was investigated. The OPEFB was treated by burning, milling and heating methods to generate ashes in a nanoparticle size. The nanoparticle palm-bunch ash was characterized by scanning electron microscopy (SEM) and x-ray diffraction (XRD). The effects of the calcination temperature and catalyst amounts for transesterification reactions were investigated. XRD analysis of palm bunch ash exhibited that the highest composition of peaks characteristic were potassium oxide (K2O). SEM analysis showed that the nano palm bunch ash have a particle size ranging of 150-400 nm. The highest conversion of palm-oil to biodiesel reach to 97.90% was observed by using of palm bunch ash nanocatalyst which heated at 600°C, 3 h reaction time and 1% catalyst amount. Reusability of palm bunch ash catalysts was also examined. It was found that of its high active sites, reusable solid catalyst was obtained by just heating of palm bunch ash. It has a capability to reduce not only the amount of catalyst consumption but also reduce the reaction time of transesterification process.

Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

Science.gov (United States)

Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan N., Pethan; Kumar Balla, Putra; Chary Komandur, V. R.

2014-08-01

Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol-gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO3) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV-vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

International Nuclear Information System (INIS)

Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan, Pethan N.; Kumar Balla, Putra; Chary Komandur, V.R.

2014-01-01

Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol–gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO 3 ) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV–vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH 3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

Energy Technology Data Exchange (ETDEWEB)

Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan, Pethan N.; Kumar Balla, Putra; Chary Komandur, V.R., E-mail: kvrchary@iict.res.in

2014-08-01

Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol–gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO{sub 3}) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV–vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH{sub 3} TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

KAUST Repository

Al-ShaikhAli, Anaam H.

2016-11-30

Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

The effect of passivation on the activity and structure of sulfided hydrotreating catalysts

NARCIS (Netherlands)

Louwers, S.P.A.; Crajé, M.W.J.; Kraan, van der A.M.; Geantet, C.; Prins, R.

1993-01-01

Air exposure (passivation) and subsequent resulfidation caused a substantial increase in the thiophene hydrodesulfurization activity of sulfided Co-Mo/Al2O3 catalysts. Since no effect was observed for Mo/Al2O3 and Co/Al2O3 catalysts, the passivation effect must be related to the Co---Mo---S

Improved ethanol electrooxidation performance by shortening Pd–Ni active site distance in Pd–Ni–P nanocatalysts

Science.gov (United States)

Chen, Lin; Lu, Lilin; Zhu, Hengli; Chen, Yueguang; Huang, Yu; Li, Yadong; Wang, Leyu

2017-01-01

Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (∼5 nm) Pd–Ni–P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mgPd, which is 6.88 times higher than commercial Pd/C (0.72 A per mgPd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni–P heterodimers into Pd–Ni–P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH3CO radicals on adjacent Pd active sites. PMID:28071650

HDS, HDN and HDA activities of nickel-molybdenum catalysts supported on alumina

Energy Technology Data Exchange (ETDEWEB)

Dominguez-Crespo, M.A. [Instituto Mexicano del Petroleo, Programa de Tratamiento de Crudo Maya. Avenida Eje Central Lazaro Cardenas No.152, Col. San Bartolo Atepehuacan, 07730, Mexico D. F. (Mexico); Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada (CICATA-Altamira, IPN) Km 14.5 Carretera Tampico-puerto Industrial 89600, Altamira, Tamaulipas (Mexico); Torres-Huerta, A.M.; Ramirez-Meneses, E. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada (CICATA-Altamira, IPN) Km 14.5 Carretera Tampico-puerto Industrial 89600, Altamira, Tamaulipas (Mexico); Diaz-Garcia, L. [Instituto Mexicano del Petroleo, Programa de Tratamiento de Crudo Maya. Avenida Eje Central Lazaro Cardenas No.152, Col. San Bartolo Atepehuacan, 07730, Mexico D. F. (Mexico); Arce-Estrada, E.M. [Instituto Politecnico Nacional, Departamento de Metalurgia y Materiales. A.P. 75-876, 07300 Mexico, D. F. (Mexico)

2008-08-15

In this work, NiMo-Al{sub 2}O{sub 3} catalysts were prepared by using different alumina precursors. The supports were impregnated by means of the spray at incipient wetness technique in both basic and acid media. Both the supports and fresh catalysts were characterized by the adsorption-desorption isotherms, Temperature-Programmed Reduction (TPR), Thermal Pyridine Adsorption-Desorption (TPD) and X-Ray Diffraction analyses (XRD). After sulfidation, the NiMoS metallic particles were characterized by Transmission Electron Microscopy (TEM). The initial analyses were performed in a trickle-bed reactor by using a real feedstock (Mexican heavy gas oil) and performing hydrotreating reactions (HDS, HDN and HDA) at three different temperatures: 613, 633 and 653 K; and 54 kg cm{sup -} {sup 2}. The catalytic activities are discussed in relation to the physicochemical properties of the NiMo catalysts, alumina phase and pH of the impregnating solution. The catalytic results show an increase in the conversion profiles with temperature. The sulfur conversion was increased from 89 to 99.25%, 91-99%, 90.8-97%, 83-95% and 78-96% when the crystal size of the support varied from 3 to 20 nm, respectively. The nitrogen and aromatic conversions were also increased in the range of 23-45 wt.%. It was found that the {gamma} phase reached a higher catalytic performance than the {eta} phase. The NiMo catalysts synthesized in a basic medium showed a better catalytic performance than that obtained with those prepared in acid solutions. The significance of the kinetic data to compare the catalysts is discussed. The maximum value of the catalytic activity was reached with the catalysts with the smallest particle sizes. (author)

Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability

Directory of Open Access Journals (Sweden)

Ariel Jackson

2018-01-01

Full Text Available Improving the performance of oxygen reduction reaction (ORR electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs. Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mgPt−1 at 0.9 V versus the reversible hydrogen electrode (RHE, which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mgPt−1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s−1, maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.

Chelating agent-assisted heat treatment of a carbon-supported iron oxide nanoparticle catalyst for PEMFC.

Science.gov (United States)

Liu, Shyh-Jiun; Huang, Chia-Hung; Huang, Chun-Kai; Hwang, Weng-Sing

2009-08-28

Iron complexes were supported on commercial carbon black and heat treated to create FeO(x)/C catalysts that showed a larger normalized current density and normalized power density than commercial Pt/C catalysts; the coordination number of the iron complexes used affected the formation of the active site for oxygen reduction in PEMFC.

Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

International Nuclear Information System (INIS)

Amende, Max; Kaftan, Andre; Bachmann, Philipp; Brehmer, Richard; Preuster, Patrick; Koch, Marcus

2016-01-01

partially restored under the applied reaction conditions. Whereas partial regeneration on facet-like sites on supported catalysts is more facile than on Pt(111), carbonaceous deposits adsorbed at low-coordinated defect sites impede full regeneration of the Pt/Al_2O_3 catalysts.

Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

Energy Technology Data Exchange (ETDEWEB)

Amende, Max, E-mail: max.amende@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Kaftan, Andre, E-mail: andre.kaftan@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Bachmann, Philipp, E-mail: philipp.bachmann@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Brehmer, Richard, E-mail: richard.brehmer@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Preuster, Patrick, E-mail: patrick.preuster@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Koch, Marcus, E-mail: marcus.koch@crt.cbi.uni-erlangen.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); and others

2016-01-01

core–shell pellet were only partially restored under the applied reaction conditions. Whereas partial regeneration on facet-like sites on supported catalysts is more facile than on Pt(111), carbonaceous deposits adsorbed at low-coordinated defect sites impede full regeneration of the Pt/Al{sub 2}O{sub 3} catalysts.

Activity of bimetallic catalysts (Pt + Me)/A12030 in butane hydrogenolysis and benzene hydrogenation

International Nuclear Information System (INIS)

Zharkov, B.B.; Rubinov, A.Z.

1986-01-01

The authors evaluate the decomposing and hydrogenating activity of some Me/Al 2 0 3 0 and (Pt + Me)/Al 203 catalysis for the reactions of butane hydrogenolysis and conversion of benzene to cyclohexane. The temperature was 180-300 C for butane transformation and 150 C for benzene hydrogenation. During both reactions some initial decrease of catalytic activity which stabilized over 2-3 h was observed. The results show that roasting Re-containing reforming catalysts at fairly high temperatures (500-550 C) balances maximum hydrogenating and average splitting activities, thus guaranteeing high resistance to coke deposition while preserving the necessary selectivity. The decreased hydrogenating capacity of Ir/A1 2 0 3 0 and (Pt + Ir)/A1 23 0 catalysts after roasting at 500 C indicates insufficient thermal stability, which can be why renewing the initial activity of iridium containing forming catalysts by oxidating regeneration is difficult

Quantification of zinc atoms in a surface alloy on copper in an industrial-type methanol synthesis catalyst

DEFF Research Database (Denmark)

Kuld, Sebastian; Moses, Poul Georg; Sehested, Jens

2014-01-01

Methanol has recently attracted renewed interest because of its potential importance as a solar fuel. Methanol is also an important bulk chemical that is most efficiently formed over the industrial Cu/ZnO/Al2O3 catalyst. The identity of the active site and, in particular, the role of ZnO as a pro......Methanol has recently attracted renewed interest because of its potential importance as a solar fuel. Methanol is also an important bulk chemical that is most efficiently formed over the industrial Cu/ZnO/Al2O3 catalyst. The identity of the active site and, in particular, the role of Zn......O as a promoter for this type of catalyst is still under intense debate. Structural changes that are strongly dependent on the pretreatment method have now been observed for an industrial-type methanol synthesis catalyst. A combination of chemisorption, reaction, and spectroscopic techniques provides a consistent...

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

Science.gov (United States)

Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

2016-12-01

One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

Allotropic Carbon Nanoforms as Advanced Metal-Free Catalysts or as Supports

Directory of Open Access Journals (Sweden)

Hermenegildo Garcia

2014-01-01

Full Text Available This perspective paper summarizes the use of three nanostructured carbon allotropes as metal-free catalysts (“carbocatalysts” or as supports of metal nanoparticles. After an introductory section commenting the interest of developing metal-free catalysts and main features of carbon nanoforms, the main body of this paper is focused on exemplifying the opportunities that carbon nanotubes, graphene, and diamond nanoparticles offer to develop advanced catalysts having active sites based on carbon in the absence of transition metals or as large area supports with special morphology and unique properties. The final section provides my personal view on future developments in this field.

Catalytic activity and effect of modifiers on Ni-based catalysts for the dry reforming of methane

Energy Technology Data Exchange (ETDEWEB)

Barroso-Quiroga, Maria Martha; Castro-Luna, Adolfo Eduardo [Facultad de Ingenieria y Ciencias Economico-Sociales INTEQUI-CONICET-UNSL, Av. 25 de Mayo 384 (5730) Villa Mercedes (S.L.) (Argentina)

2010-06-15

Ni catalysts supported on different ceramic oxides (Al{sub 2}O{sub 3}, CeO{sub 2}, La{sub 2}O{sub 3}, ZrO{sub 2}) were prepared by wet impregnation. The catalytic behavior toward hydrogen production through the dry reforming of methane using a fixed-bed reactor was evaluated under certain experimental conditions, and the catalyst supported on ZrO{sub 2} showed the highest stable activity during the period of time studied. The catalyst supported on CeO{sub 2} has a relatively good activity, but shows signs of deactivation after a certain time during the reaction. This catalyst was chosen to be studied after the addition of 0.5 wt% Li and K as activity modifiers. The introduction of the alkaline metals produces a reduction of the catalytic activity but a better stability over the reactant conversion time. The reverse water-gas shift reaction influences the global system of reactions, and as the results indicate, should be considered near equilibrium. (author)

Does Pelletizing Catalysts Influence the Efficiency Number of Activity Measurements? Spectrochemical Engineering Considerations for an Accurate Operando Study

DEFF Research Database (Denmark)

Rasmussen, Søren Birk; Perez-Ferreras, Susana; Banares, Miguel A.

2013-01-01

of, for example, support oxides might take place, which in turn affects the pore size distribution and the porosity of the catalyst, leading to the observation of lower activity values due to decreased catalyst efficiency. This phenomenon can also apply to conventional activity measurements......, in the cases that pelletizing and recrushing of samples are performed to obtain adequate particle size fractions for the catalytic bed. A case study of an operand investigation of a V2O3-WO3/TiO2-sepiolite catalyst is used as an example, and simple calculations of the influence of catalyst activity...... and internal pore diffusion properties are considered in this paper for the evaluation of catalyst performance in, for example, operando reactors. Thus, it is demonstrated that with a pelletizing pressure of...

Final Technical Report: Metal—Organic Surface Catalyst for Low-temperature Methane Oxidation: Bi-functional Union of Metal—Organic Complex and Chemically Complementary Surface

Energy Technology Data Exchange (ETDEWEB)

Tait, Steven L. [Indiana Univ., Bloomington, IN (United States)

2016-10-01

Stabilization and chemical control of transition metal centers is a critical problem in the advancement of heterogeneous catalysts to next-generation catalysts that exhibit high levels of selectivity, while maintaining strong activity and facile catalyst recycling. Supported metal nanoparticle catalysts typically suffer from having a wide range of metal sites with different coordination numbers and varying chemistry. This project is exploring new possibilities in catalysis by combining features of homogeneous catalysts with those of heterogeneous catalysts to develop new, bi-functional systems. The systems are more complex than traditional heterogeneous catalysts in that they utilize sequential active sites to accomplish the desired overall reaction. The interaction of metal—organic catalysts with surface supports and their interactions with reactants to enable the catalysis of critical reactions at lower temperatures are at the focus of this study. Our work targets key fundamental chemistry problems. How do the metal—organic complexes interact with the surface? Can those metal center sites be tuned for selectivity and activity as they are in the homogeneous system by ligand design? What steps are necessary to enable a cooperative chemistry to occur and open opportunities for bi-functional catalyst systems? Study of these systems will develop the concept of bringing together the advantages of heterogeneous catalysis with those of homogeneous catalysis, and take this a step further by pursuing the objective of a bi-functional system. The use of metal-organic complexes in surface catalysts is therefore of interest to create well-defined and highly regular single-site centers. While these are not likely to be stable in the high temperature environments (> 300 °C) typical of industrial heterogeneous catalysts, they could be applied in moderate temperature reactions (100-300 °C), made feasible by lowering reaction temperatures by better catalyst control. They also

Widely available active sites on Ni2P for electrochemical hydrogen evolution - insights from first principles calculations

DEFF Research Database (Denmark)

Hansen, Martin Hangaard; Stern, Lucas-Alexandre; Feng, Ligang

2015-01-01

We present insights into the mechanism and the active site for hydrogen evolution on nickel phosphide (Ni2P). Ni2P was recently discovered to be a very active non-precious hydrogen evolution catalyst. Current literature attributes the activity of Ni2P to a particular site on the (0001) facet....... In the present study, using Density Functional Theory (DFT) calculations, we show that several widely available low index crystal facets on Ni2P have better properties for a high catalytic activity. DFT calculations were used to identify moderately bonding nickel bridge sites and nickel hollow sites for hydrogen...... adsorption and to calculate barriers for the Tafel pathway. The investigated surfaces in this study were the (10 (1) over bar0), ((1) over bar(1) over bar 20), (11 (2) over bar0), (11 (2) over bar1) and (0001) facets of the hexagonal Ni2P crystal. In addition to the DFT results, we present experiments on Ni2...

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

Science.gov (United States)

González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

2016-08-01

A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Phosphorylated mesoporous carbon as effective catalyst for the selective fructose dehydration to HMF

Energy Technology Data Exchange (ETDEWEB)

Villa, Alberto [Universita di Milano, Italy; Schiavoni, Marco [University of Milan and INFN, Milano, Italy; Fulvio, Pasquale F [ORNL; Mahurin, Shannon Mark [ORNL; Dai, Sheng [ORNL; Mayes, Richard T [ORNL; Veith, Gabriel M [ORNL; Prati, Laura [Universita di Milano, Italy

2013-01-01

Phosphorylated mesoporous carbons (PMCs) have been synthesized using an already reported one pot methodology. These materials have been applied as acidic catalysts in the dehydration of fructose to hydroxymethylfurfural (HMF). PMCs showed better selectivity to HMF compared to sulfonated carbon catalyst (SC) despite lower activity. The concentration of P-O groups correlates to the activity/selectivity of the catalysts; the higher the P-O concentration the higher the activity. However, the higher the P-O content the lower the selectivity to HMF. Indeed a lower concentration of the P-O groups (and even the acidic groups) minimized the degradation of HMF to levulinic acid and the formation of by-products, such as humines. Stability tests showed that these systems deactivate due to the formation of humines, water insoluble by-products derived from the dehydration of fructose, blocking the active site of the catalyst. Increasing the amount of P-O groups, higher amount of humines are formed; therefore carbons containing lower amount of phosphorylated groups, such as P/N-0.25, are less prone to deactivation. Keywords: Phosphorylated mesoporous carbons; fructose dehydration; HMF

Nature of active vanadium nanospecies in MCM-41 type catalysts for olefins oxidation

Energy Technology Data Exchange (ETDEWEB)

Chanquía, Corina M., E-mail: cchanquia@cab.cnea.gov.ar [Centro Atómico Bariloche, Comisión Nacional de Energía Atómica (CAB-CNEA). Av. Bustillo 9500, R8402AGP, San Carlos de Bariloche, Río Negro (Argentina); Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Avenida Rivadavia 1917, C1033AAJ, Ciudad Autónoma de Buenos Aires (Argentina); Cánepa, Analía L. [Centro de Investigación y Tecnología Química (CITeQ), Universidad Tecnológica Nacional, Facultad Regional Córdoba (UTN-FRC), Maestro López esq. Cruz Roja Argentina, Ciudad Universitaria, 5016, Córdoba Capital (Argentina); Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Avenida Rivadavia 1917, C1033AAJ, Ciudad Autónoma de Buenos Aires (Argentina); Winkler, Elin L. [Centro Atómico Bariloche, Comisión Nacional de Energía Atómica (CAB-CNEA). Av. Bustillo 9500, R8402AGP, San Carlos de Bariloche, Río Negro (Argentina); Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Avenida Rivadavia 1917, C1033AAJ, Ciudad Autónoma de Buenos Aires (Argentina); and others

2016-06-01

A multi-technique physicochemical investigation including UV–Vis-DRS, Raman spectroscopy, XPS, ESR and FTIRS with pyridine adsorption was performed to analyze the nature of different vanadium nanospecies present on MCM-41 type catalysts. By employing a direct hydrothermal synthesis, vanadium species were incorporated into siliceous structure mainly as tetrahedrally coordinated isolated V{sup δ+} ions, which would be located inside the wall and on the wall surface of the mesoporous channels. The coexistence of both vanadium oxidation states V{sup 4+} and V{sup 5+} was also revealed. Acidity measurements permitted to infer about the majority presence of Lewis acid sites, which increase with vanadium content. The catalytic performance of these materials was evaluated in the reaction of α-pinene oxidation with H{sub 2}O{sub 2}. The highest intrinsic activity of the sample with lower V loading was attributed to the high dispersion and efficiency of the isolated V{sup δ+} species that actuate as active sites. A mixture of reaction products arising from competitive processes of epoxidation and allylic oxidation was found. - Highlights: • Nature of vanadium nanospecies in mesoporous silicates was investigated. • From hydrothermal sol–gel synthesis, isolated V{sup δ+} sites were mainly generated. • The coexistence of both vanadium oxidation states V{sup 4+} and V{sup 5+} was revealed. • The catalytic performance was evaluated in α-pinene oxidation with H{sub 2}O{sub 2}. • The high catalytic activity is attributed to high dispersion of isolated V{sup δ+} ions.

Active groups for oxidative activation of C-H bond in C{sub 2}-C{sub 5} paraffins on V-P-O catalysts

Energy Technology Data Exchange (ETDEWEB)

Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

1998-12-31

For the first time in scientific literature, in our joint work with Dr. G. Ladwig in 1978 it was established phase portraite of the oxide vanadium-phosphorus system within wide range of P/V ratios from 0.5 to 3.2. Some later those data were confirmed. By investigation of the properties of individual vanadium-phosphorus phases it was also shown that the active component of such catalysts in n-butane oxidation was vanadyl pyrophosphate phase (VO){sub 2}Pr{sub 2}O{sub 7}. From then the conclusion has been evidenced by numerous publications and at present it has been out of doubt practically all over the world. It was hypothized that the unique properties of (VO){sub 2}P{sub 2}O{sub 7} in the reaction of n-butane oxidation could be explained by the presence of paired vanadyl groups and nearness of the distances between neighbouring vanadyl pairs and that between the first and fourth carbon atoms in n-butane molecule. The molecule activation occured at the latter atoms by proton abstraction. A comparison of the results on n-butane and butenes oxidation over vanadyl pyrophosphate allowed to conclude that the paraffin oxidation did not take place due to the molecule dehydrogenation process at the first stage of its conversion. Up to now, more than 100 papers related to paraffins oxidation over vanadyl pyrophosphate and the physico-chemical properties of the catalyst have been published. The process of n-butane oxidation is realized in practice. But still, the question about the nature of active sites of the catalyst and the reaction mechanism remains open and provokes further investigations. The present paper deals with our opinion about the problem and the experimental results supporting it. (orig.)

Investigation of heterogeneous solid acid catalyst performance on low grade feedstocks for biodiesel production: A review

International Nuclear Information System (INIS)

Mansir, Nasar; Taufiq-Yap, Yun Hin; Rashid, Umer; Lokman, Ibrahim M.

2017-01-01

Highlights: • Solid acid catalysts are proficient to esterifying high free fatty acid feedstocks to biodiesel. • Heterogeneous catalysts have the advantage of easy separation and reusability. • Heterogeneous basic catalysts have limitations due to high FFA of low cost feedstocks. • Solid catalysts having acid and base sites reveal better catalyst for biodiesel production. - Abstract: The conventional fossil fuel reserves are continually declining worldwide and therefore posing greater challenges to the future of the energy sources. Biofuel alternatives were found promising to replace the diminishing fossil fuels. However, conversion of edible vegetable oils to biodiesel using homogeneous acids and base catalysts is now considered as indefensible for the future particularly due to food versus fuel competition and other environmental problems related to catalyst system and feedstock. This review has discussed the progression in research and growth related to heterogeneous catalysts used for biodiesel production for low grade feedstocks. The heterogeneous base catalysts have revealed effective way to produce biodiesel, but it has the limitation of being sensitive to high free fatty acid (FFA) or low grade feedstocks. Alternatively, solid acid catalysts are capable of converting the low grade feedstocks to biodiesel in the presence of active acid sites. The paper presents a comprehensive review towards the investigation of solid acid catalyst performance on low grade feedstock, their category, properties, advantages, limitations and possible remedy to their drawbacks for biodiesel production.

Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements.

Science.gov (United States)

Back, Seoin; Lim, Juhyung; Kim, Na-Young; Kim, Yong-Hyun; Jung, Yousung

2017-02-01

A single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown an unexpectedly high specific activity with a significant reduction in noble metal usage for CO oxidation, fuel cell and hydrogen evolution applications, although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory (DFT) calculations, we for the first time investigate the great potential of single atom catalysts for CO 2 electroreduction applications. In particular, we study a single transition metal atom anchored on defective graphene with single or double vacancies, denoted M@sv-Gr or M@dv-Gr, where M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh or Ru, as a CO 2 reduction catalyst. Many SACs are indeed shown to be highly selective for the CO 2 reduction reaction over a competitive H 2 evolution reaction due to favorable adsorption of carboxyl (*COOH) or formate (*OCHO) over hydrogen (*H) on the catalysts. On the basis of free energy profiles, we identified several promising candidate materials for different products; Ni@dv-Gr (limiting potential U L = -0.41 V) and Pt@dv-Gr (-0.27 V) for CH 3 OH production, and Os@dv-Gr (-0.52 V) and Ru@dv-Gr (-0.52 V) for CH 4 production. In particular, the Pt@dv-Gr catalyst shows remarkable reduction in the limiting potential for CH 3 OH production compared to any existing catalysts, synthesized or predicted. To understand the origin of the activity enhancement of SACs, we find that the lack of an atomic ensemble for adsorbate binding and the unique electronic structure of the single atom catalysts as well as orbital interaction play an important role, contributing to binding energies of SACs that deviate considerably from the conventional scaling relation of bulk transition metals.

Understanding the Performance and Stability of Supported Ni-Co-Based Catalysts in Phenol HDO

Directory of Open Access Journals (Sweden)

Thuan M. Huynh

2016-11-01

Full Text Available Performances of bimetallic catalysts (Ni-Co supported on different acidic carriers (HZSM-5, HBeta, HY, ZrO2 and corresponding monometallic Ni catalysts in aqueous phase hydrodeoxygenation of phenol were compared in batch and continuous flow modes. The results revealed that the support acidity plays an important role in deoxygenation as it mainly controls the oxygen-removing steps in the reaction network. At the same time, sufficient hydrothermal stability of a solid catalyst is essential. Batch experiments revealed 10Ni10Co/HZSM-5 to be the best-performing catalyst in terms of conversion and cyclohexane yield. Complementary continuous runs provided more insights into the relationship between catalyst structure, efficiency and stability. After 24 h on-stream, the catalyst still reveals 100% conversion and a slight loss (from 100% to 90% in liquid hydrocarbon selectivity. The observed alloy of Co with Ni increased dispersion and stability of Ni-active sites, and combination with HZSM-5 resulted in a well-balanced ratio of metal and acid sites which promoted all necessary steps in preferred pathways. This was proved by studies of fresh and spent catalysts using various characterization techniques (N2 physisorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscopy (TEM and infrared spectroscopy of adsorbed pyridine (pyr-IR.

The black rock series supported SCR catalyst for NO x removal.

Science.gov (United States)

Xie, Bin; Luo, Hang; Tang, Qing; Du, Jun; Liu, Zuohua; Tao, Changyuan

2017-09-01

Black rock series (BRS) is of great potential for their plenty of valued oxides which include vanadium, iron, alumina and silica oxides, etc. BRS was used for directly preparing of selective catalytic reduction (SCR) catalyst by modifying its surface texture with SiO 2 -TiO 2 sols and regulating its catalytic active constituents with V 2 O 5 and MoO 3 . Consequently, 90% NO removal ratio was obtained within 300-400 °C over the BRS-based catalyst. The structure and properties of the BRS-based catalyst were characterized by the techniques of N 2 adsorption-desorption, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), H 2 -temperature programmed reduction (H 2 -TPR), and NH 3 -temperature programmed desorption (NH 3 -TPD). The results revealed that the BRS-based catalyst possesses favorable properties for NO x removal, including highly dispersed active components, abundant surface-adsorbed oxygen O α , well redox property, and numerous Brønsted acid sites. Particularly, the BRS-based catalyst exhibited considerable anti-poisoning performance compared with commercial TiO 2 -based catalyst. The former catalyst shows a NO conversion surpassing 80% from 300 to 400 °C for potassium poisoning, and a durability of SO 2 and H 2 O exceeding 85% at temperatures from 300 to 450 °C.

In-line localized monitoring of catalyst activity in selective catalytic NO.sub.x reduction systems

Science.gov (United States)

Muzio, Lawrence J [Laguna Niguel, CA; Smith, Randall A [Huntington Beach, CA

2009-12-22

Localized catalyst activity in an SCR unit for controlling emissions from a boiler, power plant, or any facility that generates NO.sub.x-containing flue gases is monitored by one or more modules that operate on-line without disrupting the normal operation of the facility. Each module is positioned over a designated lateral area of one of the catalyst beds in the SCR unit, and supplies ammonia, urea, or other suitable reductant to the catalyst in the designated area at a rate that produces an excess of the reductant over NO.sub.x on a molar basis through the designated area. Sampling probes upstream and downstream of the designated area draw samples of the gas stream for NO.sub.x analysis, and the catalyst activity is determined from the difference in NO.sub.x levels between the two probes.

The amyloid architecture provides a scaffold for enzyme-like catalysts.

Science.gov (United States)

Al-Garawi, Z S; McIntosh, B A; Neill-Hall, D; Hatimy, A A; Sweet, S M; Bagley, M C; Serpell, L C

2017-08-03

Natural biological enzymes possess catalytic sites that are generally surrounded by a large three-dimensional scaffold. However, the proportion of the protein molecule that participates in the catalytic reaction is relatively small. The generation of artificial or miniature enzymes has long been a focus of research because enzyme mimetics can be produced with high activity at low cost. These enzymes aim to mimic the active sites without the additional architecture contributed by the protein chain. Previous work has shown that amyloidogenic peptides are able to self-assemble to create an active site that is capable of binding zinc and catalysing an esterase reaction. Here, we describe the structural characterisation of a set of designed peptides that form an amyloid-like architecture and reveal that their capability to mimic carbonic anhydrase and serve as enzyme-like catalysts is related to their ability to self-assemble. These amyloid fibril structures can bind the metal ion Zn 2+ via a three-dimensional arrangement of His residues created by the amyloid architecture. Our results suggest that the catalytic efficiency of amyloid-like assembly is not only zinc-dependent but also depends on an active centre created by the peptides which is, in turn, dependent on the ordered architecture. These fibrils have good esterase activity, and they may serve as good models for the evolution of modern-day enzymes. Furthermore, they may be useful in designing self-assembling fibrils for applications as metal ion catalysts. This study also demonstrates that the ligands surrounding the catalytic site affect the affinity of the zinc-binding site to bind the substrate contributing to the enzymatic activity of the assembled peptides.

Engineering catalytic activity via ion beam bombardment of catalyst supports for vertically aligned carbon nanotube growth

Science.gov (United States)

Islam, A. E.; Nikolaev, P.; Amama, P. B.; Zakharov, D.; Sargent, G.; Saber, S.; Huffman, D.; Erford, M.; Semiatin, S. L.; Stach, E. A.; Maruyama, B.

2015-09-01

Carbon nanotube growth depends on the catalytic activity of metal nanoparticles on alumina or silica supports. The control on catalytic activity is generally achieved by variations in water concentration, carbon feed, and sample placement on a few types of alumina or silica catalyst supports obtained via thin film deposition. We have recently expanded the choice of catalyst supports by engineering inactive substrates like c-cut sapphire via ion beam bombardment. The deterministic control on the structure and chemistry of catalyst supports obtained by tuning the degree of beam-induced damage have enabled better regulation of the activity of Fe catalysts only in the ion beam bombarded areas and hence enabled controllable super growth of carbon nanotubes. A wide range of surface characterization techniques were used to monitor the catalytically active surface engineered via ion beam bombardment. The proposed method offers a versatile way to control carbon nanotube growth in patterned areas and also enhances the current understanding of the growth process. With the right choice of water concentration, carbon feed and sample placement, engineered catalyst supports may extend the carbon nanotube growth yield to a level that is even higher than the ones reported here, and thus offers promising applications of carbon nanotubes in electronics, heat exchanger, and energy storage.

Stable amorphous georgeite as a precursor to a high-activity catalyst

DEFF Research Database (Denmark)

Kondrat, Simon A.; Smith, Paul J.; Wells, Peter P.

2016-01-01

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable-and hence little known and largely ignored-georgeite. The first three of these minerals are widely used as catalyst precursors...... for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient...

Alternative alkali resistant deNOx catalysts

DEFF Research Database (Denmark)

Putluru, Siva Sankar Reddy; Kristensen, Steffen Buus; Due-Hansen, Johannes

2012-01-01

by onepot sol–gel method. All catalysts were characterized by BET, XRPD and NH3-TPD. Initial SCR activities of 8 out of 9 catalysts showed higher NO conversion at least at one temperature in the temperature range 300–500 ◦C compared to the conventional V2O5-WO3/TiO2 catalyst. After potassium poisoning (100......Alternative alkali resistant deNOx catalysts were prepared using three different supports ZrO2, TiO2 and Mordenite zeolite. The majority of the catalysts were prepared by incipient wetness impregnation of a commercial support, with vanadium, copper or iron precursor, one catalyst was prepared......–130 µmol of K/g of catalyst) the relative drop in SCR activity and acidity was lower for all the alternative catalysts compared to the industrial V2O5-WO3/TiO2 catalyst. Furthermore, Cu/MOR and Nano-V2O5/Sul-TiO2 catalysts showed 8–16 times higher SCR activities than the conventional even after high...

Highly active self-immobilized FI-Zr catalysts in a PCP framework for ethylene polymerization.

Science.gov (United States)

Li, He; Xu, Bo; He, Jianghao; Liu, Xiaoming; Gao, Wei; Mu, Ying

2015-12-04

A series of zirconium-based porous coordination polymers (PCPs) containing FI catalysts in the frameworks have been developed and studied as catalysts for ethylene polymerization. These PCPs exhibit good catalytic activities and long life times, producing polyethylenes with high molecular weights and bimodal molecular weight distribution in the form of particles.

Sulphur poisoning of palladium catalysts used for methane combustion: Effect of the support

International Nuclear Information System (INIS)

Escandon, Lara S.; Ordonez, Salvador; Vega, Aurelio; Diez, Fernando V.

2008-01-01

Four different supported palladium catalysts (using alumina, silica, zirconia and titania as supports), prepared by incipient wetness impregnation, were tested as catalysts for methane oxidation in presence of sulphur dioxide. The catalyst supported on zirconia showed the best performance, whereas the silica-supported one showed the fastest deactivation. Temperature-programmed desorption experiments of the poisoned catalysts suggest that SO 2 adsorption capacity of the support plays a key role in the catalyst poisoning. In order to study the effect of promoters, expected to improve the thermal stability and thioresistance of the catalyst, commercial zirconia modified by yttrium and lantane was tested as supports. It was found that the presence of these promoters does not improve the performance of the zirconia-supported catalyst. A deactivation model - considering two different active sites (fresh and poisoning), pseudo-first order dependence on methane concentration and poisoning rate depending on sulphur concentration and fraction of non-poisoned palladium - was used for modelling the deactivation behaviour

Extended Catalyst Longevity Via Supercritical Isobutane Regeneration of a Partially Deactivated USY Alkylation Catalyst

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar; David N. Thompson; Kyle C. Burch; David J. Zalewski

2005-05-01

Off-line, in situ activity recovery of a partially deactivated USY zeolite catalyst used for isobutane/butene alkylation was examined in a continuous-flow reaction system employing supercritical isobutane. Catalyst samples were deactivated in a controlled manner by running them to either to a fixed butene conversion level of 95% or a fixed time on stream of three hours, and then exposing the catalyst to supercritical isobutane to restore activity. Activity recovery was determined by comparing alkylation activity before and after the regeneration step. Both single and multiple regenerations were performed. Use of a 95% butene conversion level criterion to terminate the reaction step afforded 86% activity recovery for a single regeneration and provided nine sequential reaction steps for the multiple regeneration studies. Employing a fixed 3 h time on stream criterion resulted in nearly complete activity recovery for a single regeneration, and 24 reaction steps were demonstrated in sequence for the multiple regeneration process, producing only minor product yield declines per step. This resulted in a 12-fold increase in catalyst longevity versus unregenerated catalyst.

Behaviour of Co-Mo-Al/sub 2/O/sub 3/ catalysts in the hydrogenation of phenols

Energy Technology Data Exchange (ETDEWEB)

Weigold, H.

1982-10-01

The activity of a number of ring alkyl-substituted phenols in the direct hydrodeoxygenation reaction (i.e. C-O bond scission without prior ring hydrogenation) in the presence of a commercial Co-Mo-Al/sub 2/O/sub 3/ catalyst has been investigated. The results indicate that the catalytically active site is stereochemically demanding. It is proposed that the phenol ring hydrogenation and the direct hydrodeoxygenation reaction proceed on the same catalytic site. The ease of the direct hydrodeoxygenation reaction is retarded mainly when transfer of the substrate hydroxyl group onto a co-ordinatively unsaturated metal site on the catalyst is inhibited. This occurs when the catalyst hydroxyl group receptor site is occupied by a co-ordinating ligand (poison) or when substituents on the substrate direct the phenolic hydroxyl group away from this metal site. The catalytic behaviour of Co-Mo-Al/sub 2/O/sub 3/ can be 'transformed' to resemble more closely that of Ni-Mo-Al/sub 2/O/sub 3/ (high reductive capacity) when the reaction medium contains both excess H/sub 2/S and a co-ordinating ligand. It is proposed that this 'transformed' species is of importance in hydrodenitrogenation reactions in an H/sub 2/S-rich environment.

Hierarchical Pd-Sn alloy nanosheet dendrites: an economical and highly active catalyst for ethanol electrooxidation.

Science.gov (United States)

Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren

2013-01-01

Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures.

Unravelling Site-Specific Photo-Reactions of Ethanol on Rutile TiO2(110)

Science.gov (United States)

Hansen, Jonas Ø.; Bebensee, Regine; Martinez, Umberto; Porsgaard, Soeren; Lira, Estephania; Wei, Yinying; Lammich, Lutz; Li, Zheshen; Idriss, Hicham; Besenbacher, Flemming; Hammer, Bjørk; Wendt, Stefan

2016-01-01

Finding the active sites of catalysts and photo-catalysts is crucial for an improved fundamental understanding and the development of efficient catalytic systems. Here we have studied the photo-activated dehydrogenation of ethanol on reduced and oxidized rutile TiO2(110) in ultrahigh vacuum conditions. Utilizing scanning tunnelling microscopy, various spectroscopic techniques and theoretical calculations we found that the photo-reaction proceeds most efficiently when the reactants are adsorbed on regular Ti surface sites, whereas species that are strongly adsorbed at surface defects such as O vacancies and step edges show little reaction under reducing conditions. We propose that regular Ti surface sites are the most active sites in photo-reactions on TiO2. PMID:26915303

CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

Science.gov (United States)

Gao, Doudou; Zhang, Yuhong; Zhou, Liqun; Yang, Kunzhou

2018-01-01

The catalysts containing Cu, Ni bi-metallic nanoparticles were successfully synthesized by in-situ reduction of Cu2+ and Ni2+ salts into the highly porous and hydrothermally stable metal-organic framework MIL-101 via a simple liquid impregnation method. When the total amount of loading metal is 3 × 10-4 mol, Cu2Ni1@MIL-101 catalyst shows higher catalytic activity comparing to CuxNiy@MIL-101 with different molar ratio of Cu and Ni (x, y = 0, 0.5, 1.5, 2, 2.5, 3). Cu2Ni1@MIL-101 catalyst has the highest catalytic activity comparing to mono-metallic Cu and Ni counterparts and pure bi-metallic CuNi nanoparticles in hydrolytic dehydrogeneration of ammonia borane (AB) at room temperature. Additionally, in the hydrolysis reaction, the Cu2Ni1@MIL- 101 catalyst possesses excellent catalytic performances, which exhibit highly catalytic activity with turn over frequency (TOF) value of 20.9 mol H2 min-1 Cu mol-1 and a very low activation energy value of 32.2 kJ mol-1. The excellent catalytic activity has been successfully achieved thanks to the strong bi-metallic synergistic effects, uniform distribution of nanoparticles and the bi-functional effects between CuNi nanoparticles and the host of MIL-101. Moreover, the catalyst also displays satisfied durable stability after five cycles for the hydrolytically releasing H2 from AB. The non-noble metal catalysts have broad prospects for commercial applications in the field of hydrogen-stored materials due to the low prices and excellent catalytic activity.

Catalysts for synthetic liquid fuels

Energy Technology Data Exchange (ETDEWEB)

Bruce, L.A.; Turney, T.W.

1987-12-01

Fischer-Tropsch catalysts have been designed, characterized and tested for the selective production of hydrocarbons suitable as synthetic liquid transport fuels from synthesis gas (i.e., by the reduction of carbon monoxide with hydrogen). It was found that hydrocarbons in the middle distillate range, or suitable for conversion to that range, could be produced over several of the new catalyst systems. The various catalysts examined included: (1) synthetic cobalt clays, mainly cobalt chlorites; (2) cobalt hydrotalcites; (3) ruthenium metal supported on rare earth oxides of high surface area; and (4) a novel promoted cobalt catalyst. Active and selective catalysts have been obtained, in each category. With the exception of the clays, reproducibility of catalyst performance has been good. Catalysts in groups 2 and 4 have exhibited very high activity, with long lifetimes and easy regeneration.

Improved hydrogen generation from alkaline NaBH{sub 4} solution using cobalt catalysts supported on modified activated carbon

Energy Technology Data Exchange (ETDEWEB)

Xu, Dongyan; Guo, Qingjie; Yue, Xuehai [College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Dai, Ping [College of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao 266061 (China)

2008-12-15

Hydrogen production from alkaline sodium borohydride (NaBH{sub 4}) solution via hydrolysis process over activated carbon supported cobalt catalysts is studied. Activated carbons are used in their original form and after liquid phase oxidation with HNO{sub 3}. The changes in surface functional groups of the activated carbon are detected by FTIR spectroscopy. The effects of HNO{sub 3} oxidation on the properties of the activated carbon and the resulting catalyst performance are investigated. FTIR analysis reveals that the oxidative treatment leads to the formation of various functional groups on the surface of the activated carbon. Cobalt catalysts supported on the modified activated carbon are found to exhibit higher activity and stability. (author)

Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

Science.gov (United States)

Yik, Edwin Shyn-Lo

The presence of heteroatoms (e.g. S, N) in crude oil poses formidable challenges in petroleum refining processes as a result of their irreversible binding on catalytically active sites at industrially relevant conditions. With increasing pressures from legislation that continues to lower the permissible levels of sulfur content in fuels, hydrodesulfurization (HDS), the aptly named reaction for removing heteroatoms from organosulfur compounds, has become an essential feedstock pretreatment step to remove deleterious species from affecting downstream processing. Extensive research in the area has identified the paradigm catalysts for desulfurization; MoSx or WSx, promoted with Co or Ni metal; however, despite the vast library of both empirical and fundamental studies, a clear understanding of site requirements, the elementary steps of C-S hydrogenolysis, and the properties that govern HDS reactivity and selectivity have been elusive. While such a lack of rigorous assessments has not prevented technological advancements in the field of HDS catalysis, fundamental interpretations can inform rational catalyst and process design, particularly in light of new requirements for "deep" desulfurization and in the absence of significant hydrotreatment catalyst developments in recent decades. We report HDS rates of thiophene, which belongs to a class of compounds that are most resistant to sulfur removal (i.e. substituted alkyldibenzothiophenes), over a range of industrially relevant temperatures and pressures, measured at differential conditions and therefore revealing their true kinetic origins. These rates, normalized by the number of exposed metal atoms, on various SiO 2-supported, monometallic transition metals (Re, Ru, Pt), range several orders of magnitude. Under relevant HDS conditions, Pt and Ru catalysts form a layer of chemisorbed sulfur on surfaces of a metallic bulk, challenging reports that assume the latter exists as its pyrite sulfide phase during reaction. While

Critical Surface Parameters for the Oxidative Coupling of Methane over the Mn-Na-W/SiO2 Catalyst.

Science.gov (United States)

Hayek, Naseem S; Lucas, Nishita S; Warwar Damouny, Christine; Gazit, Oz M

2017-11-22

The work here presents a thorough evaluation of the effect of Mn-Na-W/SiO 2 catalyst surface parameters on its performance in the oxidative coupling of methane (OCM). To do so, we used microporous dealuminated β-zeolite (Zeo), or mesoporous SBA-15 (SBA), or macroporous fumed silica (Fum) as precursors for catalyst preparation, together with Mn nitrate, Mn acetate and Na 2 WO 4 . Characterizing the catalysts by inductively coupled plasma-optical emission spectroscopy, N 2 physisorption, X-ray diffraction, high-resolution scanning electron microscopy-energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, and catalytic testing enabled us to identify critical surface parameters that govern the activity and C 2 selectivity of the Mn-Na-W/SiO 2 catalyst. Although the current paradigm views the phase transition of silica to α-cristobalite as the critical step in obtaining dispersed and stable metal sites, we show that the choice of precursors is equally or even more important with respect to tailoring the right surface properties. Specifically, the SBA-based catalyst, characterized by relatively closed surface porosity, demonstrated low activity and low C 2 selectivity. By contrast, for the same composition, the Zeo-based catalyst showed an open surface pore structure, which translated up to fourfold higher activity and enhanced selectivity. By varying the overall composition of the Zeo catalysts, we show that reducing the overall W concentration reduces the size of the Na 2 WO 4 species and increases the catalytic activity linearly as much as fivefold higher than the SBA catalyst. This linear dependence correlates well to the number of interfaces between the Na 2 WO 4 and Mn 2 O 3 species. Our results combined with prior studies lead us to single out the interface between Na 2 WO 4 and Mn 2 O 3 as the most probable active site for OCM using this catalyst. Synergistic interactions between the various precursors used and the phase transition are discussed in

Highly active Pd-In/mesoporous alumina catalyst for nitrate reduction.

Science.gov (United States)

Gao, Zhenwei; Zhang, Yonggang; Li, Deyi; Werth, Charles J; Zhang, Yalei; Zhou, Xuefei

2015-04-09

The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd-In/Al2O3 with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO2-buffered water and under continuous H2 as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd-In ratio of 4, with a first-order rate constant (k(obs) = 0.241 L min(-1) g(cata)(-1)) that was 1.3× higher than that of conventional Pd-In/Al2O3 (5 wt% Pd; 0.19 L min(-1) g(cata)(-1)). The Pd-In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate. Copyright © 2015 Elsevier B.V. All rights reserved.

Kaolin and commercial fcc catalysts in the cracking of loads of polypropylene under refinary conditions

Directory of Open Access Journals (Sweden)

A. M. Ribeiro

2013-12-01

Full Text Available The efficiency of Commercial FCC catalysts (low, medium and high activities was evaluated by the catalytic cracking process of combined feeds of polypropylene (PP and vaseline, using a microactivity test unit (M.A.T. for the production of fuel fractions (gasoline, diesel and residue. The PP/vaseline loads, at 2.0% and 4.0% wt, were processed under refinery conditions (load/catalyst ratio and temperature of process. For the PP/vaseline load (4.0% wt, the production of the gasoline fraction was favored by all catalysts, while the diesel fraction was favored by PP/vaseline load (2.0% wt, showing a preferential contact of the zeolite external surface with the end of the polymer chains for the occurrence of the catalytic cracking. All the loads produced a bigger quantity of the gaseous products in the presence of highly active commercial FCC catalyst. The improvement in the activity of the commercial FCC catalyst decreased the production of the liquid fractions and increased the quantity of the solid fractions, independent of the concentration of the loads. These results can be related to the difficulty of the polymer chains to access the catalyst acid sites, occurring preferentially end-chain scission at the external surface of the catalyst.

CO methanation over supported bimetallic Ni-Fe catalysts: From computational studies towards catalyst optimization

DEFF Research Database (Denmark)

Kustov, Arkadii; Frey, Anne Mette; Larsen, Kasper Emil

2007-01-01

with compositions 25Fe75Ni and 50Fe50Ni showed significantly better activity and in some cases also a higher selectivity to methane compared with the traditional monometallic Ni and Fe catalysts. A catalyst with composition 25Fe75Ni was found to be the most active in CO hydrogenation for the MgAl2O4 support at low...... metal loadings. At high metal concentrations, the maximum for the methanation activity was found for catalysts with composition 50Ni50Fe both on the MgAl2O4 and Al2O3 supports. This difference can be attributed to a higher reducibility of the constituting metals with increasing metal concentration......DFT calculations combined with a computational screening method have previously shown that bimetallic Ni-Fe alloys should be more active than the traditional Ni-based catalyst for CO methanation. That was confirmed experimentally for a number of bimetallic Ni-Fe catalysts supported on MgAl2O4. Here...

Autothermal reforming catalyst having perovskite structure

Science.gov (United States)

Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

2009-03-24

The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

Science.gov (United States)

Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

2018-01-01

Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

Ethanol-selective catalytic reduction of NO by Ag/Al2O3 catalysts: Activity and deactivation by alkali salts

DEFF Research Database (Denmark)

Schill, Leonhard; Putluru, Siva Sankar Reddy; Jacobsen, Casper Funk

2012-01-01

Ag/Al2O3 catalysts with and without potassium doping were prepared by incipient wetness impregnation and characterized by N2 physisorption, XRPD, NH3-TPD and SEM. The influence of the Ag content from 1 to 5 wt.% was investigated for the selective catalytic reduction (SCR) of NO with ethanol. The 3...... wt.% Ag/Al2O3 catalyst was found to be the most active and CO2 selective over a wide temperature window (300–500 ◦C). Addition of 500 ppm of H2 has a mild promotional effect on the activity while SO2 has a strong negative influence on the SCR activity. Furthermore, the Ag/Al2O3 ethanol-SCR catalyst......3 ethanol-SCR catalyst compared to the conventional NH3-SCR catalyst. The still low potassium resistance, in combination with the high sensitivity to SO2, seems not to make these catalysts a real option for biomass fired boilers....

Influence of liquid medium on the activity of a low-alpha Fischer-Tropsch catalyst

Energy Technology Data Exchange (ETDEWEB)

Gormley, R.J.; Zarochak, M.F.; Deffenbaugh, P.W.; Rao, K.R.P.M.

1995-12-31

The purpose of this research was to measure activity, selectivity, and the maintenance of these properties in slurry autoclave experiments with a Fischer-Tropsch (FT) catalyst that was used in the {open_quotes}FT II{close_quotes} bubble-column test, conducted at the Alternative Fuels Development Unit (AFDU) at LaPorte, Texas during May 1994. The catalyst contained iron, copper, and potassium and was formulated to produce mainly hydrocarbons in the gasoline range with lesser production of diesel-range products and wax. The probability of chain growth was thus deliberately kept low. Principal goals of the autoclave work have been to find the true activity of this catalyst in a stirred tank reactor, unhindered by heat or mass transfer effects, and to obtain a steady conversion and selectivity over the approximately 15 days of each test. Slurry autoclave testing of the catalyst in heavier waxes also allows insight into operation of larger slurry bubble column reactors. The stability of reactor operation in these experiments, particularly at loadings exceeding 20 weight %, suggests the likely stability of operations on a larger scale.

Esterification of Glycerol with Acetic Acid over Highly Active and Stable Alumina-based Catalysts: A Reaction Kinetics Study

OpenAIRE

Rane, S. A.; Pudi, S. M.; Biswas, P.

2016-01-01

The catalytic activity of Cu- or Ni monometallic and Cu-Ni bimetallic (Cu/Ni ratio = 3, 1, 0.33) catalysts supported on γ-Al2O3 and SO42–/γ-Al2O3 catalysts were evaluated for esterification of glycerol. The reactions were performed in a batch reactor under reflux at standard reaction conditions: temperature 110 °C, atmospheric pressure, glycerol to acetic acid molar ratio 1:9, and catalyst loading 0.25 g. The best catalytic activity was observed over 2 M SO42–/γ-Al2O3 catalyst, which showed t...

Design of Embedded Metal Catalysts via Reverser Micro-Emulsion System: a Way to Suppress Catalyst Deactivation by Metal Sintering

KAUST Repository

AlMana, Noor

2016-06-19

The development of highly selective and active, long-lasting, robust, low-cost and environmentally benign catalytic materials is the greatest challenge in the area of catalysis study. In this context, core-shell structures where the active sites are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between the core and shell may increases the activity and efficiency of the catalyst in catalytic reactions especially for oxide shells that exhibit redox properties such as TiO2 and CeO2. Moreover, coating oxide layer over metal nanoparticles (NPs) can be designed to provide porosity (micropore/mesopore) that gives selectivity of the various reactants by the different gas diffusion rates. In this thesis, we will discuss the concept of catalyst stabilization against metal sintering by a core-shell system. In particular we will study the mechanistic of forming core-shell particles and the key parameters that can influence the properties and morphology of the Pt metal particle core and SiO2 shell (Pt@SiO2) using the reverse micro-emulsion method. The Pt@SiO2 core-shell catalysts were investigated for low-temperature CO oxidation reaction. The study was further extended to other catalytic applications by varying the composition of the core as well as the chemical nature of the shell material. The Pt NPs were embedded within another oxide matrix such as ZrO2 and TiO2 for CO oxidation reaction. These materials were studied in details to identify the factors governing the coating of the oxide around the metal NPs. Next, a more challenging system, namely, bimetallic Ni9Pt NPs embedded in TiO2 and ZrO2 matrix were investigated for dry reforming of methane reaction at high temperatures. The challenges of designing Ni9Pt@oxide core-shell structure with TiO2 and ZrO2 and their tolerance

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

International Nuclear Information System (INIS)

González, J.; Chen, L.F.; Wang, J.A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J.L.

2016-01-01

Highlights: • Oxidative desulfurization of model diesel was tested in a biphasic system. • ODS activity was proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts. • Lewis acidity was related to vanadium content and catalytic activity. • 99.9% DBT was oxidized using 25%V 2 O 5 /Ti-MCM-41 at 60 °C within 60 min. - Abstract: A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H 2 O 2 as oxidant. ODS activity was found to be proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts, indicating that the surface vanadium pentoxide (V 2 O 5 ) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V 2 O 5 ) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V 2 O 5 /Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti-Stabilized MnO2

DEFF Research Database (Denmark)

Frydendal, Rasmus; Paoli, Elisa Antares; Chorkendorff, Ib

2015-01-01

Catalysts are required for the oxygen evolution reaction, which are abundant, active, and stable in acid. MnO2 is a promising candidate material for this purpose. However, it dissolves at high overpotentials. Using first-principles calculations, a strategy to mitigate this problem by decorating...... undercoordinated surface sites of MnO2 with a stable oxide is developed here. TiO2 stands out as the most promising of the different oxides in the simulations. This prediction is experimentally verified by testing sputter-deposited thin films of MnO2 and Ti-MnO2. A combination of electrochemical measurements...

Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

Directory of Open Access Journals (Sweden)

Paul P. Kelly

2015-09-01

Full Text Available Cytochrome P450 monooxygenases are useful biocatalysts for C–H activation, and there is a need to expand the range of these enzymes beyond what is naturally available. A panel of 93 variants of active self-sufficient P450cam[Tyr96Phe]-RhFRed fusion enzymes with a broad diversity in active site amino acids was developed by screening a large mutant library of 16,500 clones using a simple, highly sensitive colony-based colorimetric screen against indole. These mutants showed distinct fingerprints of activity not only when screened in oxidations of substituted indoles but also for unrelated oxidations such as benzylic hydroxylations.