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Sample records for active catalyst sites

  1. Characterization of active sites in zeolite catalysts

    SciTech Connect

    Eckert, J.; Bug, A.; Nicol, J.M.

    1997-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Atomic-level details of the interaction of adsorbed molecules with active sites in catalysts are urgently needed to facilitate development of more effective and/or environmentally benign catalysts. To this end the authors have carried out neutron scattering studies combined with theoretical calculations of the dynamics of small molecules inside the cavities of zeolite catalysts. The authors have developed the use of H{sub 2} as a probe of adsorption sites by observing the hindered rotations of the adsorbed H{sub 2} molecule, and they were able to show that an area near the four-rings is the most likely adsorption site for H{sub 2} in zeolite A while adsorption of H{sub 2} near cations located on six-ring sites decreases in strength as Ni {approximately} Co > Ca > Zn {approximately} Na. Vibrational and rotational motions of ethylene and cyclopropane adsorption complexes were used as a measure for zeolite-adsorbate interactions. Preliminary studies of the binding of water, ammonia, and methylamines were carried out in a number of related guest-host materials.

  2. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts

    PubMed Central

    Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian; Zhang, Yuanjian; Thomas, Arne; Reier, Tobias; Paraknowitsch, Jens-Peter; Strasser, Peter

    2015-01-01

    Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and 57Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity. PMID:26486465

  3. The calculation of surface orbital energies for specific types of active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.; Cole, F.

    1992-11-01

    An angular overlap calculation has been used to determine the s, p, and d orbital energy levels of the different types of surface sites present on dispersed metal catalysts. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  4. The calculation of surface orbital energies for specific types of active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.; Cole, F.

    1992-01-01

    An angular overlap calculation has been used to determine the s, p, and d orbital energy levels of the different types of surface sites present on dispersed metal catalysts. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  5. Computational approaches to the determination of active site structures and reaction mechanisms in heterogeneous catalysts.

    PubMed

    Catlow, C R A; French, S A; Sokol, A A; Thomas, J M

    2005-04-15

    We apply quantum chemical methods to the study of active site structures and reaction mechanisms in mesoporous silica and metal oxide catalysts. Our approach is based on the use of both molecular cluster and embedded cluster (QM/MM) techniques, where the active site and molecular complex are described using density functional theory (DFT) and the embedding matrix simulated by shell model potentials. We consider three case studies: alkene epoxidation over the microporous TS-1 catalyst; methanol synthesis on ZnO and Cu/ZnO and C-H bond activation over Li-doped MgO.

  6. Computational approaches to the determination of active site structures and reaction mechanisms in heterogeneous catalysts.

    PubMed

    Catlow, C R A; French, S A; Sokol, A A; Thomas, J M

    2005-04-15

    We apply quantum chemical methods to the study of active site structures and reaction mechanisms in mesoporous silica and metal oxide catalysts. Our approach is based on the use of both molecular cluster and embedded cluster (QM/MM) techniques, where the active site and molecular complex are described using density functional theory (DFT) and the embedding matrix simulated by shell model potentials. We consider three case studies: alkene epoxidation over the microporous TS-1 catalyst; methanol synthesis on ZnO and Cu/ZnO and C-H bond activation over Li-doped MgO. PMID:15901543

  7. Active sites and mechanisms for direct oxidation of benzene to phenol over carbon catalysts.

    PubMed

    Wen, Guodong; Wu, Shuchang; Li, Bo; Dai, Chunli; Su, Dang Sheng

    2015-03-23

    The direct oxidation of benzene to phenol with H2 O2 as the oxidizer, which is regarded as an environmentally friendly process, can be efficiently catalyzed by carbon catalysts. However, the detailed roles of carbon catalysts, especially what is the active site, are still a topic of debate controversy. Herein, we present a fundamental consideration of possible mechanisms for this oxidation reaction by using small molecular model catalysts, Raman spectra, static secondary ion mass spectroscopy (SIMS), DFT calculations, quasi in situ ATR-IR and UV spectra. Our study indicates that the defects, being favorable for the formation of active oxygen species, are the active sites for this oxidation reaction. Furthermore, one type of active defect, namely the armchair configuration defect was successfully identified.

  8. Catalyst activator

    DOEpatents

    McAdon, Mark H.; Nickias, Peter N.; Marks, Tobin J.; Schwartz, David J.

    2001-01-01

    A catalyst activator particularly adapted for use in the activation of metal complexes of metals of Group 3-10 for polymerization of ethylenically unsaturated polymerizable monomers, especially olefins, comprising two Group 13 metal or metalloid atoms and a ligand structure including at least one bridging group connecting ligands on the two Group 13 metal or metalloid atoms.

  9. ZrO2 -Based Alternatives to Conventional Propane Dehydrogenation Catalysts: Active Sites, Design, and Performance.

    PubMed

    Otroshchenko, Tatyana; Sokolov, Sergey; Stoyanova, Mariana; Kondratenko, Vita A; Rodemerck, Uwe; Linke, David; Kondratenko, Evgenii V

    2015-12-21

    Non-oxidative dehydrogenation of propane to propene is an established large-scale process that, however, faces challenges, particularly in catalyst development; these are the toxicity of chromium compounds, high cost of platinum, and catalyst durability. Herein, we describe the design of unconventional catalysts based on bulk materials with a certain defect structure, for example, ZrO2 promoted with other metal oxides. Comprehensive characterization supports the hypothesis that coordinatively unsaturated Zr cations are the active sites for propane dehydrogenation. Their concentration can be adjusted by varying the kind of ZrO2 promoter and/or supporting tiny amounts of hydrogenation-active metal. Accordingly designed Cu(0.05 wt %)/ZrO2 -La2 O3 showed industrially relevant activity and durability over ca. 240 h on stream in a series of 60 dehydrogenation and oxidative regeneration cycles between 550 and 625 °C. PMID:26566072

  10. Active Site Dependent Reaction Mechanism over Ru/CeO2 Catalyst toward CO2 Methanation.

    PubMed

    Wang, Fei; He, Shan; Chen, Hao; Wang, Bin; Zheng, Lirong; Wei, Min; Evans, David G; Duan, Xue

    2016-05-18

    Oxygen vacancy on the surface of metal oxides is one of the most important defects which acts as the reactive site in a variety of catalytic reactions. In this work, operando spectroscopy methodology was employed to study the CO2 methanation reaction catalyzed by Ru/CeO2 (with oxygen vacancy in CeO2) and Ru/α-Al2O3 (without oxygen vacancy), respectively, so as to give a thorough understanding on active site dependent reaction mechanism. In Ru/CeO2 catalyst, operando XANES, IR, and Raman were used to reveal the generation process of Ce(3+), surface hydroxyl, and oxygen vacancy as well as their structural evolvements under practical reaction conditions. The steady-state isotope transient kinetic analysis (SSITKA)-type in situ DRIFT infrared spectroscopy undoubtedly substantiates that CO2 methanation undergoes formate route over Ru/CeO2 catalyst, and the formate dissociation to methanol catalyzed by oxygen vacancy is the rate-determining step. In contrast, CO2 methanation undergoes CO route over Ru surface in Ru/α-Al2O3 with the absence of oxygen vacancy, demonstrating active site dependent catalytic mechanism toward CO2 methanation. In addition, the catalytic activity evaluation and the oscillating reaction over Ru/CeO2 catalyst further prove that the oxygen vacancy catalyzes the rate-determining step with a much lower activation temperature compared with Ru surface in Ru/α-Al2O3 (125 vs 250 °C).

  11. Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts.

    PubMed

    Wang, Lu-Cun; Friend, C M; Fushimi, Rebecca; Madix, Robert J

    2016-07-01

    The activation of molecular O2 as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O2 activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O2 dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O2 dissociation is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O2 dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction. PMID:27376884

  12. Active Site Dependent Reaction Mechanism over Ru/CeO2 Catalyst toward CO2 Methanation.

    PubMed

    Wang, Fei; He, Shan; Chen, Hao; Wang, Bin; Zheng, Lirong; Wei, Min; Evans, David G; Duan, Xue

    2016-05-18

    Oxygen vacancy on the surface of metal oxides is one of the most important defects which acts as the reactive site in a variety of catalytic reactions. In this work, operando spectroscopy methodology was employed to study the CO2 methanation reaction catalyzed by Ru/CeO2 (with oxygen vacancy in CeO2) and Ru/α-Al2O3 (without oxygen vacancy), respectively, so as to give a thorough understanding on active site dependent reaction mechanism. In Ru/CeO2 catalyst, operando XANES, IR, and Raman were used to reveal the generation process of Ce(3+), surface hydroxyl, and oxygen vacancy as well as their structural evolvements under practical reaction conditions. The steady-state isotope transient kinetic analysis (SSITKA)-type in situ DRIFT infrared spectroscopy undoubtedly substantiates that CO2 methanation undergoes formate route over Ru/CeO2 catalyst, and the formate dissociation to methanol catalyzed by oxygen vacancy is the rate-determining step. In contrast, CO2 methanation undergoes CO route over Ru surface in Ru/α-Al2O3 with the absence of oxygen vacancy, demonstrating active site dependent catalytic mechanism toward CO2 methanation. In addition, the catalytic activity evaluation and the oscillating reaction over Ru/CeO2 catalyst further prove that the oxygen vacancy catalyzes the rate-determining step with a much lower activation temperature compared with Ru surface in Ru/α-Al2O3 (125 vs 250 °C). PMID:27135417

  13. Hydrogenation of biofuels with formic acid over a palladium-based ternary catalyst with two types of active sites.

    PubMed

    Wang, Liang; Zhang, Bingsen; Meng, Xiangju; Su, Dang Sheng; Xiao, Feng-Shou

    2014-06-01

    A composite catalyst including palladium nanoparticles on titania (TiO2) and on nitrogen-modified porous carbon (Pd/TiO2@N-C) is synthesized from palladium salts, tetrabutyl titanate, and chitosan. N2 sorption isotherms show that the catalyst has a high BET surface area (229 m(2)  g(-1)) and large porosity. XPS and TEM characterization of the catalyst shows that palladium species with different chemical states are well dispersed across the TiO2 and nitrogen-modified porous carbon, respectively. The Pd/TiO2@N-C catalyst is very active and shows excellent stability towards hydrogenation of vanillin to 2-methoxy-4-methylphenol using formic acid as hydrogen source. This activity can be attributed to a synergistic effect between the Pd/TiO2 (a catalyst for dehydrogenation of formic acid) and Pd/N-C (a catalyst for hydrogenation of vanillin) sites.

  14. Counting Active Sites on Titanium Oxide-Silica Catalysts for Hydrogen Peroxide Activation through In Situ Poisoning with Phenylphosphonic Acid

    SciTech Connect

    Eaton, Todd R.; Boston, Andrew M.; Thompson, Anthony B.; Gray, Kimberly A.; Notestein, Justin M.

    2015-06-04

    Quantifying specific active sites in supported catalysts improves our understanding and assists in rational design. Supported oxides can undergo significant structural changes as surface densities increase from site-isolated cations to monolayers and crystallites, which changes the number of kinetically relevant sites. Herein, TiOx domains are titrated on TiOx–SiO2 selectively with phenylphosphonic acid (PPA). An ex situ method quantifies all fluid-accessible TiOx, whereas an in situ titration during cis-cyclooctene epoxidation provides previously unavailable values for the number of tetrahedral Ti sites on which H2O2 activation occurs. We use this method to determine the active site densities of 22 different catalysts with different synthesis methods, loadings, and characteristic spectra and find a single intrinsic turnover frequency for cis-cyclooctene epoxidation of (40±7) h-1. This simple method gives molecular-level insight into catalyst structure that is otherwise hidden when bulk techniques are used.

  15. A Frontier Molecular Orbital determination of the active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.

    1992-11-01

    An angular overlap calculation has been used to determine the s, p and d orbital energy levels of the different types of surface sites present on a dispersed metal catalysts. The basis for these calculations is the reported finding that a large number of catalyzed reactions take place on single atom active sites on the metal surface. Thus, these sites can be considered as surface complexes made up of the central active atom surrounded by near-neighbor metal atom ``ligands`` with localized surface orbitals perturbed only by these ``ligands``. These ``complexes`` are based on a twelve coordinate species with the ``ligands`` attached to the t{sub 2g} orbitals and the coordinate axes coincident with the direction of the e{sub g} orbitals on the central atom. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  16. A Frontier Molecular Orbital determination of the active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.

    1992-01-01

    An angular overlap calculation has been used to determine the s, p and d orbital energy levels of the different types of surface sites present on a dispersed metal catalysts. The basis for these calculations is the reported finding that a large number of catalyzed reactions take place on single atom active sites on the metal surface. Thus, these sites can be considered as surface complexes made up of the central active atom surrounded by near-neighbor metal atom ligands'' with localized surface orbitals perturbed only by these ligands''. These complexes'' are based on a twelve coordinate species with the ligands'' attached to the t{sub 2g} orbitals and the coordinate axes coincident with the direction of the e{sub g} orbitals on the central atom. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  17. Active sites and mechanisms for H2O2 decomposition over Pd catalysts

    PubMed Central

    Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

    2016-01-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  18. Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Wang, Ziyun; Liu, Xinyi; Rooney, D. W.; Hu, P.

    2015-10-01

    The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

  19. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis.

    PubMed

    Pucino, Margherita; Mougel, Victor; Schowner, Roman; Fedorov, Alexey; Buchmeiser, Michael R; Copéret, Christophe

    2016-03-18

    Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong σ-donating N-heterocyclic carbene ligands with weak σ-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(OTf)] and [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(+) ][B(Ar(F) )4 (-) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar(F) )4 =B(3,5-(CF3 )2 C6 H3 )4 ] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene.

  20. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis.

    PubMed

    Pucino, Margherita; Mougel, Victor; Schowner, Roman; Fedorov, Alexey; Buchmeiser, Michael R; Copéret, Christophe

    2016-03-18

    Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong σ-donating N-heterocyclic carbene ligands with weak σ-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(OTf)] and [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(+) ][B(Ar(F) )4 (-) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar(F) )4 =B(3,5-(CF3 )2 C6 H3 )4 ] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene. PMID:26928967

  1. Selectivity loss of Pt/CeO{sub 2} PROX catalysts at low CO concentrations: mechanism and active site study.

    SciTech Connect

    Polster, C. S.; Zhang, R.; Cyb, M. T.; Miller, J. T.; Baertsch, C. D.

    2010-07-01

    CO and H{sub 2} oxidation were studied over a series of Pt/CeO{sub 2} catalysts with differing Pt loadings and dispersions. Kinetic rate analysis confirms the presence of dual Langmuir-Hinshelwood (L-H) and Mars and van Krevelen (M-vK) pathways and is used to explain the loss in CO oxidation selectivity at low CO concentrations. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) shows the strong CO coverage dependence on both CO and O{sub 2} concentrations and explains the transition from L-H to M-vK reaction character. Redox site measurements are performed on Pt/CeO{sub 2} catalysts by anaerobic titrations under conditions where the M-vK pathway dominates the reaction rate. Similar redox site densities per interfacial Pt atom suggest that interfacial Pt-O-Ce sites are responsible for M-vK redox activity.

  2. Effect of Mo on the active sites of VPO catalysts upon the selective oxidation of n-butane

    SciTech Connect

    Irusta, S.; Boix, A.; Pierini, B.; Caspani, C.; Petunchi, J.

    1999-10-25

    The effect of the addition of Mo to VPO formulations on the physiochemical and catalytic properties of VPO solids was studied using X-ray diffraction (XRD), Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, Laser Raman spectroscopy (LRS), temperature-programmed reduction, and a flow reactor system. The addition of Mo to the oxides increases the activity and selectivity of the VPO catalysts. The promoting effect is a function of both the Mo loading and the way such cation was added to the VPO matrix. The best catalyst was obtained when 1% Mo was impregnated on the NOHPO{sub 4}-0.5H{sub 2}O phase. At 400 C 36% of molar yield to maleic anhydride was obtained in this catalyst against 12% of the unpromoted catalysts and only 3% of the solids where Mo was added during the phosphatation step. The impregnated 1% Mo catalyst achieved a molar yield of 50% after 700 h under reaction stream (equilibrated catalysts). (VO){sub 2}P{sub 2}O{sub 7} was the only phase detected by XRD and LRS in all the catalysts studied. They showed comparable BET surface areas and crystallinity after 400 h under reaction conditions. A local order distortion of the O{sub 3}-P-O-P-O{sub 3} structure was detected by LRS in the impregnated Mo VPO catalysts. After 400 h on stream, both promoted and unpromoted solids only showed V{sup IV} on the surface layer. The main effect on the addition of Mo by impregnation to VPO oxides was enhanced by the very strong Lewis acid sites and the liability of the oxygen of (VO){sub 2}P{sub 2}O{sub 7}. This suggests that the promoting effect is more electronic in nature than structural. Polymeric MO{sub 3} species were detected neither by TPR nor by LRS. All the promoted catalysts presented a surface molybdenum enrichment but whereas the coprecipitated Mo VPO solid only shows surface Mo{sup VI}, both Mo{sup VI} coexist in the impregnated catalyst.

  3. Linking structure to function: The search for active sites in non-platinum group metal oxygen reduction reaction catalysts

    DOE PAGES

    Holby, Edward F.; Zelenay, Piotr

    2016-05-17

    Atomic-scale structures of oxygen reduction reaction (ORR) active sites in non-platinum group metal (non-PGM) catalysts, made from pyrolysis of carbon, nitrogen, and transition-metal (TM) precursors have been the subject of continuing discussion in the fuel cell electrocatalysis research community. We found that quantum chemical modeling is a path forward for understanding of these materials and how they catalyze the ORR. Here, we demonstrate through literature examples of how such modeling can be used to better understand non-PGM ORR active site relative stability and activity and how such efforts can also aid in the interpretation of experimental signatures produced by thesemore » materials.« less

  4. Hydrogen activation by magnesia catalysts

    SciTech Connect

    Yulin Gu; Brenner, A. )

    1992-07-01

    Hydrogen activation by magnesia catalysts was investigated by studying H{sub 2}-D{sub 2} exchange. The number of active sites, surface composition, rate, and mechanism of the reaction were investigated as a function of the activation temperature. Behavior of a commercial magnesia and a catalyst synthesized from Mg(OH){sub 2} were similar, although the latter catalyst had a much larger surface area. The upper limit for the number of active sites was determined in the classical manner by using selective poisoning by CO. A novel technique involving monitoring the stoichiometric reaction between magnesia and D{sub 2}(g) enabled the very unusual determination of the lower limit for the number of active sites. Thus, the true number of active sites is bracketed within the upper and lower limits. Maximal activity occurred after activation at 700 C. The number of active sites is about 10{sup 12}/cm{sup 2}, which is 10{sup 3}-fold higher than formerly reported on the basis of EPR data. The turnover frequency at 273 K and a partial pressure of 20 Torr of an equimolar mixture of H{sub 2}-D{sub 2} is 4 s{sup {minus}1}, roughly 10{sup 3}-fold less than previously reported. The site density and activity are now consistent with expected values, rather than the anomalous values previously reported. The hydroxyl coverage of the surface was determined in a novel manner using thermogravimetric analysis over the temperature range of 300 to 1,400 K. The catalysts are of low activity when the surface is either of very high or very low hydroxyl content. A mechanism in which the active site includes an ensemble consisting of a Mg{sup 2+} center and neighboring surface OH and O{sup 2{minus}} is proposed.

  5. Active sites in Cu-SSZ-13 deNOx catalyst under reaction conditions: a XAS/XES perspective

    NASA Astrophysics Data System (ADS)

    Lomachenko, Kirill A.; Borfecchia, Elisa; Bordiga, Silvia; Soldatov, Alexander V.; Beato, Pablo; Lamberti, Carlo

    2016-05-01

    Cu-SSZ-13 is a highly active catalyst for the NH3-assisted selective catalytic reduction (SCR) of the harmful nitrogen oxides (NOx, x=1, 2). Since the catalytically active sites for this reaction are mainly represented by isolated Cu ions incorporated into the zeolitic framework, element-selective studies of Cu local environment are crucial to fully understand the enhanced catalytic properties of this material. Herein, we highlight the recent advances in the characterization of the most abundant Cu-sites in Cu-SSZ-13 upon different reaction-relevant conditions made employing XAS and XES spectroscopies, complemented by computational analysis. A concise review of the most relevant literature is also presented.

  6. Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

    PubMed Central

    Herter, Susanne; Kranz, David C; Turner, Nicholas J

    2015-01-01

    Summary 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. PMID:26664590

  7. Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions.

    PubMed

    Kelly, Paul P; Eichler, Anja; Herter, Susanne; Kranz, David C; Turner, Nicholas J; Flitsch, Sabine L

    2015-01-01

    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.

  8. Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions.

    PubMed

    Kelly, Paul P; Eichler, Anja; Herter, Susanne; Kranz, David C; Turner, Nicholas J; Flitsch, Sabine L

    2015-01-01

    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. PMID:26664590

  9. Use of H2S to Probe the Active Sites in FeNC Catalysts for the Oxygen Reduction Reaction (ORR) in Acidic Media

    SciTech Connect

    Singh, Deepika; Mamtani, Kuldeep; Bruening, Christopher R.; Miller, Jeffrey T.; Ozkan, Umit S.

    2014-10-01

    H2S has been used as a probe molecule both in an “in situ” poisoning experiment and in intermediate-temperature heat-treatment steps during and after the preparation of FeNC catalysts in an attempt to analyze its effect on their ORR activity. The heat treatments were employed either on the ball-milled precursor of FeNC or after the Ar-NH3 high temperature heat treatments. ORR activity of the H2S-treated catalysts was seen to be significantly lower than the sulfur-free catalysts, whether the sulfur exposure was during a half-cell testing, or as an intermediate-temperature exposure to H2S. The incorporation of sulfur species and interaction of Fe with sulfur were confirmed by characterization using XPS, EXAFS, TPO, and TPD. This study provides crucial evidence regarding differences in active sites in FeNC versus nitrogen-containing carbon nanostructured (CNx) catalysts.

  10. Evidences of the presence of different types of active sites for the oxygen reduction reaction with Fe/N/C based catalysts

    NASA Astrophysics Data System (ADS)

    Pérez-Alonso, Francisco J.; Domínguez, Carlota; Al-Thabaiti, Shaeel A.; Al-Youbi, Abdulrahman O.; Abdel Salam, Mohamed; Alshehri, Abdulmohsen A.; Retuerto, María; Peña, Miguel A.; Rojas, Sergio

    2016-09-01

    Fe/N/C catalysts are very active for the oxygen reduction reaction (ORR); however, the nature of the active site(s) is not fully understood. In this work, we study the performance of different types of N/C and Fe/N/C catalysts for the ORR, and the effect of the addition of NaCN. Phthalocyanine and graphene have been studied as model metal-free catalysts for the ORR. Fe-phthalocyanine (FePhcy), Fe-phthalocyanine dispersed in graphene (FePhcy/G) and Fe/N/G, have been used as model Fe-containing catalysts. FePhcy and FePhcy/G only contain Fe atoms coordinated to 4 nitrogen atoms. On the other hand, different species such as Fe-Nx and Fe3C coexist in Fe/N/G. In addition, Csbnd C ensembles are present in the graphene present in FePhcy/G and Fe/N/G. The ORR activity is characteristic of each catalyst, being the highest for the catalysts containing FeN4 ensembles. The addition of CN- results in the selective poisoning of the Fe-containing sites but it does not suppress the ORR activity of the Graphene containing samples. In-situ infrared spectroscopy studies during the ORR reveal that CN- poisoning of the Fe sites is reversible, desorbing at potentials less positive than ca. 600 mV. As a consequence, the ORR activity of the Fe-containing sites is recovered gradually.

  11. Niobium-silica catalysts for the selective epoxidation of cyclic alkenes: the generation of the active site by grafting niobocene dichloride.

    PubMed

    Tiozzo, Cristina; Bisio, Chiara; Carniato, Fabio; Gallo, Alessandro; Scott, Susannah L; Psaro, Rinaldo; Guidotti, Matteo

    2013-08-28

    Niobium-containing silica materials obtained by deposition via liquid-phase grafting or dry impregnation of niobocene(iv) dichloride are active and selective catalysts in the epoxidation of alkenes in the presence of aqueous hydrogen peroxide. The generation of the catalytically-active Nb species was followed step-by-step, and investigated using a combined DR-UV-Vis, NIR, Raman, XRD, XANES and EXAFS analyses. At the end of the grafting procedure, the nature of the surface active species can be described as an oxo-Nb(v) site, tripodally grafted onto the silica surface in close proximity to other Nb(v) centres. The liquid-phase methodology provides a better dispersion of the metal sites onto the siliceous support than the dry-impregnation approach. The niobium-silica catalysts were then tested in the epoxidation of cyclohexene and 1-methylcyclohexene, as model substrates.

  12. Active sites over CuO/CeO2 and inverse CeO2/CuO catalysts for preferential CO oxidation

    NASA Astrophysics Data System (ADS)

    Zeng, Shanghong; Wang, Yan; Ding, Suping; Sattler, Jesper J. H. B.; Borodina, Elena; Zhang, Lu; Weckhuysen, Bert M.; Su, Haiquan

    2014-06-01

    A series of CuO/CeO2 and inverse CeO2/CuO catalysts are prepared by the surfactant-templated method and characterized via XRD, HRTEM, H2-TPR, SEM, XPS, in situ XRD, in situ UV-Vis and N2 adsorption-desorption techniques. It is found that there are two kinds of surface sites in the CuO-CeO2 system, including CuO surface sites for CO chemisorption and CeO2 surface sites with oxygen vacancies for oxygen sorption. The active sites for CO oxidation are located on the contact interface of two-kind surface sites and the lattice oxygen can make a significant contribution to the CO-PROX reaction. The resistance to H2O and CO2 is related to BET surface area, the crystallite sizes of CuO and the reduction behavior of catalysts. The Ce4Cu4 and Ce4Cu1 catalysts exhibit the best resistance against H2O and CO2.

  13. A stable single-site palladium catalyst for hydrogenations.

    PubMed

    Vilé, Gianvito; Albani, Davide; Nachtegaal, Maarten; Chen, Zupeng; Dontsova, Dariya; Antonietti, Markus; López, Núria; Pérez-Ramírez, Javier

    2015-09-14

    We report the preparation and hydrogenation performance of a single-site palladium catalyst that was obtained by the anchoring of Pd atoms into the cavities of mesoporous polymeric graphitic carbon nitride. The characterization of the material confirmed the atomic dispersion of the palladium phase throughout the sample. The catalyst was applied for three-phase hydrogenations of alkynes and nitroarenes in a continuous-flow reactor, showing its high activity and product selectivity in comparison with benchmark catalysts based on nanoparticles. Density functional theory calculations provided fundamental insights into the material structure and attributed the high catalyst activity and selectivity to the facile hydrogen activation and hydrocarbon adsorption on atomically dispersed Pd sites.

  14. Temperature-programmed sulfiding of precursor cobalt oxide genesis of highly active sites on sulfided cobalt catalyst for hydrogenation and isomerization

    SciTech Connect

    Inamura, Kazuhiro; Takyu, Toshiyuki ); Okamoto, Yasuaki; Nagata, Kozo; Imanaka, Toshinobu )

    1992-02-01

    It was found that the method of sulfidation of cobalt oxide strongly affects the catalytic activities and selectivities of the resultant cobalt sulfide catalyst, as well as the calcination temperature of the cobalt oxide. When cobalt oxide was sulfided at 673 K by a temperature-programmed sulfiding method (a heating rate of 6 K/min), catalytic activities for the hydrogenation of butadiene and the isomerization of 1-butene were considerably enhanced compared with those for cobalt sulfide prepared by isothermal sulfidation at 673 K. Results of temperature-programmed sulfiding (TPS), temperature-programmed reduction (TPR), and X-ray diffraction (XRD) suggest that the catalysts showing high catalytic activities after sulfidation are partially sulfided at 673 K and consist of the unsulfided cobalt core phases (CoO or metallic Co). The sulfidation property of precursor cobalt oxides has been studied using TPS, simulating the sulfidation process of the cobalt sulfide catalysts. Two distinctly different kinds of sulfidation process are estimated by TPS measurements of the cobalt oxides. The calcination temperature of the precursor cobalt oxides strongly affects the sulfidation paths. They are differentiated in terms of the presence of a metallic Co intermediate. The relationship of the mechanism of sulfidation of the cobalt oxides to the generation of highly active sites is discussed.

  15. Catalysis: Elusive active site in focus

    NASA Astrophysics Data System (ADS)

    Labinger, Jay A.

    2016-08-01

    The identification of the active site of an iron-containing catalyst raises hopes of designing practically useful catalysts for the room-temperature conversion of methane to methanol, a potential fuel for vehicles. See Letter p.317

  16. Investigation of the Structure and Active Sites of TiO2 Nanorod Supported VOx Catalysts by High-Field and Fast-Spinning 51V MAS NMR

    SciTech Connect

    Hu, Jian Z.; Xu, Suochang; Li, Weizhen; Hu, Mary Y.; Deng, Xuchu; Dixon, David A.; Vasiliu, Monica; Craciun, Raluca; Wang, Yong; Bao, Xinhe; Peden, Charles HF

    2015-07-02

    Supported VOx/TiO2-Rod catalysts were studied by 51V MAS NMR at high field using a sample spinning rate of 55 kHz. The superior spectral resolution allows for the observation of at least five vanadate species. The assignment of these vanadate species was carried out by quantum mechanical calculations of 51V NMR chemical shifts of model V-surface structures. Methanol oxidative dehydrogenation (ODH) was used to establish the correlation between the reaction rate and the various surface V-sites. It is found that monomeric V-species dominated the catalyst at low vanadium loadings with two peaks observed at about -502 and -529 ppm. V-dimers with two bridged oxygen appeare at about -555 ppm. Vanadate dimers and polyvanadates connected by one bridged oxygen atom between two adjacent V atoms resonate at about -630 ppm. A positive correlation is found between the V-dimers related to the -555 ppm peak and the ODH rate while a better correlation is obtained by including monomeric contributions. This result indicates that surface V-dimers related to the -555 ppm peak are the major active sites for ODH reaction despite mono-V species are more catalytic active but their relative ratios are decreased dramatically at high V-loadings. Furthermore, a portion of the V-species is found invisible. In particular, the level of such invisibility increases with decreased level of V-loading, suggesting the existence of paramagnetic V-species at the surface.

  17. Effect of location and filling of d-states on methane activation in single site Fe-based catalysts

    NASA Astrophysics Data System (ADS)

    Sahoo, Sanjubala; Reber, Arthur C.; Khanna, Shiv N.

    2016-09-01

    Theoretical studies on the activation of the C-H bond in methane by an Iron atom bound to four different sites on a silica model support indicate that the lowest activation barrier is found for the case when the Fe is bound to three exposed silicon sites. A molecular orbital analysis reveals that the transition state is stabilized by two filled 3d orbitals that mix with the HOMO and LUMO of methane respectively, indicating how the energy and occupation of the 3d orbitals determine the reaction barrier. The studies offer a strategy for identifying candidates with optimal electronic structure for maximizing C-H bond activation using non-precious metals.

  18. Characterization of the active site structure of Pd and Pd-promoted Mo sulfide catalysts by means of XAFS.

    PubMed

    Kubota, T; Okamoto, Y

    2001-03-01

    Recently, noble metal catalysts are noted as promising candidates for new super-deep-hydrodesulfurization (HDS) catalysts. In this study, we investigated the structure of Pd particles supported on zeolite and Al2O3 under a sulfidation or reduction condition. From EXAFS analysis, it was found for sulfided Pd catalysts that small Pd sulfide clusters are formed without sintering. It was also revealed that no extensive growth of metal Pd particles occurs in Pd/NaY sulfide catalysts even after a treatment with H2 at 673 K. The dispersion of Pd metal particles is improved by H2/H2S treatment. These results indicate that in the presence of H2S, Pd shows high resistance against particle growth. A comparison of the Mo and Pd K-edge EXAFS spectra for MoS(x)/Pd-NaY and Pd-NaY catalysts revealed the existence of Mo-Pd bondings by the addition of Mo sulfide, indicating a direct interaction between Mo and Pd sulfides.

  19. Oxygen activation and CO oxidation over size-selected Pt(n)/alumina/Re(0001) model catalysts: correlations with valence electronic structure, physical structure, and binding sites.

    PubMed

    Roberts, F Sloan; Kane, Matthew D; Baxter, Eric T; Anderson, Scott L

    2014-12-28

    Oxidation of CO over size-selected Ptn clusters (n = 1, 2, 4, 7, 10, 14, 18) supported on alumina thin films grown on Re(0001) was studied using temperature-programmed reaction/desorption (TPR/TPD), X-ray and ultraviolet photoelectron spectroscopy (XPS/UPS), and low energy ion scattering spectroscopy (ISS). The activity of the model catalysts was found to vary by a factor of five with deposited Ptn size during the first reaction cycle (TPR) and by a factor of two during subsequent cycles, with Pt2 being the least active and Pt14 the most active. The limiting step in the reaction appears to be the binding of oxygen; however, this does not appear to be an activated process as reaction is equally efficient for 300 K and 180 K oxidation temperatures. Size-dependent shifts in the valence band onset energy correlate strongly with CO oxidation activity, and there is also an apparent correlation with the availability of a particular binding site, as probed by CO TPD. The morphology of the clusters also becomes more three dimensional over the same size range, but with a distinctly different size-dependence. The results suggest that both electronic structure and the availability of particular binding sites control activity.

  20. Co-ordinatively Unsaturated Al3+ Centers as Binding Sites for Active Catalyst Phases of Platinum on -Al2O3

    SciTech Connect

    Kwak, Ja Hun; Hu, Jiangzhi; Mei, Donghei; Yi, Cheol-Woo; Kim, Do Heui; Peden, Charles; Allard Jr, Lawrence Frederick; Szanyi, Janos

    2009-01-01

    In many heterogeneous catalysts, the interaction of metal particles with their oxide support can alter the electronic properties of the metal and can play a critical role in determining particle morphology and maintaining dispersion. We used a combination of ultrahigh magnetic field, solid-state magic-angle spinning nuclear magnetic resonance spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy coupled with density functional theory calculations to reveal the nature of anchoring sites of a catalytically active phase of platinum on the surface of a {gamma}-Al{sub 2}O{sub 3} catalyst support material. The results obtained show that coordinatively unsaturated pentacoordinate Al{sup 3+} (Al{sub penta}{sup 3+}) centers present on the (100) facets of the {gamma}-Al{sub 2}O{sub 3} surface are anchoring Pt. At low loadings, the active catalytic phase is atomically dispersed on the support surface (Pt/Al{sub penta}{sup 3+} = 1), whereas two-dimensional Pt rafts form at higher coverages.

  1. Synthesis, Characterization, and Catalytic Properties of Novel Single-Site and Nanosized Platinum Catalysts

    SciTech Connect

    Bonati, Matteo L.M.; Douglas, Thomas M.; Gaemers, Sander; Guo, Neng

    2013-01-10

    Novel single-site platinum catalysts have been synthesized by reacting platinum(II) organometallics with partially dehydroxylated silica. The resulting materials have been characterized by various methods such as IR, MAS NMR, and EXAFS. Further, the single-site platinum catalysts were calcined in air to remove the ligand and produce nanosized platinum particles, that were characterized by TEM and H{sub 2} chemisorption. All catalysts were tested for the hydrogenation of toluene. The single-site platinum catalysts were less active than a commercial Pt/SiO{sub 2} catalyst with comparable platinum loading, and this has been ascribed to ligand effects. Conversely, the nanosized platinum catalysts were more active than the commercial Pt/SiO{sub 2} catalyst due to their high dispersion and small particle sizes.

  2. Multifunctional Single-Site Catalysts for Alkoxycarbonylation of Terminal Alkynes.

    PubMed

    Chen, Xingkun; Zhu, Hejun; Wang, Wenlong; Du, Hong; Wang, Tao; Yan, Li; Hu, Xiangping; Ding, Yunjie

    2016-09-01

    A multifunctional copolymer (PyPPh2 -SO3 H@porous organic polymers, POPs) was prepared by combining acidic groups and heterogeneous P,N ligands through the copolymerization of vinyl-functionalized 2-pyridyldiphenylphosphine (2-PyPPh2 ) and p-styrene sulfonic acid under solvothermal conditions. The morphology and chemical structure of the copolymer were evaluated using a series of characterization techniques. Compared with traditional homogeneous Pd(OAc)2 /2-PyPPh2 / p-toluenesulfonic acid catalyst, the copolymer supported palladium catalyst (Pd-PyPPh2 -SO3 H@POPs) exhibited higher activity for alkoxycarbonylation of terminal alkynes under the same conditions. This phenomenon could be attributed to the synergistic effect between the single-site Pd centers, 2-PyPPh2 ligands, and SO3 H groups, the outstanding swelling properties as well as the high enrichment of the reactant concentration by the porous catalyst. In addition, the catalyst could be reused at least 4 times without any apparent loss of activity. The excellent catalytic reactivity and good recycling properties make it an attractive catalyst for industrial applications. This work paves the way for advanced multifunctional porous organic polymers as a new type of platform for heterogeneous catalysis in the future. PMID:27530651

  3. Catalyst Activity Comparison of Alcohols over Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-01-01

    Alcohol transformation to transportation fuel range hydrocarbon on HZSM-5 (SiO2 / Al2O3 = 30) catalyst was studied at 360oC and 300psig. Product distributions and catalyst life were compared using methanol, ethanol, 1-propanol or 1-butanol as a feed. The catalyst life for 1-propanol and 1-butanol was more than double compared to that for methanol and ethanol. For all the alcohols studied, the product distributions (classified to paraffin, olefin, napthene, aromatic and naphthalene compounds) varied with time on stream (TOS). At 24 hours TOS, liquid product from 1-propanol and 1-butanol transformation primarily contains higher olefin compounds. The alcohol transformation process to higher hydrocarbon involves a complex set of reaction pathways such as dehydration, oligomerization, dehydrocyclization, and hydrogenation. Compared to ethylene generated from methanol and ethanol, oligomerization of propylene and butylene has a lower activation energy and can readily take place on weaker acidic sites. On the other hand, dehydrocyclization of propylene and butylene to form the cyclic compounds requires the sits with stronger acid strength. Combination of the above mentioned reasons are the primary reasons for olefin rich product generated in the later stage of the time on stream and for the extended catalyst life time for 1 propanol and 1 butanol compared to methanol and ethanol conversion over HZSM-5.

  4. Catalysts of DNA Strand Cleavage at Apurinic/Apyrimidinic Sites

    PubMed Central

    Minko, Irina G.; Jacobs, Aaron C.; de Leon, Arnie R.; Gruppi, Francesca; Donley, Nathan; Harris, Thomas M.; Rizzo, Carmelo J.; McCullough, Amanda K.; Lloyd, R. Stephen

    2016-01-01

    Apurinic/apyrimidinic (AP) sites are constantly formed in cellular DNA due to instability of the glycosidic bond, particularly at purines and various oxidized, alkylated, or otherwise damaged nucleobases. AP sites are also generated by DNA glycosylases that initiate DNA base excision repair. These lesions represent a significant block to DNA replication and are extremely mutagenic. Some DNA glycosylases possess AP lyase activities that nick the DNA strand at the deoxyribose moiety via a β- or β,δ-elimination reaction. Various amines can incise AP sites via a similar mechanism, but this non-enzymatic cleavage typically requires high reagent concentrations. Herein, we describe a new class of small molecules that function at low micromolar concentrations as both β- and β,δ-elimination catalysts at AP sites. Structure-activity relationships have established several characteristics that appear to be necessary for the formation of an iminium ion intermediate that self-catalyzes the elimination at the deoxyribose ring. PMID:27363485

  5. Catalysts of DNA Strand Cleavage at Apurinic/Apyrimidinic Sites.

    PubMed

    Minko, Irina G; Jacobs, Aaron C; de Leon, Arnie R; Gruppi, Francesca; Donley, Nathan; Harris, Thomas M; Rizzo, Carmelo J; McCullough, Amanda K; Lloyd, R Stephen

    2016-01-01

    Apurinic/apyrimidinic (AP) sites are constantly formed in cellular DNA due to instability of the glycosidic bond, particularly at purines and various oxidized, alkylated, or otherwise damaged nucleobases. AP sites are also generated by DNA glycosylases that initiate DNA base excision repair. These lesions represent a significant block to DNA replication and are extremely mutagenic. Some DNA glycosylases possess AP lyase activities that nick the DNA strand at the deoxyribose moiety via a β- or β,δ-elimination reaction. Various amines can incise AP sites via a similar mechanism, but this non-enzymatic cleavage typically requires high reagent concentrations. Herein, we describe a new class of small molecules that function at low micromolar concentrations as both β- and β,δ-elimination catalysts at AP sites. Structure-activity relationships have established several characteristics that appear to be necessary for the formation of an iminium ion intermediate that self-catalyzes the elimination at the deoxyribose ring. PMID:27363485

  6. Combinatorial evolution of site- and enantioselective catalysts for polyene epoxidation

    NASA Astrophysics Data System (ADS)

    Lichtor, Phillip A.; Miller, Scott J.

    2012-12-01

    Selectivity in the catalytic functionalization of complex molecules is a major challenge in chemical synthesis. The problem is magnified when there are several possible stereochemical outcomes and when similar functional groups occur repeatedly within the same molecule. Selective polyene oxidation provides an archetypical example of this challenge. Historically, enzymatic catalysis has provided the only precedents. Although non-enzymatic catalysts that meet some of these challenges became known, a comprehensive solution has remained elusive. Here, we describe low molecular weight peptide-based catalysts, discovered through a combinatorial synthesis and screening protocol, that exhibit site- and enantioselective oxidation of certain positions of various isoprenols. This diversity-based approach, which exhibits features reminiscent of the directed evolution of enzymes, delivers catalysts that compare favourably to the state-of-the-art for the asymmetric oxidation of these compounds. Moreover, the approach culminated in catalysts that exhibit alternative-site selectivity in comparison to oxidation catalysts previously described.

  7. Combinatorial evolution of site- and enantioselective catalysts for polyene epoxidation

    PubMed Central

    Lichtor, Phillip A.; Miller, Scott J.

    2012-01-01

    Selectivity in the catalytic functionalization of complex molecules is a major challenge in chemical synthesis. The problem is magnified when there are several possible stereochemical outcomes and when similar functional groups occur repeatedly within the same molecule. Selective polyene oxidation provides an archetypical example of this challenge. Historically, enzymatic catalysis provided the only precedents. Although nonenzymatic catalysts are now known that meet some of these challenges, a comprehensive solution has remained elusive. Here, we describe low molecular weight, peptide-based catalysts discovered through a combinatorial synthesis and screening protocol that exhibit site- and enantioselective oxidation of certain positions of various isoprenols. This diversity-based approach, which exhibits features remiscent of the directed evolution of enzymes, delivers catalysts that compare favourably to the state-of-the-art for asymmertric oxidation of these compounds. Moreover, the approach culminated in catalysts that exhibit alternate site-selectivity in comparison to previously described oxidation catalysts. PMID:23174978

  8. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes.

    PubMed

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X; Urban, Ania; Thacker, Nathan C; Lin, Wenbin

    2016-01-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  9. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes

    NASA Astrophysics Data System (ADS)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-08-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  10. Spectroscopic study on the active site of a SiO2 supported niobia catalyst used for the gas-phase Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam.

    PubMed

    Maronna, M M; Kruissink, E C; Parton, R F; Soulimani, F; Weckhuysen, B M; Hoelderich, W F

    2016-08-10

    NbOx/SiO2 with a very high catalytic activity for the gas-phase Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam, was investigated by different spectroscopic methods in order to obtain new insights in the formation and nature of the active sites. FT-IR spectroscopy in combination with pyridine adsorption measurements revealed that the catalyst material contains Lewis-acidic sites, most probably related to the Nb[double bond, length as m-dash]O groups of isolated tetrahedral NbO4 surface species, whereas no Brønsted-acidic sites were observed. Results from in situ Raman and complementary FT-IR measurements strongly suggest that Brønsted-acidic Nb-OH sites can be generated from Nb[double bond, length as m-dash]O groups by reaction with ethanol. This is in agreement with the observation that ethanol is essential for obtaining a very good catalyst performance. However, the Brønsted-acidic sites can be detected in significant amounts in particular in the presence of a Lewis-base, e.g. pyridine, most probably because the formation and/or the stability of these Brønsted-acidic sites are enhanced by a basic molecule. Assuming that cyclohexanone oxime, being a base, can play a similar role as pyridine, we propose on the basis of the spectroscopic findings obtained in this work and our kinetic results published recently, a reaction scheme for the formation of the active site at the Nb[double bond, length as m-dash]O group as well as for the recovery of the Nb[double bond, length as m-dash]O site during the final stage of the gas-phase Beckmann rearrangement.

  11. Highly Stable and Active Catalyst for Sabatier Reactions

    NASA Technical Reports Server (NTRS)

    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.

  12. Self-Supporting Metal-Organic Layers as Single-Site Solid Catalysts.

    PubMed

    Cao, Lingyun; Lin, Zekai; Peng, Fei; Wang, Weiwei; Huang, Ruiyun; Wang, Cheng; Yan, Jiawei; Liang, Jie; Zhang, Zhiming; Zhang, Teng; Long, Lasheng; Sun, Junliang; Lin, Wenbin

    2016-04-11

    Metal-organic layers (MOLs) represent an emerging class of tunable and functionalizable two-dimensional materials. In this work, the scalable solvothermal synthesis of self-supporting MOLs composed of [Hf6O4(OH)4(HCO2)6] secondary building units (SBUs) and benzene-1,3,5-tribenzoate (BTB) bridging ligands is reported. The MOL structures were directly imaged by TEM and AFM, and doped with 4'-(4-benzoate)-(2,2',2''-terpyridine)-5,5''-dicarboxylate (TPY) before being coordinated with iron centers to afford highly active and reusable single-site solid catalysts for the hydrosilylation of terminal olefins. MOL-based heterogeneous catalysts are free from the diffusional constraints placed on all known porous solid catalysts, including metal-organic frameworks. This work uncovers an entirely new strategy for designing single-site solid catalysts and opens the door to a new class of two-dimensional coordination materials with molecular functionalities.

  13. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    PubMed Central

    Guo, Wei; Vlachos, Dionisios G.

    2015-01-01

    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. PMID:26443525

  14. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    SciTech Connect

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, 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.

  15. Patched bimetallic surfaces are active catalysts for ammonia decomposition.

    PubMed

    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.

  16. Glutamates 78 and 122 in the active site of saccharopine dehydrogenase contribute to reactant binding and modulate the basicity of the acid-base catalysts.

    PubMed

    Ekanayake, Devi K; Andi, Babak; Bobyk, Kostyantyn D; West, Ann H; Cook, Paul F

    2010-07-01

    Saccharopine dehydrogenase catalyzes the NAD-dependent oxidative deamination of saccharopine to give l-lysine and alpha-ketoglutarate. There are a number of conserved hydrophilic, ionizable residues in the active site, all of which must be important to the overall reaction. In an attempt to determine the contribution to binding and rate enhancement of each of the residues in the active site, mutations at each residue are being made, and double mutants are being made to estimate the interrelationship between residues. Here, we report the effects of mutations of active site glutamate residues, Glu(78) and Glu(122), on reactant binding and catalysis. Site-directed mutagenesis was used to generate E78Q, E122Q, E78Q/E122Q, E78A, E122A, and E78A/E122A mutant enzymes. Mutation of these residues increases the positive charge of the active site and is expected to affect the pK(a) values of the catalytic groups. Each mutant enzyme was completely characterized with respect to its kinetic and chemical mechanism. The kinetic mechanism remains the same as that of wild type enzymes for all of the mutant enzymes, with the exception of E78A, which exhibits binding of alpha-ketoglutarate to E and E.NADH. Large changes in V/K(Lys), but not V, suggest that Glu(78) and Glu(122) contribute binding energy for lysine. Shifts of more than a pH unit to higher and lower pH of the pK(a) values observed in the V/K(Lys) pH-rate profile of the mutant enzymes suggests that the presence of Glu(78) and Glu(122) modulates the basicity of the catalytic groups.

  17. Effect of catalyst preparation on catalytic activity

    SciTech Connect

    Huang, Y.J.R.

    1987-01-01

    Design parameters have been identified for Ni/Al{sub 2}O{sub 3} catalysts prepared by wet impregnation and incipient wetness from nickel nitrate solution in contact with a {gamma}-Al{sub 2}O{sub 3} support. The metal dispersion, activity for C{sub 1}, C{sub 2}, and C{sub 3} formation under synthesis conditions, and the carbon deposited during reaction have been shown to be predictable based solely on the properties of the electrolytes from which these catalysts were formed. Regardless of the method of preparation, NiAl{sub 2}O{sub 4} was found to be the only active Ni species on low weight loading Ni/Al{sub 2}O{sub 3} catalysts; both Ni and NiAl{sub 2}O{sub 4} are present on high weight loading catalysts. The high-temperature methane peak observed only from CO-TRP spectra of low weight loading catalysts is due to NiAl{sub 2}O{sub 4}; the low-temperature peak that appears as the weight loading is increased is due to Ni. Steady-state reaction kinetics for CH{sub 4} production yield activation energies which increase with increasing weight loading. The apparent activation energies for catalysts with a single methane peak in their CO-TPR spectra were found to be normally distributed. The apparent activation energies for catalysts with two methane peaks in their CO-TPR spectra were found to also be normally distributed when the method of preparation was considered in testing the statistical nature of the distribution. Titration experiments of the carbon pool subsequent to steady-state reaction of H{sub 2} and CO in conjunction with temperature-programmed surface reaction were used to asses the impact of Ni speciation on the rate-determining in step in the methanation reaction. In situ ESCA experiments and microreactor studies were used to examined the existence of metal-support interaction between dispersed Ni and the Al{sub 2}O{sub 3} carrier.

  18. Design of a high activity and selectivity alcohol catalyst

    SciTech Connect

    Foley, H.C.; Mills, G.A.

    1992-07-30

    In methanol dehydration by K-doped Rh-Mo/[gamma]-Al[sub 2]O[sub 3], while higher K levels reduced the dehydration propensity of the surface, at higher levels the potassium oxide layer formed after doping and calcining the surface interferes detrimentally with the Rh-Mo active metallic sites. Silica- and alumina-supported catalysts with 0.5% Rh loading were synthesized and tested for hydrogenation of CO.

  19. Monomolecular Siloxane Film as a Model of Single Site Catalysts.

    PubMed

    Martynowycz, Michael W; Hu, Bo; Kuzmenko, Ivan; Bu, Wei; Hock, Adam; Gidalevitz, David

    2016-09-28

    Achieving structurally well-defined catalytic species requires a fundamental understanding of surface chemistry. Detailed structural characterization of the catalyst binding sites in situ, such as single site catalysts on silica supports, is technically challenging or even unattainable. Octadecyltrioxysilane (OTOS) monolayers formed from octadecyltrimethoxysilane (OTMS) at the air-liquid interface after hydrolysis and condensation at low pH were chosen as a model system of surface binding sites in silica-supported Zn(2+) catalysts. We characterize the system by grazing incidence X-ray diffraction, X-ray reflectivity (XR), and X-ray fluorescence spectroscopy (XFS). Previous X-ray and infrared surface studies of OTMS/OTOS films at the air-liquid interface proposed the formation of polymer OTOS structures. According to our analysis, polymer formation is inconsistent with the X-ray observations and structural properties of siloxanes; it is energetically unfavorable and thus highly unlikely. We suggest an alternative mechanism of hydrolysis/condensation in OTMS leading to the formation of structurally allowed cyclic trimers with the six-membered siloxane rings, which explain well both the X-ray and infrared results. XR and XFS consistently demonstrate that tetrahedral [Zn(NH3)4](2+) ions bind to hydroxyl groups of the film at a stoichiometric ratio of OTOS:Zn ∼ 2:1. The high binding affinity of zinc ions to OTOS trimers suggests that the six-membered siloxane rings are binding locations for single site Zn/SiO2 catalysts. Our results show that OTOS monolayers may serve as a platform for studying silica surface chemistry or hydroxyl-mediated reactions. PMID:27598340

  20. Single-Site Cobalt Catalysts at New Zr8(μ2-O)8(μ2-OH)4 Metal-Organic Framework Nodes for Highly Active Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles.

    PubMed

    Ji, Pengfei; Manna, Kuntal; Lin, Zekai; Urban, Ania; Greene, Francis X; Lan, Guangxu; Lin, Wenbin

    2016-09-21

    We report here the synthesis of robust and porous metal-organic frameworks (MOFs), M-MTBC (M = Zr or Hf), constructed from the tetrahedral linker methane-tetrakis(p-biphenylcarboxylate) (MTBC) and two types of secondary building units (SBUs): cubic M8(μ2-O)8(μ2-OH)4 and octahedral M6(μ3-O)4(μ3-OH)4. While the M6-SBU is isostructural with the 12-connected octahedral SBUs of UiO-type MOFs, the M8-SBU is composed of eight M(IV) ions in a cubic fashion linked by eight μ2-oxo and four μ2-OH groups. The metalation of Zr-MTBC SBUs with CoCl2, followed by treatment with NaBEt3H, afforded highly active and reusable solid Zr-MTBC-CoH catalysts for the hydrogenation of alkenes, imines, carbonyls, and heterocycles. Zr-MTBC-CoH was impressively tolerant of a range of functional groups and displayed high activity in the hydrogenation of tri- and tetra-substituted alkenes with TON > 8000 for the hydrogenation of 2,3-dimethyl-2-butene. Our structural and spectroscopic studies show that site isolation of and open environments around the cobalt-hydride catalytic species at Zr8-SBUs are responsible for high catalytic activity in the hydrogenation of a wide range of challenging substrates. MOFs thus provide a novel platform for discovering and studying new single-site base-metal solid catalysts with enormous potential for sustainable chemical synthesis. PMID:27598720

  1. Process of activation of a palladium catalyst system

    DOEpatents

    Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

    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.

  2. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes.

    PubMed

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X; Urban, Ania; Thacker, Nathan C; Lin, Wenbin

    2016-01-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

  3. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    PubMed Central

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-01-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

  4. Probing the active site of MIO-dependent 2,3-aminomutases, key catalysts in the biosynthesis of beta-amino acids incorporated in secondary metabolites

    PubMed Central

    Bruner, Steven D.; Cooke, Heather

    2012-01-01

    The tyrosine aminomutase SgTAM produces (S)-β-tyrosine from l-tyrosine in the biosynthesis of the enediyne antitumor antibiotic C-1027. This conversion is promoted by the methylideneimidazole-5-one (MIO) prosthetic group. MIO was first identified in the homologous family of ammonia lyases, which deaminate aromatic amino acids to form α,β-unsaturated carboxylates. Studies of substrate specificity have been described for lyases but there have been no reports in altering the substrate specificity of aminomutases. Furthermore, it remains unclear as to what structural properties are responsible for catalyzing the presumed readdition of the amino group into the α,β-unsaturated intermediates to form β-amino acids. Attempts to elucidate specificity and mechanistic determinants of SgTAM have also proved to be difficult as it is recalcitrant to perturbations to the active site via mutagenesis. An X-ray co-crystal structure of the SgTAM mutant of the catalytic base with l-tyrosine verified important substrate binding residues as well as the enzymatic base. Further mutagenesis revealed that removal of these crucial interactions renders the enzyme inactive. Proposed structural determinants for mutase activity probed via mutagenesis, time-point assays and X-ray crystallography revealed a complicated role for these residues in maintaining key quaternary structure properties that aid in catalysis. PMID:20577998

  5. Probing the Active Site of MIO-dependent Aminomutases, Key Catalysts in the Biosynthesis of amino Acids Incorporated in Secondary Metabolites

    SciTech Connect

    Cooke, H.; Bruner, S

    2010-01-01

    The tyrosine aminomutase SgTAM produces (S)-{beta}-tyrosine from L-tyrosine in the biosynthesis of the enediyne antitumor antibiotic C-1027. This conversion is promoted by the methylideneimidazole-5-one (MIO) prosthetic group. MIO was first identified in the homologous family of ammonia lyases, which deaminate aromatic amino acids to form {alpha},{beta}-unsaturated carboxylates. Studies of substrate specificity have been described for lyases but there have been limited reports in altering the substrate specificity of aminomutases. Furthermore, it remains unclear as to what structural properties are responsible for catalyzing the presumed readdition of the amino group into the {alpha},{beta}-unsaturated intermediates to form {beta}-amino acids. Attempts to elucidate specificity and mechanistic determinants of SgTAM have also proved to be difficult as it is recalcitrant to perturbations to the active site via mutagenesis. An X-ray cocrystal structure of the SgTAM mutant of the catalytic base with L-tyrosine verified important substrate binding residues as well as the enzymatic base. Further mutagenesis revealed that removal of these crucial interactions renders the enzyme inactive. Proposed structural determinants for mutase activity probed via mutagenesis, time-point assays and X-ray crystallography revealed a complicated role for these residues in maintaining key quaternary structure properties that aid in catalysis.

  6. Hydrodenitrification catalyst and a method for improving the activity of the catalyst

    SciTech Connect

    Ryan, R. C.

    1985-03-12

    Hydroconversion catalysts containing Group VIII and/or Group VIB catalytically active metals on a support, and particularly those containing nickel and molybdenum on alumina, are improved in hydrodenitrification (HDN) activity by impregnation of additional molybdenum and/or tungsten carbonyls onto the catalyst by sublimation. Preferably from about 1 to 5% w molybdenum is added. The carbonyl impregnated catalyst is then dried, calcined and, generally sulfided before use in a hydrocarbon conversion process.

  7. Single-Site Heterogeneous Catalysts: Innovations, Advantages, and Future Potential in Green Chemistry and Sustainable Technology

    NASA Astrophysics Data System (ADS)

    Raja, Robert; Thomas, John Meurig

    The advantages that flow from the availability of single-site heterogeneous catalysts are many. They facilitate the determination of the kinetics and mechanism of catalytic turnover and render accessible the energetics of various intermediates. More importantly, it is possible to prepare soluble molecular fragments that circumscribe the single site, thus enabling a direct comparison to be made between the catalytic performance of the same active site when functioning as a heterogeneous or a homogeneous catalyst. Our approach adopts the principles and practices of solid-state chemistry, augmented by lessons derived from enzymology, as well as computational chemistry. We have succeeded in designing a range of new catalysts to effect, inter alia, shape-selective, regioselective, bifunctional, and enantioselective catalytic conversions. In particular, large fractions of these catalysts are ideally suited for the era of clean technology in which single-step and/or solvent-free processes abound, and in which benign oxidants such as air or oxygen and inexpensive nanoporous materials are employed.

  8. Activation of catalysts for synthesizing methanol from synthesis gas

    DOEpatents

    Blum, David B.; Gelbein, Abraham P.

    1985-01-01

    A method for activating a methanol synthesis catalyst is disclosed. In this method, the catalyst is slurried in an inert liquid and is activated by a reducing gas stream. The activation step occurs in-situ. That is, it is conducted in the same reactor as is the subsequent step of synthesizing methanol from a methanol gas stream catalyzed by the activated catalyst still dispersed in a slurry.

  9. Dehydration of lactic acid to acrylic acid over lanthanum phosphate catalysts: the role of Lewis acid sites.

    PubMed

    Guo, Zhen; Theng, De Sheng; Tang, Karen Yuanting; Zhang, Lili; Huang, Lin; Borgna, Armando; Wang, Chuan

    2016-09-14

    Lanthanum phosphate (LaP) nano-rods were synthesized using n-butylamine as a shape-directing agent (SDA). The resulting catalysts were applied in the dehydration of lactic acid to acrylic acid. Aiming to understand the nature of the active sites, the chemical and physical properties of LaP materials were studied using a variety of characterization techniques. This study showed that the SDA not only affected the porosity of the LaP materials but also modified the acid-base properties. Clearly, the modification of the acid-base properties played a more critical role in determining the catalytic performance than porosity. An optimized catalytic performance was obtained on the LaP catalyst with a higher concentration of Lewis acid sites. Basic sites showed negative effects on the stability of the catalysts. Good stability was achieved when the catalyst was prepared using the appropriate SDA/La ratio. PMID:27514871

  10. Dehydration of lactic acid to acrylic acid over lanthanum phosphate catalysts: the role of Lewis acid sites.

    PubMed

    Guo, Zhen; Theng, De Sheng; Tang, Karen Yuanting; Zhang, Lili; Huang, Lin; Borgna, Armando; Wang, Chuan

    2016-09-14

    Lanthanum phosphate (LaP) nano-rods were synthesized using n-butylamine as a shape-directing agent (SDA). The resulting catalysts were applied in the dehydration of lactic acid to acrylic acid. Aiming to understand the nature of the active sites, the chemical and physical properties of LaP materials were studied using a variety of characterization techniques. This study showed that the SDA not only affected the porosity of the LaP materials but also modified the acid-base properties. Clearly, the modification of the acid-base properties played a more critical role in determining the catalytic performance than porosity. An optimized catalytic performance was obtained on the LaP catalyst with a higher concentration of Lewis acid sites. Basic sites showed negative effects on the stability of the catalysts. Good stability was achieved when the catalyst was prepared using the appropriate SDA/La ratio.

  11. Phosphine-Free EWG-Activated Ruthenium Olefin Metathesis Catalysts

    NASA Astrophysics Data System (ADS)

    Grela, Karol; Szadkowska, Anna; Michrowska, Anna; Bieniek, Michal; Sashuk, Volodymyr

    Hoveyda-Grubbs catalyst has been successfully fine-tuned by us in order to increase its activity and applicability by the introduction of electron-withdrawing groups (EWGs) to diminish donor properties of the oxygen atom. As a result, the stable and easily accessible nitro-substituted Hoveyda-Grubbs catalyst has found a number of successful applications in various research and industrial laboratories. Some other EWG-activated Hoveyda-type catalysts are commercially available. The results described herewith demonstrate that the activity of ruthenium (Ru) metathesis catalysts can be enhanced by introduction of EWGs without detriment to catalysts stability. Equally noteworthy is the observation that different Ru catalysts turned out to be optimal for different applications. This shows that no single catalyst outperforms all others in all possible applications.

  12. Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

    PubMed Central

    2011-01-01

    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%). PMID:22047220

  13. Structure and activity of tellurium/molybdenum oxide acrylonitrile catalysts. [Ammoxidation

    SciTech Connect

    Bart, J.C.J.; Giordano, N.

    1980-08-01

    The tellurium/molybdenum mixed oxides ((TeMo)O) catalyst system was investigated as part of the development of an industrial cerium/tellurium/molybdenum mixed oxides catalyst for propylene ammoxidation Catalysts containing 25% active phase on silica were prepared, characterized by BET surface area measurement, mercury porosimetry, X-ray diffraction, and optical microscopy, and tested for the ammoxidation of propylene at 400/sup 0/-460/sup 0/C in a flow reactor. The results suggested that Te/sub 2/MoO/sub 7/ is the active phase. The mechanism probably involves activation of propylene on a tellurium site and oxygen insertion at isolated and highly distorted MoO/sub 6/ octahedral sites. The addition of cerium to the binary catalyst prevents the reductive degradation of (TeMo)O which occurs under reactor flow conditions by a phase-separation process.

  14. Increasing the hydrogenation activity of commercial catalysts for selective hydrocracking

    SciTech Connect

    Khashagul`gova, N.S.; Freiman, L.L.; Zelentsov, Yu.N.

    1994-07-01

    The catalysts generally used in hydrodewaxing or selective hydrocracking of n-paraffins are zeolites with the pentasil structure: TsVK, TsVM, TsVN, and Ultrasil. For use in the production of high-quality transformer oils from paraffinic feedstocks, these catalysts have not only a high cracking activity but also an adequate hydrogenating activity. Catalysts containing a nickel-molybdenum complex (or nickel molybdate synthesized by a specific method) are higher in hydrogenating activity in comparison with catalysts in which the metals are introduced by coextrusion or impregnation. Precipitation of a nickel-molybdenum complex on a solid support (aluminosilicate or zeolite) tends to increase its hydrogenating activity, so that the content of the hydrogenating metals in the catalyst can be reduced. This report describes studies on catalysts based on TsVM and TsVN high-silica zeolites.

  15. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    DOE PAGES

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, 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-Hmore » 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.« less

  16. Iridium Oxide Coatings with Templated Porosity as Highly Active Oxygen Evolution Catalysts: Structure-Activity Relationships.

    PubMed

    Bernicke, Michael; Ortel, Erik; Reier, Tobias; Bergmann, Arno; Ferreira de Araujo, Jorge; Strasser, Peter; Kraehnert, Ralph

    2015-06-01

    Iridium oxide is the catalytic material with the highest stability in the oxygen evolution reaction (OER) performed under acidic conditions. However, its high cost and limited availability demand that IrO2 is utilized as efficiently as possible. We report the synthesis and OER performance of highly active mesoporous IrO2 catalysts with optimized surface area, intrinsic activity, and pore accessibility. Catalytic layers with controlled pore size were obtained by soft-templating with micelles formed from amphiphilic block copolymers poly(ethylene oxide)-b-poly(butadiene)-b-poly(ethylene oxide). A systematic study on the influence of the calcination temperature and film thickness on the morphology, phase composition, accessible surface area, and OER activity reveals that the catalytic performance is controlled by at least two independent factors, that is, accessible surface area and intrinsic activity per accessible site. Catalysts with lower crystallinity show higher intrinsic activity. The catalyst surface area increases linearly with film thickness. As a result of the templated mesopores, the pore surface remains fully active and accessible even for thick IrO2 films. Even the most active multilayer catalyst does not show signs of transport limitations at current densities as high as 75 mA cm(-2) . PMID:25958795

  17. Iridium Oxide Coatings with Templated Porosity as Highly Active Oxygen Evolution Catalysts: Structure-Activity Relationships.

    PubMed

    Bernicke, Michael; Ortel, Erik; Reier, Tobias; Bergmann, Arno; Ferreira de Araujo, Jorge; Strasser, Peter; Kraehnert, Ralph

    2015-06-01

    Iridium oxide is the catalytic material with the highest stability in the oxygen evolution reaction (OER) performed under acidic conditions. However, its high cost and limited availability demand that IrO2 is utilized as efficiently as possible. We report the synthesis and OER performance of highly active mesoporous IrO2 catalysts with optimized surface area, intrinsic activity, and pore accessibility. Catalytic layers with controlled pore size were obtained by soft-templating with micelles formed from amphiphilic block copolymers poly(ethylene oxide)-b-poly(butadiene)-b-poly(ethylene oxide). A systematic study on the influence of the calcination temperature and film thickness on the morphology, phase composition, accessible surface area, and OER activity reveals that the catalytic performance is controlled by at least two independent factors, that is, accessible surface area and intrinsic activity per accessible site. Catalysts with lower crystallinity show higher intrinsic activity. The catalyst surface area increases linearly with film thickness. As a result of the templated mesopores, the pore surface remains fully active and accessible even for thick IrO2 films. Even the most active multilayer catalyst does not show signs of transport limitations at current densities as high as 75 mA cm(-2) .

  18. Activation of molecular catalysts using semiconductor quantum dots

    DOEpatents

    Meyer, Thomas J.; Sykora, Milan; Klimov, Victor I.

    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.

  19. Crystallographic dependence of CO activation on cobalt catalysts: HCP versus FCC.

    PubMed

    Liu, Jin-Xun; Su, Hai-Yan; Sun, Da-Peng; Zhang, Bing-Yan; Li, Wei-Xue

    2013-11-01

    Identifying the structure sensitivity of catalysts in reactions, such as Fischer-Tropsch synthesis from CO and H2 over cobalt catalysts, is an important yet challenging issue in heterogeneous catalysis. Based on a first-principles kinetic study, we find for the first time that CO activation on hexagonal close-packed (HCP) Co not only has much higher intrinsic activity than that of face centered-cubic (FCC) Co but also prefers a different reaction route, i.e., direct dissociation with HCP Co but H-assisted dissociation on the FCC Co. The origin is identified from the formation of various denser yet favorable active sites on HCP Co not available for FCC Co, due to their distinct crystallographic structure and morphology. The great dependence of the activity on the crystallographic structure and morphology of the catalysts revealed here may open a new avenue for better, stable catalysts with maximum mass-specific reactivity.

  20. Synthesis of ethanol via syngas on Cu/SiO2 catalysts with balanced Cu0-Cu+ sites.

    PubMed

    Gong, Jinlong; Yue, Hairong; Zhao, Yujun; Zhao, Shuo; Zhao, Li; Lv, Jing; Wang, Shengping; Ma, Xinbin

    2012-08-29

    This paper describes an emerging synthetic route for the production of ethanol (with a yield of ~83%) via syngas using Cu/SiO(2) catalysts. The remarkable stability and efficiency of the catalysts are ascribed to the unique lamellar structure and the cooperative effect between surface Cu(0) and Cu(+) obtained by an ammonia evaporation hydrothermal method. Characterization results indicated that the Cu(0) and Cu(+) were formed during the reduction process, originating from well-dispersed CuO and copper phyllosilicate, respectively. A correlation between the catalytic activity and the Cu(0) and Cu(+) site densities suggested that Cu(0) could be the sole active site and primarily responsible for the activity of the catalyst. Moreover, we have shown that the selectivity for ethanol or ethylene glycol can be tuned simply by regulating the reaction temperature.

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

    SciTech Connect

    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.

  2. Isolated catalyst sites on amorphous supports: A systematic algorithm for understanding heterogeneities in structure and reactivity

    NASA Astrophysics Data System (ADS)

    Goldsmith, Bryan R.; Sanderson, Evan D.; Bean, Daniel; Peters, Baron

    2013-05-01

    Methods for modeling catalytic sites on amorphous supports lag far behind methods for modeling catalytic sites on metal surfaces, zeolites, and other crystalline materials. One typical strategy for amorphous supports uses cluster models with arbitrarily chosen constraints to model the rigid amorphous support, but these constraints arbitrarily influence catalyst site activity. An alternative strategy is to use no constraints, but this results in catalytic sites with unrealistic flexibility. We present a systematic ab initio method to model isolated active sites on insulating amorphous supports using small cluster models. A sequential quadratic programming framework helps us relate chemical properties, such as the activation energy, to active site structure. The algorithm is first illustrated on an empirical valence bond model energy landscape. We then use the algorithm to model an off-pathway kinetic trap in olefin metathesis by isolated Mo sites on amorphous SiO2. The cluster models were terminated with basis set deficient fluorine atoms to mimic the properties of an extended silica framework. We also discuss limitations of the current algorithm formulation and future directions for improvement.

  3. Catalyst recognition of cis-1,2-diols enables site-selective functionalization of complex molecules

    NASA Astrophysics Data System (ADS)

    Sun, Xixi; Lee, Hyelee; Lee, Sunggi; Tan, Kian L.

    2013-09-01

    Carbohydrates and natural products serve essential roles in nature, and also provide core scaffolds for pharmaceutical agents and vaccines. However, the inherent complexity of these molecules imposes significant synthetic hurdles for their selective functionalization and derivatization. Nature has, in part, addressed these issues by employing enzymes that are able to orient and activate substrates within a chiral pocket, which increases dramatically both the rate and selectivity of organic transformations. In this article we show that similar proximity effects can be utilized in the context of synthetic catalysts to achieve general and predictable site-selective functionalization of complex molecules. Unlike enzymes, our catalysts apply a single reversible covalent bond to recognize and bind to specific functional group displays within substrates. By combining this unique binding selectivity and asymmetric catalysis, we are able to modify the less reactive axial positions within monosaccharides and natural products.

  4. C-O cleavage of aromatic oxygenates over ruthenium catalysts. A computational study of reactions at step sites.

    PubMed

    Chiu, Cheng-chau; Genest, Alexander; Borgna, Armando; Rösch, Notker

    2015-06-21

    We studied the C-O cleavage of phenolate and catecholate at step sites of a Ru catalyst using periodic DFT methods at the GGA level. Both C-O scission steps are associated with activation barriers of about 75 kJ mol(-1), hence are significantly more facile than the analogous reactions on Ru terraces. With these computational results, we offer an interpretation of recent experiments on the hydrodeoxygenation of guaiacol (2-methoxyphenol) over Ru/C. We hypothesize that the experimentally observed dependency of the product selectivity on the H2 pressure is related to the availability of step sites on a Ru catalyst.

  5. Method for regeneration and activity improvement of syngas conversion catalyst

    DOEpatents

    Lucki, Stanley J.; Brennan, James A.

    1980-01-01

    A method is disclosed for the treatment of single particle iron-containing syngas (synthes.s gas) conversion catalysts comprising iron, a crystalline acidic aluminosilicate zeolite having a silica to alumina ratio of at least 12, a pore size greater than about 5 Angstrom units and a constraint index of about 1-12 and a matrix. The catalyst does not contain promoters and the treatment is applicable to either the regeneration of said spent single particle iron-containing catalyst or for the initial activation of fresh catalyst. The treatment involves air oxidation, hydrogen reduction, followed by a second air oxidation and contact of the iron-containing single particle catalyst with syngas prior to its use for the catalytic conversion of said syngas. The single particle iron-containing catalysts are prepared from a water insoluble organic iron compound.

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

    PubMed Central

    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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    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.

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

    PubMed

    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

  9. Catalytic deactivation of methane steam reforming catalysts. I. Activation

    SciTech Connect

    Agnelli, M.E.; Demicheli, M.C.; Ponzi, E.N.

    1987-08-01

    An alumina-supported catalyst was studied both in its original state and after activation and sintering. Chemical composition and textural properties were determined, and crystalline compounds were identified. Active-phase and support transformations occurring during activation were determined by differential thermoanalysis (DTA), temperature-programmed reduction (TPR), and X-ray diffraction. The catalyst activated by means of various procedures was characterized by measuring crystallite size.

  10. The structure and activity of titania supported cobalt catalysts

    SciTech Connect

    Ho Suiwen; Houalla, M.; Hercules, D.M. ); Cruz, J.M. )

    1992-05-01

    A series of titania supported cobalt catalysts (0.5-6%) were prepared by incipient wetness impregnation, and were characterized by ESCA, XRD, and hydrogen chemisorption. After calcination at 400 C, a surface CoTiO[sub 3]-like phase was the main species present in the 0.5 and 1% cobalt catalysts. For higher cobalt loadings, discrete Co[sub 3]O[sub 4] particles were formed in addition to surface CoTiO[sub 3]. ESCA indicates that after reduction the cobalt metal particle size (6-13 nm) increases with increasing cobalt loadings, but does not vary with reduction temperature (400-500 C). Hydrogen chemisorption was found to be activated and suppressed. The extent of hydrogen chemisorption suppression increases with increasing reduction temperature and decreasing cobalt particle size. The turnover frequency (based on cobalt dispersion derived from ESCA) for benzene and CO hydrogenation decreases with increasing reduction temperature and decreasing cobalt particle size. The decline in activity correlates with the extent of suppression of H[sub 2] chemisorption. The results were interpreted in terms of a decrease in the fraction of exposed surface cobalt due to site blocking by reduced TiO[sub 3] moieties.

  11. Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts.

    PubMed

    Pelletier, Jérémie D A; Basset, Jean-Marie

    2016-04-19

    Heterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity). Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the support taken

  12. Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts.

    PubMed

    Pelletier, Jérémie D A; Basset, Jean-Marie

    2016-04-19

    Heterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity). Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the support taken

  13. The role of catalyst activation on the activity and attrition of precipitated iron Fischer-Tropsch catalysts

    SciTech Connect

    Datye, A.K.; Shroff, M.D.; Harrington, M.S.; Coulter, K.E.; Sault, A.G.; Jackson, N.B.

    1995-12-31

    The results of this work indicate that magnetite is not catalytically active for Fischer-Tropsch Synthesis (FTS) in precipitated, unsupported iron catalysts, but the formation of the carbide phase is necessary to obtain FTS activity. The transformation of magnetite to carbide, though essential to obtain FTS activity, also causes the catalyst to break down. This can lead to severe problems during operation in a commercial slurry phase reactor. The results presented here imply that activation and attrition are simultaneous and complementary processes. In another study, we show that the catalyst can also under go attrition on a micron scale which is caused by lack of strength of the forces binding the catalyst primary particles in the agglomerates. Both these processes can make wax separation and product recovery extremely difficult. In this study, we have also shown that H{sub 2} reduction of this catalyst to metallic iron is detrimental to subsequent catalyst activity and causes a loss of surface area due to sintering of the iron crystallites. Reduction to metallic Fe also causes impurities such as S to segregate to the surface causing a complete loss of FTS activity. It has been shown that even submonolayer amounts of S can cause a dramatic decrease in FTS activity, hence reduction to metallic Fe should be avoided during activation of these catalysts. We have shown, however, that a mild H{sub 2} reduction to magnetite does not lead to S segregation to the surface, and is therefore acceptable.

  14. Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents.

    PubMed

    Mougel, Victor; Chan, Ka-Wing; Siddiqi, Georges; Kawakita, Kento; Nagae, Haruki; Tsurugi, Hayato; Mashima, Kazushi; Safonova, Olga; Copéret, Christophe

    2016-08-24

    Alkene metathesis is a widely and increasingly used reaction in academia and industry because of its efficiency in terms of atom economy and its wide applicability. This reaction is notably responsible for the production of several million tons of propene annually. Such industrial processes rely on inexpensive silica-supported tungsten oxide catalysts, which operate at high temperatures (>350 °C), in contrast with the mild room temperature reaction conditions typically used with the corresponding molecular alkene metathesis homogeneous catalysts. This large difference in the temperature requirements is generally thought to arise from the difficulty in generating active sites (carbenes or metallacyclobutanes) in the classical metal oxide catalysts and prevents broader applicability, notably with functionalized substrates. We report here a low temperature activation process of well-defined metal oxo surface species using organosilicon reductants, which generate a large amount of active species at only 70 °C (0.6 active sites/W). This high activity at low temperature broadens the scope of these catalysts to functionalized substrates. This activation process can also be applied to classical industrial catalysts. We provide evidence for the formation of a metallacyclopentane intermediate and propose how the active species are formed.

  15. Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents

    PubMed Central

    2016-01-01

    Alkene metathesis is a widely and increasingly used reaction in academia and industry because of its efficiency in terms of atom economy and its wide applicability. This reaction is notably responsible for the production of several million tons of propene annually. Such industrial processes rely on inexpensive silica-supported tungsten oxide catalysts, which operate at high temperatures (>350 °C), in contrast with the mild room temperature reaction conditions typically used with the corresponding molecular alkene metathesis homogeneous catalysts. This large difference in the temperature requirements is generally thought to arise from the difficulty in generating active sites (carbenes or metallacyclobutanes) in the classical metal oxide catalysts and prevents broader applicability, notably with functionalized substrates. We report here a low temperature activation process of well-defined metal oxo surface species using organosilicon reductants, which generate a large amount of active species at only 70 °C (0.6 active sites/W). This high activity at low temperature broadens the scope of these catalysts to functionalized substrates. This activation process can also be applied to classical industrial catalysts. We provide evidence for the formation of a metallacyclopentane intermediate and propose how the active species are formed. PMID:27610418

  16. Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents.

    PubMed

    Mougel, Victor; Chan, Ka-Wing; Siddiqi, Georges; Kawakita, Kento; Nagae, Haruki; Tsurugi, Hayato; Mashima, Kazushi; Safonova, Olga; Copéret, Christophe

    2016-08-24

    Alkene metathesis is a widely and increasingly used reaction in academia and industry because of its efficiency in terms of atom economy and its wide applicability. This reaction is notably responsible for the production of several million tons of propene annually. Such industrial processes rely on inexpensive silica-supported tungsten oxide catalysts, which operate at high temperatures (>350 °C), in contrast with the mild room temperature reaction conditions typically used with the corresponding molecular alkene metathesis homogeneous catalysts. This large difference in the temperature requirements is generally thought to arise from the difficulty in generating active sites (carbenes or metallacyclobutanes) in the classical metal oxide catalysts and prevents broader applicability, notably with functionalized substrates. We report here a low temperature activation process of well-defined metal oxo surface species using organosilicon reductants, which generate a large amount of active species at only 70 °C (0.6 active sites/W). This high activity at low temperature broadens the scope of these catalysts to functionalized substrates. This activation process can also be applied to classical industrial catalysts. We provide evidence for the formation of a metallacyclopentane intermediate and propose how the active species are formed. PMID:27610418

  17. Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents

    PubMed Central

    2016-01-01

    Alkene metathesis is a widely and increasingly used reaction in academia and industry because of its efficiency in terms of atom economy and its wide applicability. This reaction is notably responsible for the production of several million tons of propene annually. Such industrial processes rely on inexpensive silica-supported tungsten oxide catalysts, which operate at high temperatures (>350 °C), in contrast with the mild room temperature reaction conditions typically used with the corresponding molecular alkene metathesis homogeneous catalysts. This large difference in the temperature requirements is generally thought to arise from the difficulty in generating active sites (carbenes or metallacyclobutanes) in the classical metal oxide catalysts and prevents broader applicability, notably with functionalized substrates. We report here a low temperature activation process of well-defined metal oxo surface species using organosilicon reductants, which generate a large amount of active species at only 70 °C (0.6 active sites/W). This high activity at low temperature broadens the scope of these catalysts to functionalized substrates. This activation process can also be applied to classical industrial catalysts. We provide evidence for the formation of a metallacyclopentane intermediate and propose how the active species are formed.

  18. Highly active and highly selective aromatization catalyst

    SciTech Connect

    Santilli, D.S.; Long, J.J.; Lewis, R.T.

    1987-10-06

    This patent describes a reforming catalyst comprising an L zeolite containing platinum metal and at least one promoter metal selected from the group consisting of iron, cobalt, titanium, and rare earth metal. The catalyst has a platinum to promoter metal mole ratio of less than 10:1. The patent also includes a method of preparing the reforming catalyst of claim 1, comprising steps of: (a) forming an aqueous solution of alkali hydroxide, aluminum hydroxide, and ferric salt; (b) combining the solution with an aqueous solution of silica to form a thickening gel in a mother liquor; (c) heating the thickening gel to form an L zeolite; (d) cooling the gel containing the L zeolite; (e) decanting the mother liquor from the gel; (f) filtering the L zeolite from the gel; (g) washing the filtered L zeolite; (h) drying the washed L zeolite; (i) adding platinum to the dried L zeolite to form a catalyst; (j) drying the catalyst; and (k) calcining the dried catalyst.

  19. Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts.

    PubMed

    Varnell, Jason A; Tse, Edmund C M; Schulz, Charles E; Fister, Tim T; Haasch, Richard T; Timoshenko, Janis; Frenkel, Anatoly I; Gewirth, Andrew A

    2016-01-01

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites.

  20. Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

    NASA Astrophysics Data System (ADS)

    Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

    2016-08-01

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites.

  1. Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

    PubMed Central

    Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

    2016-01-01

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

  2. Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts.

    PubMed

    Varnell, Jason A; Tse, Edmund C M; Schulz, Charles E; Fister, Tim T; Haasch, Richard T; Timoshenko, Janis; Frenkel, Anatoly I; Gewirth, Andrew A

    2016-01-01

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

  3. Decoupling HZSM-5 catalyst activity from deactivation during upgrading of pyrolysis oil vapors.

    PubMed

    Wan, Shaolong; Waters, Christopher; Stevens, Adam; Gumidyala, Abhishek; Jentoft, Rolf; Lobban, Lance; Resasco, Daniel; Mallinson, Richard; Crossley, Steven

    2015-02-01

    The independent evaluation of catalyst activity and stability during the catalytic pyrolysis of biomass is challenging because of the nature of the reaction system and rapid catalyst deactivation that force the use of excess catalyst. In this contribution we use a modified pyroprobe system in which pulses of pyrolysis vapors are converted over a series of HZSM-5 catalysts in a separate fixed-bed reactor controlled independently. Both the reactor-bed temperature and the Si/Al ratio of the zeolite are varied to evaluate catalyst activity and deactivation rates independently both on a constant surface area and constant acid site basis. Results show that there is an optimum catalyst-bed temperature for the production of aromatics, above which the production of light gases increases and that of aromatics decrease. Zeolites with lower Si/Al ratios give comparable initial rates for aromatics production, but far more rapid catalyst deactivation rates than those with higher Si/Al ratios. PMID:25504857

  4. Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells.

    PubMed

    Kramm, Ulrike I; Herranz, Juan; Larouche, Nicholas; Arruda, Thomas M; Lefèvre, Michel; Jaouen, Frédéric; Bogdanoff, Peter; Fiechter, Sebastian; Abs-Wurmbach, Irmgard; Mukerjee, Sanjeev; Dodelet, Jean-Pol

    2012-09-01

    Fe-based catalytic sites for the reduction of oxygen in acidic medium have been identified by (57)Fe Mössbauer spectroscopy of Fe/N/C catalysts containing 0.03 to 1.55 wt% Fe, which were prepared by impregnation of iron acetate on carbon black followed by heat-treatment in NH(3) at 950 °C. Four different Fe-species were detected at all iron concentrations: three doublets assigned to molecular FeN(4)-like sites with their ferrous ions in a low (D1), intermediate (D2) or high (D3) spin state, and two other doublets assigned to a single Fe-species (D4 and D5) consisting of surface oxidized nitride nanoparticles (Fe(x)N, with x≤ 2.1). A fifth Fe-species appears only in those catalysts with Fe-contents ≥0.27 wt%. It is characterized by a very broad singlet, which has been assigned to incomplete FeN(4)-like sites that quickly dissolve in contact with an acid. Among the five Fe-species identified in these catalysts, only D1 and D3 display catalytic activity for the oxygen reduction reaction (ORR) in the acid medium, with D3 featuring a composite structure with a protonated neighbour basic nitrogen and being by far the most active species, with an estimated turn over frequency for the ORR of 11.4 e(-) per site per s at 0.8 V vs. RHE. Moreover, all D1 sites and between 1/2 and 2/3 of the D3 sites are acid-resistant. A scheme for the mechanism of site formation upon heat-treatment is also proposed. This identification of the ORR-active sites in these catalysts is of crucial importance to design strategies to improve the catalytic activity and stability of these materials.

  5. Sulphate-activated growth of bamboo-like carbon nanotubes over copper catalysts

    NASA Astrophysics Data System (ADS)

    Lin, Jarrn-Horng; Chen, Ching-Shiun; Zeng, Zhi-Yan; Chang, Chia-Wei; Chen, Hsiu-Wei

    2012-07-01

    A sulphate-activated mechanism is proposed to describe the growth of bamboo-like carbon nanotubes (CNTs) over copper catalysts using chemical vapour deposition with helium-diluted ethylene. Sulphate-assisted copper catalysts afford a high-yield growth of bamboo-like CNTs at a mild temperature, 800 °C however, non-sulphate-assisted copper catalysts, e.g., copper acetate and copper nitrate prepared catalysts, were inert to CNT growth and only gave amorphous carbons (a-C) surrounding copper nanoparticles under the same conditions. Nevertheless, the addition of sulphate ions in the preparation step for the two inert catalysts can activate their abilities for CNT growth with remarkable yields. Furthermore, Raman spectra analysis demonstrates a linear dependence between the concentration of sulphate ions in copper catalysts and the ratio of CNT-a-C in the as-grown carbon soot. The sulphate-activated effect on CNT growth over copper catalysts could be related to a three-way interaction of sulphate ions, copper nanoparticles and support. In situ TEM images of an as-grown CNT irradiated by electron beams without the inlet of carbon sources reveal a new pathway of carbon diffusion through the bulk of copper nanoparticles and an enlarged inner-wall thickness of the on-site CNT. This carbon diffusion model over copper catalysts can provide new insights into the CNT growth mechanism over non-magnetic metal catalysts.A sulphate-activated mechanism is proposed to describe the growth of bamboo-like carbon nanotubes (CNTs) over copper catalysts using chemical vapour deposition with helium-diluted ethylene. Sulphate-assisted copper catalysts afford a high-yield growth of bamboo-like CNTs at a mild temperature, 800 °C however, non-sulphate-assisted copper catalysts, e.g., copper acetate and copper nitrate prepared catalysts, were inert to CNT growth and only gave amorphous carbons (a-C) surrounding copper nanoparticles under the same conditions. Nevertheless, the addition of

  6. Ruthenium-based olefin metathesis catalysts bearing pH-responsive ligands: External control of catalyst solubility and activity

    NASA Astrophysics Data System (ADS)

    Balof, Shawna Lynn

    2011-12-01

    Sixteen novel, Ru-based olefin metathesis catalysts bearing pH responsive ligands were synthesized. The pH-responsive groups employed with these catalysts included dimethylamino (NMe2) modified NHC ligands as well as N-donor dimethylaminopyridine (DMAP) and 3-(o-pyridyl)propylidene ligands. These pH-responsive ligands provided the means by which the solubility and/or activity profiles of the catalysts produced could be controlled via acid addition. The main goal of this dissertation was to design catalyst systems capable of performing ring opening metathesis (ROMP) and ring closing metathesis (RCM) reactions in both organic and aqueous media. In an effort to quickly gain access to new catalyst structures, a template synthesis for functionalized NHC ligand precursors was designed, in addition to other strategies, to obtain ligand precursors with ancillary NMe2 groups. Kinetic studies for the catalysts produced from these precursors showed external control of catalyst solubility was afforded via protonation of the NMe2 groups of their NHC ligands. Additionally, this protonation afforded external control of catalyst propagation rates for several catalysts. This is the first known independent external control for the propagation rates of ROMP catalysts. The incorporation of pH-responsive N-donor ligands into catalyst structures also provided the means for the external control of metathesis activity, as the protonation of these ligands resulted in an increased initiation rate based on their fast and irreversible dissociation from the metal center. The enhanced external control makes these catalysts applicable to a wide range of applications, some of which have been explored by us and/or through collaboration. Three of the catalysts designed showed remarkable metathesis activity in aqueous media. These catalysts displayed comparable RCM activity in aqueous media to a class of water-soluble catalysts reported by Grubbs et al., considered to be the most active catalyst for

  7. A dual site catalyst for mild, selective nitrile reduction.

    PubMed

    Lu, Zhiyao; Williams, Travis J

    2014-05-25

    We report a novel ruthenium bis(pyrazolyl)borate scaffold that enables cooperative reduction reactivity in which boron and ruthenium centers work in concert to effect selective nitrile reduction. The pre-catalyst compound [κ(3)-(1-pz)2HB(N = CHCH3)]Ru(cymene)(+) TfO(-) (pz = pyrazolyl) was synthesized using readily-available materials through a straightforward route, thus making it an appealing catalyst for a number of reactions.

  8. Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells

    PubMed Central

    Kramm, Ulrike I.; Herranz, Juan; Larouche, Nicholas; Arruda, Thomas M.; Lefèvre, Michel; Jaouen, Frédéric; Bogdanoff, Peter; Fiechter, Sebastian; Abs-Wurmbach, Irmgard; Mukerjee, Sanjeev; Dodelet, Jean-Pol

    2012-01-01

    Fe-based catalytic sites for the reduction of oxygen in acidic medium have been identified by 57Fe Mössbauer spectroscopy of Fe/N/C catalysts containing 0.03 to 1.55 wt% Fe, which were prepared by impregnation of iron acetate on carbon black followed by heat-treatment in NH3 at 950°C. Four different Fe-species were detected at all iron concentrations: three doublets assigned to molecular FeN4-like sites with their ferrous ion in low (D1), medium (D2) or high spin state (D3), and two other doublets assigned to a single Fe-species (D4 and D5) consisting of surface oxidized nitride nanoparticles (FexN, with x≤2.1). A fifth Fe-species appears only in those catalysts with Fe-contents ≥ 0.27 wt%. It is characterized by a very broad singlet, which has been assigned to incomplete FeN4-like sites that quickly dissolve in contact with an acid. Among the five Fe-species identified in these catalysts, only D1 and D3 display catalytic activity for the oxygen reduction reaction (ORR) in the acid medium, with D3 featuring a composite structure with a protonated neighbour basic nitrogen and being by far the most active species, with an estimated turn over frequency for the ORR of 11.4 e− site−1 s−1 at 0.8V vs RHE. Moreover, all D1 sites and between 1/2 to 2/3 of the D3 sites are acid-resistant. A scheme for the mechanism of site formation upon heat-treatment is also proposed. This identification of the ORR-active sites in these catalysts is of crucial importance to design strategies to improve the catalytic activity and stability of these materials. PMID:22824866

  9. Low dielectric response in enzyme active site

    PubMed Central

    Mertz, Edward L.; Krishtalik, Lev I.

    2000-01-01

    The kinetics of charge transfer depend crucially on the dielectric reorganization of the medium. In enzymatic reactions that involve charge transfer, atomic dielectric response of the active site and of its surroundings determines the efficiency of the protein as a catalyst. We report direct spectroscopic measurements of the reorganization energy associated with the dielectric response in the active site of α-chymotrypsin. A chromophoric inhibitor of the enzyme is used as a spectroscopic probe. We find that water strongly affects the dielectric reorganization in the active site of the enzyme in solution. The reorganization energy of the protein matrix in the vicinity of the active site is similar to that of low-polarity solvents. Surprisingly, water exhibits an anomalously high dielectric response that cannot be described in terms of the dielectric continuum theory. As a result, sequestering the active site from the aqueous environment inside low-dielectric enzyme body dramatically reduces the dielectric reorganization. This reduction is particularly important for controlling the rate of enzymatic reactions. PMID:10681440

  10. The activation mechanism of Fe-based olefin metathesis catalysts

    NASA Astrophysics Data System (ADS)

    Poater, Albert; Pump, Eva; Vummaleti, Sai Vikrama Chaitanya; Cavallo, Luigi

    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.

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

    SciTech Connect

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

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

  12. Active Gold-Ceria and Gold-Ceria/titania Catalysts for CO Oxidation. From Single-Crystal Model Catalysts to Powder Catalysts

    SciTech Connect

    Rodriguez, Jose A.; Si, Rui; Evans, Jaime; Xu, Wenqian; Hanson, Jonathan C.; Tao, Jing; Zhu, Yimei

    2014-07-23

    We studied CO oxidation on model and powder catalysts of Au-CeO2 and Au-CeOx/TiO2. Phenomena observed in Au-CeO2(1 1 1) and Au-CeO2/TiO2(1 1 0) provided useful concepts for designing and preparing highly active and stable Au-CeOx/TiO2 powder catalysts for CO oxidation. Small particles of Au dispersed on CeO2(1 1 1) displayed high catalytic activity, making Au-CeO2(1 1 1) a better CO oxidation catalyst than Au-TiO2(1 1 0) or Au-MgO(1 0 0). An excellent support for gold was found after depositing nanoparticles of ceria on TiO2(1 1 0). The CeOx nanoparticles act as nucleation centers for gold, improving dispersion of the supported metal and helping in the creation of reaction sites efficient for the adsorption of CO and the dissociation of the O2 molecule. High-surface area catalysts were prepared by depositing gold on ceria nanorods and CeOx/TiO2 powders. The samples were tested for the low-temperature (10–70 °C) oxygen-rich (1%CO/4%O2/He) CO oxidation reaction after pre-oxidation (20%O2/He, 300 °C) and pre-reduction (5%H2/He, 300 °C) treatments. Moreover, synchrotron-based operando X-ray diffraction (XRD) and X-ray absorption (XAS) spectroscopy were used to study the Au-CeO2 and Au-CeOx/TiO2 catalysts under reaction conditions. Our operando findings indicate that the most active phase of these catalysts for low-temperature CO oxidation consist of small particles of metallic Au dispersed on CeO2 or CeOx/TiO2.

  13. The synergic effect between Mo species and acid sites in Mo/HMCM-22 catalysts for methane aromatization.

    PubMed

    Ma, Ding; Zhu, Qingjun; Wu, Zili; Zhou, Danhong; Shu, Yuying; Xin, Qin; Xu, Yide; Bao, Xinhe

    2005-08-21

    The acid properties of Mo/HMCM-22 catalyst, which is the precursor form of the working catalyst for methane aromatization reaction, and the synergic effect between Mo species and acid sites were studied and characterized by various characterization techniques. It is concluded that Brønsted and Lewis acidities of HMCM-22 are modified due to the introduction of molybdenum. We suggest a monomer of Mo species is formed by the exchange of Mo species with the Brønsted acid sites. On the other hand, coordinate unsaturated sites (CUS) are suggested to be responsible for the formation of newly detected Lewis acid sites. Computer modelling is established and coupling with experimental results, it is then speculated that the effective activation of methane is properly accomplished on Mo species accommodated in the 12 MR supercages of MCM-22 zeolite whereas the Brønsted acid sites in the same channel system play a key role for the formation of benzene. A much more pronounced volcano-typed reactivity curve of the Mo/HMCM-22 catalysts, as compared with that of the Mo/HZSM-5, with respect to Mo loading is found and this can be well understood due to the unique channel structure of MCM-22 zeolite and synergic effect between Mo species and acid sites.

  14. Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions

    NASA Astrophysics Data System (ADS)

    Wang, Qi-Qiang; Gonell, Sergio; Leenders, Stefan H. A. M.; Dürr, Maximilian; Ivanović-Burmazović, Ivana; Reek, Joost N. H.

    2016-03-01

    Tuning reagent and catalyst concentrations is crucial in the development of efficient catalytic transformations. In enzyme-catalysed reactions the substrate is bound—often by multiple non-covalent interactions—in a well-defined pocket close to the active site of the enzyme; this pre-organization facilitates highly efficient transformations. Here we report an artificial system that co-encapsulates multiple catalysts and substrates within the confined space defined by an M12L24 nanosphere that contains 24 endohedral guanidinium-binding sites. Cooperative binding means that sulfonate guests are bound much more strongly than carboxylates. This difference has been used to fix gold-based catalysts firmly, with the remaining binding sites left to pre-organize substrates. This strategy was applied to a Au(I)-catalysed cyclization of acetylenic acid to enol lactone in which the pre-organization resulted in much higher reaction rates. We also found that the encapsulated sulfonate-containing Au(I) catalysts did not convert neutral (acid) substrates, and so could have potential in the development of substrate-selective catalysis and base-triggered on/off switching of catalysis.

  15. Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions.

    PubMed

    Wang, Qi-Qiang; Gonell, Sergio; Leenders, Stefan H A M; Dürr, Maximilian; Ivanović-Burmazović, Ivana; Reek, Joost N H

    2016-03-01

    Tuning reagent and catalyst concentrations is crucial in the development of efficient catalytic transformations. In enzyme-catalysed reactions the substrate is bound-often by multiple non-covalent interactions-in a well-defined pocket close to the active site of the enzyme; this pre-organization facilitates highly efficient transformations. Here we report an artificial system that co-encapsulates multiple catalysts and substrates within the confined space defined by an M12L24 nanosphere that contains 24 endohedral guanidinium-binding sites. Cooperative binding means that sulfonate guests are bound much more strongly than carboxylates. This difference has been used to fix gold-based catalysts firmly, with the remaining binding sites left to pre-organize substrates. This strategy was applied to a Au(I)-catalysed cyclization of acetylenic acid to enol lactone in which the pre-organization resulted in much higher reaction rates. We also found that the encapsulated sulfonate-containing Au(I) catalysts did not convert neutral (acid) substrates, and so could have potential in the development of substrate-selective catalysis and base-triggered on/off switching of catalysis. PMID:26892553

  16. Role of Tricoordinate Al Sites in CH3ReO3/Al2O3 Olefin Metathesis Catalysts.

    PubMed

    Valla, Maxence; Wischert, Raphael; Comas-Vives, Aleix; Conley, Matthew P; Verel, René; Copéret, Christophe; Sautet, Philippe

    2016-06-01

    Re2O7 supported on γ-alumina is an alkene metathesis catalyst active at room temperature, compatible with functional groups, but the exact structures of the active sites are unknown. Using CH3ReO3/Al2O3 as a model for Re2O7/Al2O3, we show through a combination of reactivity studies, in situ solid-state NMR, and an extensive series of DFT calculations, that μ-methylene structures (Al-CH2-ReO3-Al) containing a Re═O bound to a tricoordinated Al (AlIII) and CH2 bound to a four-coordinated Al (AlIVb) are the precursors of the most active sites for olefin metathesis. The resting state of CH3ReO3/Al2O3 is a distribution of μ-methylene species formed by the activation of the C-H bond of CH3ReO3 on different surface Al-O sites. In situ reaction with ethylene results in the formation of Re metallacycle intermediates, which were studied in detail through a combination of solid-state NMR experiments, using labeled ethylene, and DFT calculations. In particular, we were able to distinguish between metallacycles in TBP (trigonal-bipyramidal) and SP (square-pyramidal) geometry, the latter being inactive and detrimental to catalytic activity. The SP sites are more likely to be formed on other Al sites (AlIVa/AlIVa). Experimentally, the activity of CH3ReO3/Al2O3 depends on the activation temperature of alumina; catalysts activated at or above 500 °C contain more active sites than those activated at 300 °C. We show that the dependence of catalytic activity on the Al2O3 activation temperature is related to the quantity of available AlIII-defect sites and adsorbed H2O.

  17. Role of Tricoordinate Al Sites in CH3ReO3/Al2O3 Olefin Metathesis Catalysts.

    PubMed

    Valla, Maxence; Wischert, Raphael; Comas-Vives, Aleix; Conley, Matthew P; Verel, René; Copéret, Christophe; Sautet, Philippe

    2016-06-01

    Re2O7 supported on γ-alumina is an alkene metathesis catalyst active at room temperature, compatible with functional groups, but the exact structures of the active sites are unknown. Using CH3ReO3/Al2O3 as a model for Re2O7/Al2O3, we show through a combination of reactivity studies, in situ solid-state NMR, and an extensive series of DFT calculations, that μ-methylene structures (Al-CH2-ReO3-Al) containing a Re═O bound to a tricoordinated Al (AlIII) and CH2 bound to a four-coordinated Al (AlIVb) are the precursors of the most active sites for olefin metathesis. The resting state of CH3ReO3/Al2O3 is a distribution of μ-methylene species formed by the activation of the C-H bond of CH3ReO3 on different surface Al-O sites. In situ reaction with ethylene results in the formation of Re metallacycle intermediates, which were studied in detail through a combination of solid-state NMR experiments, using labeled ethylene, and DFT calculations. In particular, we were able to distinguish between metallacycles in TBP (trigonal-bipyramidal) and SP (square-pyramidal) geometry, the latter being inactive and detrimental to catalytic activity. The SP sites are more likely to be formed on other Al sites (AlIVa/AlIVa). Experimentally, the activity of CH3ReO3/Al2O3 depends on the activation temperature of alumina; catalysts activated at or above 500 °C contain more active sites than those activated at 300 °C. We show that the dependence of catalytic activity on the Al2O3 activation temperature is related to the quantity of available AlIII-defect sites and adsorbed H2O. PMID:27140286

  18. Toward "metalloMOFzymes": Metal-Organic Frameworks with Single-Site Metal Catalysts for Small-Molecule Transformations.

    PubMed

    Cohen, Seth M; Zhang, Zhenjie; Boissonnault, Jake A

    2016-08-01

    Metal-organic frameworks (MOFs) are being increasingly studied as scaffolds and supports for catalysis. The solid-state structures of MOFs, combined with their high porosity, suggest that MOFs may possess advantages shared by both heterogeneous and homogeneous catalysts, with few of the shortcomings of either. Herein, efforts to create single-site catalytic metal centers appended to the organic ligand struts of MOFs will be discussed. Reactions important for advanced energy applications, such as H2 production and CO2 reduction, will be highlighted. Examining how these active sites can be introduced, their performance, and their existing limitations should provide direction for design of the next generation of MOF-based catalysts for energy-relevant, small-molecule transformations. Finally, the introduction of second-sphere interactions (e.g., hydrogen bonding via squaramide groups) as a possible route to enhancing the activity of these metal centers is reported. PMID:27231968

  19. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia

    2009-09-22

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  20. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    SciTech Connect

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  1. Schiff base structured acid-base cooperative dual sites in an ionic solid catalyst lead to efficient heterogeneous knoevenagel condensations.

    PubMed

    Zhang, Mingjue; Zhao, Pingping; Leng, Yan; Chen, Guojian; Wang, Jun; Huang, Jun

    2012-10-01

    An acid-base bifunctional ionic solid catalyst [PySaIm](3)PW was synthesized by the anion exchange of the ionic-liquid (IL) precursor 1-(2-salicylaldimine)pyridinium bromide ([PySaIm]Br) with the Keggin-structured sodium phosphotungstate (Na(3) PW). The catalyst was characterized by FTIR, UV/Vis, XRD, SEM, Brunauer-Emmett-Teller (BET) theory, thermogravimetric analysis, (1)H NMR spectroscopy, ESI-MS, elemental analysis, and melting points. Together with various counterparts, [PySaIm](3)PW was evaluated in Knoevenagel condensation under solvent and solvent-free conditions. The Schiff base structure attached to the IL cation of [PySaIm](3)PW involves acidic salicyl hydroxyl and basic imine, and provides a controlled nearby position for the acid-base dual sites. The high melting and insoluble properties of [PySaIm](3)PW are relative to the large volume and high valence of PW anions, as well as the intermolecular hydrogen-bonding networks among inorganic anions and IL cations. The ionic solid catalyst [PySaIm](3)PW leads to heterogeneous Knoevenagel condensations. In solvent-free condensation of benzaldehyde with ethyl cyanoacetate, it exhibits a conversion of 95.8 % and a selectivity of 100 %; the conversion is even much higher than that (78.2 %) with ethanol as a solvent. The solid catalyst has a convenient recoverability with only a slight decrease in conversion following subsequent recyclings. Furthermore, the new catalyst is highly applicable to many substrates of aromatic aldehydes with activated methylene compounds. On the basis of the characterization and reaction results, a unique acid-base cooperative mechanism within a Schiff base structure is proposed and discussed, which thoroughly explains not only the highly efficient catalytic performance of [PySaIm](3)PW, but also the lower activities of various control catalysts.

  2. Copper-catalyst-controlled site-selective allenylation of ketones and aldehydes with propargyl boronates.

    PubMed

    Fandrick, Keith R; Ogikubo, Junichi; Fandrick, Daniel R; Patel, Nitinchandra D; Saha, Jaideep; Lee, Heewon; Ma, Shengli; Grinberg, Nelu; Busacca, Carl A; Senanayake, Chris H

    2013-03-15

    A practical and highly site-selective copper-PhBPE-catalyst-controlled allenylation with propargyl boronates has been developed. The methodology has shown to be tolerant of diverse ketones and aldehydes providing the allenyl adducts in high selectivity. The BPE ligand and boronate substituents were shown to direct the site selectivity for which either propargyl or allenyl adducts can be acquired in high selectivity. A model is proposed that explains the origin of the site selectivity. PMID:23438081

  3. HDS activity and characterization of zeolite-supported nickel sulfide catalysts

    SciTech Connect

    Welters, W.J.J.; Vorbeck, G.; Haan, J.W. de; Beer, V.H.J. de; Santen, R.A. van; Zandbergen, H.W.

    1994-11-01

    Catalysts of nickel sulfide supported on zeolite Y have been prepared (by impregnation or ion exchange) and characterized by means of thiophene hydrodesulfurization (HDS), sulfur analysis, temperature-programmed sulfiding, {sup 129}Xe-NMR, HREM and dynamic oxygen chemisorption. The catalysts show large differences in catalytic behavior dependent on the preparation method (impregnation vs ion exchange) and the pretreatment conditions (method of sulfidation). Especially the ion-exchanged catalysts show a high initial activity, but due to the presence of acid sites deactivation is very strong. The initial activity of these catalysts can be improved significantly by drying prior to sulfidation. In all cases sulfidation results in quantitative formation of nickel sulfide, with Ni{sub 3}S{sub 2} being the main product. Occasionally, also some NiS appears to be present. The major part of the nickel sulfide phase is invariably located on the outside of the zeolite particles. The fraction of nickel sulfide in the zeolite pores depends on the preparation method and the pretreatment conditions. The differences in catalytic activity are ascribed not only to variations in overall nickel sulfide dispersion but also to the acidity of the support, and the presence of very active small nickel sulfide clusters in the pores of the zeolite can have a strong influence on the thiophene HDS activity. 40 refs., 13 figs., 3 tabs.

  4. Structural and mechanistic basis for the high activity of Fe–N–C catalysts toward oxygen reduction

    SciTech Connect

    Li, Jingkun; Ghoshal, Shraboni; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Halevi, Barr; McKinney, Samuel; McCool, Geoff; Ma, Chunrong; Yuan, Xianxia; Ma, Zi-Feng; Mukerjee, Sanjeev; Jia, Qingying

    2016-01-01

    The development of efficient non-platinum group metal (non-PGM) catalysts for oxygen reduction reaction (ORR) is of paramount importance for clean and sustainable energy storage and conversion devices. The major bottleneck in developing Fe–N–C materials as the leading non-PGM catalysts lies in the poor understanding of the nature of active sites and reaction mechanisms. Herein, we report a scalable metal organic framework-derived Fe–N–C catalyst with high ORR activity demonstrated in practical H2/air fuel cells, and an unprecedented turnover frequency (TOF) in acid in rotating disk electrode. By characterizing the catalyst under both ex situ and operando conditions using combined microscopic and spectroscopic techniques, we show that the structures of active sites under ex situ and working conditions are drastically different. Resultantly, the active site proposed here, a non-planar ferrous Fe–N4 moiety embedded in distorted carbon matrix characterized by a high Fe2+/3+ redox potential, is in contrast with those proposed hitherto derived from ex situ characterizations. This site reversibly switches to an in-plane ferric Fe–N4 moiety poisoned by oxygen adsorbates during the redox transition, with the population of active sites controlled by the Fe2+/3+ redox potential. The unprecedented TOF of the active site is correlated to its near-optimal Fe2+/3+ redox potential, and essentially originated from its favorable biomimetic dynamic nature that balances the site-blocking effect and O2 dissociation. The porous and disordered carbon matrix of the catalyst plays pivotal roles for its measured high ORR activity by hosting high population of reactant-accessible active sites.

  5. Activity and Stability of Nanoscale Oxygen Reduction Catalysts

    SciTech Connect

    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).

  6. Efficient solid acid catalyst containing Lewis and Brønsted Acid sites for the production of furfurals.

    PubMed

    Mazzotta, Michael G; Gupta, Dinesh; Saha, Basudeb; Patra, Astam K; Bhaumik, Asim; Abu-Omar, Mahdi M

    2014-08-01

    Self-assembled nanoparticulates of porous sulfonated carbonaceous TiO2 material that contain Brønsted and Lewis acidic sites were prepared by a one-pot synthesis method. The material was characterized by XRD, FTIR spectroscopy, NH3 temperature-programmed desorption, pyridine FTIR spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, N2 -sorption, atomic absorbance spectroscopy, and inductively coupled plasma optical emission spectroscopy. The carbonaceous heterogeneous catalyst (Glu-TsOH-Ti) with a Brønsted-to-Lewis acid density ratio of 1.2 and more accessible acid sites was effective to produce 5-hydroxymethylfurfural and furfural from biomass-derived mono- and disaccharides and xylose in a biphasic solvent that comprised water and biorenewable methyltetrahydrofuran. The catalyst was recycled in four consecutive cycles with a total loss of only 3 % activity. Thus, Glu-TsOH-Ti, which contains isomerization and dehydration catalytic sites and is based on a cheap and biorenewable carbon support, is a sustainable catalyst for the production of furfurals, platform chemicals for biofuels and chemicals. PMID:24807741

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

    NASA Astrophysics Data System (ADS)

    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

  8. Studies of the activity of catalysts based on heteropolyacids

    NASA Astrophysics Data System (ADS)

    Turek, Wincenty; Lapkowski, Mieczyslaw; Debiec, Joanna; Krowiak, Agnieszka

    2005-10-01

    The catalytic activity of samples such as PPy(H 4SiW 12O 40), PPy(H 5PMo 10V 2O 40), PPy(H 2Fe(III)PMo 10V 2O 40), PPy(H 3Cu(II)PMo 10V 2O 40) has been examined in two different test reactions. The acid-base and oxidation-reduction properties were studied using the conversion of isopropyl alcohol to propene and acetone. Redox ability of catalysts was examined in the reaction of oxidation of allyl alcohol to glycidol. It was found that the activity of catalysts in the oxidation of allyl alcohol increases as the oxidation properties determined from the conversion of isopropyl alcohol increase. It was also observed that stronger oxidation-reduction properties of the catalyst result in a high rate of the consecutive reaction of glycidol to 3-hydroxypropanone. The phase composition of catalysts was determined by means of X-ray diffraction (XRD).

  9. Investigating the performance of CoxOy/activated carbon catalysts for ethyl acetate catalytic combustion

    NASA Astrophysics Data System (ADS)

    Xie, Hongmei; Zhao, Xiaoping; Zhou, Guilin; He, Xiaoling; Lan, Hai; Jiang, Zongxuan

    2015-01-01

    The catalytic properties of Co-supported activated carbon (AC) catalysts for ethyl acetate catalytic elimination in air were investigated. Results showed that air atmosphere promoted the generation of high-valence state cobalt oxides, and promote the production of reactive oxygen species (ROS) in the Co3O4/AC catalyst. ROS crucially functioned in improving the catalytic activity of Co3O4/AC catalysts. Therefore, CoACA catalyst prepared in air exhibited higher catalytic activity than CoACN catalyst prepared in nitrogen, and CoACA catalyst led to high ethyl acetate conversion (>93%) and stability at a low reaction temperature (210 °C).

  10. XAFS study on structure-activity correlations of α-Co(OH)2 nanosheets water oxidation catalysts

    NASA Astrophysics Data System (ADS)

    Huang, Junheng; Liu, Qinghua; Yao, Tao; Pan, Zhiyun; Wei, Shiqiang

    2016-05-01

    Understanding the structure-activity of the metal hydroxide materials is critical to the design of an efficient oxygen evolution reaction (OER) catalyst for water oxidation. A challenge is to identify and collect surface active site relative to bulk. Here, we have prepared an ultrathin α-Co(OH)2 nanosheet with large exposed surface Co sites as an high-efficiency O2 evolution catalyst. Using XAFS technique, we have investigated the oxidation state and local structural evolutions of the α-Co(OH)2 nanosheets catalyst. A coordination-miss Co sites (CoO6-x) with oxidation state of +3.3 on the nanosheet surface is revealed after the OER procedure, indicating the in situ formation of y-CoOOH nanosheet is a key factor leading to an enhanced water oxidation performance.

  11. Quantifying accessible sites and reactivity on titania–silica (photo)catalysts: Refining TOF calculations

    SciTech Connect

    Eaton, Todd R.; Campos, Michael P.; Gray, Kimberly A.; Notestein, Justin M.

    2014-01-01

    It can be difficult to determine the number of active atoms accessible to the fluid phase in mixed oxide catalysts, as required for obtaining true turnover frequencies (TOF). Here, we utilize the selective titration of surface Ti atoms with phenylphosphonic acid (PPA) on TiO2–SiO2 materials to estimate the number of reactant-accessible sites. TiO2–SiO2 composites were synthesized over a range of Ti loadings from grafting of titanocene dichloride (Cp2TiCl2) or tetraethoxy orthotitanate (TEOT) on SiO2 and sol–gel co-hydrolysis of Si and Ti alkoxides. The materials were characterized by DRUV–vis, XRD, BET, and XANES. Despite the significant morphological and electronic differences, materials prepared by Cp2TiCl2 and TEOT yielded a near-constant TOF of 0.14 h-1 (±0.04) across Ti loadings, for benzyl alcohol photooxidation, when normalizing rates by sites titrated by PPA. The fraction of Ti atoms titrated by PPA was strongly dependent on synthesis method and surface density. PPA titration and benzyl alcohol photooxidation may be useful measures of surface accessibility in other supported oxides.

  12. Conversion of isoamyl alcohol over acid catalysts: Reaction dependence on nature of active centers

    SciTech Connect

    Babu, G.P.; Murthy, R.S.; Krishnan, V.

    1997-02-01

    Acid catalysts are known to catalyze the dehydration of alcohols. In addition some oxide catalysts with basic properties have also been shown to play an important role in such dehydration reactions. The dehydration of aliphatic alcohols to olefins has been studied in detail using alumina silica-alumina and zeolite catalysts. The olefin products further undergo isomerization in presence of acidic sites. The reaction of isoamyl alcohol on catalytic surfaces has not been investigated in greater detail. The dehydration of isoamyl alcohol is of considerable interest in fine chemicals. Isoamyl alcohol may also undergo dehydrogenation as observed in the case of n-butanol. The scope of the present work is to identify the nature of the active sites selective for dehydration and dehydrogenation of isoamyl alcohol and to modify the active sites to promote isomerization of dehydrated products. Four catalytic surfaces on which the acidic strength can be varied, as well as selectively suppressed, are chosen for this study. 17 refs., 1 fig., 3 tabs.

  13. Activity and stability of pyrolyzed iron ethylenediaminetetraacetic acid as cathode catalyst in microbial fuel cells.

    PubMed

    Wang, Li; Liang, Peng; Zhang, Jian; Huang, Xia

    2011-04-01

    A low-cost and effective iron-chelated catalyst was developed as an electrocatalyst for the oxygen reduction reaction (ORR) in microbial fuel cells (MFCs). The catalyst was prepared by pyrolyzing carbon mixed iron-chelated ethylenediaminetetraacetic acid (PFeEDTA/C) in an argon atmosphere. Cyclic voltammetry measurements showed that PFeEDTA/C had a high catalytic activity for ORR. The MFC with a PFeEDTA/C cathode produced a maximum power density of 1122 mW/m(2), which was close to that with a Pt/C cathode (1166 mW/m(2)). The PFeEDTA/C was stable during an operation period of 31 days. Based on X-ray diffraction and X-ray photoelectron spectroscopy measurements, quaternary-N modified with iron might be the active site for the oxygen reduction reaction. The total cost of a PFeEDTA/C catalyst was much lower than that of a Pt catalyst. Thus, PFeEDTA/C can be a good alternative to Pt in MFC practical applications.

  14. Structure-activity relationship of CuO/MnO2 catalysts in CO oxidation

    NASA Astrophysics Data System (ADS)

    Qian, Kun; Qian, Zhaoxia; Hua, Qing; Jiang, Zhiquan; Huang, Weixin

    2013-05-01

    A series of CuO/MnO2 catalysts with different CuO loadings were synthesized by the incipient wetness impregnation method. The catalysts were characterized by N2 adsorption-desorption isotherms, powder X-ray diffraction, X-ray photoelectron spectroscopy, H2-temperature programmed reduction, CO-temperature programmed reduction and scanning electron microscope. The CuO/MnO2 catalysts with CuO loading of 1-40% exhibit almost the same catalytic performance toward CO oxidation while those with higher CuO loadings exhibit a much poorer catalytic activity. The structural characterization results demonstrate that the CuO-MnO2 interface is the active site for CO oxidation in CuO/MnO2 catalysts and CO oxidation over CuO/MnO2 probably follows the interfacial reaction mechanism in which CO chemisorbed on CuO reacts with oxygen species on MnO2 at the CuO-MnO2 interface.

  15. NREL Team Creates High-Activity, Durable Platinum Extended Surface Catalyst for Fuel Cells (Fact Sheet)

    SciTech Connect

    Not Available

    2011-02-01

    Researchers with NREL's Fuel Cell team showed that platinum can replace copper nanowires in such a way that high-surface-area and high-specific-activity catalysts are produced, potentially allowing for lower-cost catalysts.

  16. Alumina-supported sulfided catalysts: V. Effect of P and F on the catalytic activity of hydrodesulfurization sulfided catalysts

    SciTech Connect

    Startsev, A.N.; Klimov, O.V.; Kalinkin, A.V.; Mastikhin, V.M.

    1994-07-01

    Phosphorus and flourine additives incorporated into the Ni-Mo/Al{sub 2}O{sub 3} sulfided catalysts on various stages of their preparation considerably lower the activation energy of the thiophene hydrogenolysis reaction. The interaction of promoting additives with the active component of the hydrodesulfurization catalyst is proved by XPS and {sup 31}P NMR. The effect of additives is discussed in terms of a synchronous mechanism involving interaction of reacting molecules in the coordination sphere of a bimetallic sulfide compound.

  17. Lewis acid activation of carbodicarbene catalysts for Rh-catalyzed hydroarylation of dienes.

    PubMed

    Roberts, Courtney C; Matías, Desirée M; Goldfogel, Matthew J; Meek, Simon J

    2015-05-27

    The activation of carbodicarbene (CDC)-Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydro-heteroarylation of dienes (up to 98% yield and >98:2 γ:α). Reactions are promoted by 5 mol % of a readily available tridentate (CDC)-Rh complex in the presence of an inexpensive lithium salt. The reaction is compatible with a variety of terminal and internal dienes and tolerant of ester, alkyl halide, and boronate ester functional groups. X-ray data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. PMID:25961506

  18. Salt site performance assessment activities

    SciTech Connect

    Kircher, J.F.; Gupta, S.K.

    1983-01-01

    During this year the first selection of the tools (codes) for performance assessments of potential salt sites have been tentatively selected and documented; the emphasis has shifted from code development to applications. During this period prior to detailed characterization of a salt site, the focus is on bounding calculations, sensitivity and with the data available. The development and application of improved methods for sensitivity and uncertainty analysis is a focus for the coming years activities and the subject of a following paper in these proceedings. Although the assessments to date are preliminary and based on admittedly scant data, the results indicate that suitable salt sites can be identified and repository subsystems designed which will meet the established criteria for protecting the health and safety of the public. 36 references, 5 figures, 2 tables.

  19. Heterogeneous ceria catalyst with water-tolerant Lewis acidic sites for one-pot synthesis of 1,3-diols via Prins condensation and hydrolysis reactions.

    PubMed

    Wang, Yehong; Wang, Feng; Song, Qi; Xin, Qin; Xu, Shutao; Xu, Jie

    2013-01-30

    The use of a heterogeneous Lewis acid catalyst, which is insoluble and easily separable during the reaction, is a promising option for hydrolysis reactions from both environmental and practical viewpoints. In this study, ceria showed excellent catalytic activity in the hydrolysis of 4-methyl-1,3-dioxane to 1,3-butanediol in 95% yield and in the one-pot synthesis of 1,3-butanediol from propylene and formaldehyde via Prins condensation and hydrolysis reactions in an overall yield of 60%. In-depth investigations revealed that ceria is a water-tolerant Lewis acid catalyst, which has seldom been reported previously. The ceria catalysts showed rather unusual high activity in hydrolysis, with a turnover number (TON) of 260, which is rather high for bulk oxide catalysts, whose TONs are usually less than 100. Our conclusion that ceria functions as a Lewis acid catalyst in hydrolysis reactions is firmly supported by thorough characterizations with IR and Raman spectroscopy, acidity measurements with IR and (31)P magic-angle-spinning NMR spectroscopy, Na(+)/H(+) exchange tests, analyses using the in situ active-site capping method, and isotope-labeling studies. A relationship between surface vacancy sites and catalytic activity has been established. CeO(2)(111) has been confirmed to be the catalytically active crystalline facet for hydrolysis. Water has been found to be associatively adsorbed on oxygen vacancy sites with medium strength, which does not lead to water dissociation to form stable hydroxides. This explains why the ceria catalyst is water-tolerant. PMID:23228093

  20. A simple synthesis method of sulfur-free Fe-N-C catalyst witih high ORR activity

    SciTech Connect

    Ding, Zhongfen; Johnston, Christina M; Zelenay, Piotr

    2010-01-01

    To try to deconvolute which factors affect the activity and durability of metal-nitrogen-carbon (M-N-C) type non-precious catalysts for oxygen reduction reaction (ORR), M-N-C catalysts based on ion chloride, polyaniline (PANI) and Ketjen Black carbon support were synthesized using different synthetic conditions. The catalysts were characterized electrochemically and tested as cathodes for Hydrogen fuel cells. PANI is usually chemically oxidative polymerized using ammonium persulfate (APS) as oxidant. To eliminate sulfur in the synthesized catalysts, a simple synthesis method using ion chloride as oxidant for aniline polymerization was developed. Two different aniline polymerization conditions led to very different product morphologies. Synthesized at low initial proton concentration, the final product was composed of dense micrometer sized particles. A decomposable salt was found to be able to prohibit PANI cross linking during the drying and annealing process and thus led to porous product. The porous catalyst has much higher ORR activity than the dense product due to more accessible active sites. Synthesized at high proton concentration, the catalyst appeared to be porous. The decomposable salt treatment did not make too much improvement in the porous structure and electrochemical activity. However, fuel cell testing using air as cathode feeder indicates that the salt treatment improves mass transfer in the cathode layer. Catalyst synthesized using this simple method has performance comparable to our state-of-the art catalyst synthesized in a much more complicated procedure. The factor that sulfur sources are completely eliminated in the synthesis suggests that sulfur is not necessary for the ORR catalysis activity.

  1. Pd/MgO: Catalyst characterization and phenol hydrogenation activity

    SciTech Connect

    Claus, P.; Berndt, H.; Mohr, C.; Radnik, J.; Shin, E.J.; Keane, M.A.

    2000-05-15

    The gas-phase hydrogenation of phenol has been studied over a 1% w/w Pd/MgO catalyst prepared by impregnation of MgO with (NH{sub 4}){sub 2}PdCl{sub 6}. The catalyst precursor was activated by precalcination in air at 473 K followed by reduction in hydrogen at 573 K. Temperature-programmed reduction/desorption has revealed the presence of ammonium carbonate and/or ammonium hydrogen carbonate on the active surface in addition to a metallic palladium component. Whereas the latter was not detectable by X-ray diffraction due to the high metal dispersion, transmission electron microscopy revealed that the mean palladium particle diameter is 1.3 {+-} 0.2 nm, which corresponds to a palladium dispersion of D{sub Pd} = 71%. Impregnation followed by calcination is shown to transform MgO to Mg(OH){sub 2} while the additional reduction step generates a surface phase that is composed of both needle-like Periclase MgO and Mg(OH){sub 2}. X-ray photoelectron spectrometric analyses of the activated catalyst has established the presence of zero-valent palladium which appears to be electron rich as a result of metal-support interaction; a degree of palladium charging is also evident as well as residual surface chlorine. The effects on fractional phenol conversion and reaction selectivity of varying such process variables as reaction time, temperature, and phenol molar feed rate are considered and the possibility of thermodynamic limitations is addressed. Hydrogenation was observed to proceed in a stepwise fashion with cyclohexanone as the partially hydrogenated product and cyclohexanol as the fully hydrogenated product. The catalyst delivered a 96% selectivity with respect to cyclohexanone production at 423 K but the cyclohexanone yield decreased at higher temperatures as conversion declined and cyclohexanol was increasingly preferred. Conversion and selectivity were both stable with prolonged catalyst use, i.e., time on stream in excess of 55 h.

  2. Designing for selectivity: weak interactions and the competition for reactive sites on gold catalysts.

    PubMed

    Siler, C G F; Madix, R J; Friend, C M

    2016-07-01

    A major challenge in heterogeneous catalysis is controlling reaction selectivity, especially in complex environments. When more than one species is present in the gas mixture, the competition for binding sites on the surface of a catalyst is an important factor in determining reaction selectivity and activity. We establish an experimental hierarchy for the binding of a series of reaction intermediates on Au(111) and demonstrate that this hierarchy accounts for reaction selectivity on both the single crystal surface and under operating catalytic conditions at atmospheric pressure using a nanoporous Au catalyst. A partial set of measurements of relative binding has been measured by others on other catalyst materials, including Ag, Pd and metal oxide surfaces; a comparison demonstrates the generality of this concept and identifies differences in the trends. Theoretical calculations for a subset of reactants on Au(111) show that weak van der Waals interactions are key to predicting the hierarchy of binding strengths for alkoxides bound to Au(111). This hierarchy is key to the control of the selectivity for partial oxidation of alcohols to esters on both Au surfaces and under working catalytic conditions using nanoporous gold. The selectivity depends on the competition for active sites among key intermediates. New results probing the effect of fluorine substitution are also presented to extend the relation of reaction selectivity to the hierarchy of binding. Motivated by an interest in synthetic manipulation of fluorinated organics, we specifically investigated the influence of the -CF3 group on alcohol reactivity and selectivity. 2,2,2-Trifluoroethanol couples on O-covered Au(111) to yield CF3CH2O-C([double bond, length as m-dash]O)(CF3), but in the presence of methanol or ethanol it preferentially forms the respective 2,2,2-trifluoroethoxy-esters. The ester is not the dominant product in any of these cases, though, indicating that the rate of β-H elimination from

  3. Sol immobilization technique: a delicate balance between activity, selectivity and stability for gold catalyst

    SciTech Connect

    Villa, Alberto; Wang, Di; Veith, Gabriel M; Prati, Laura

    2013-01-01

    Sol immobilization is a widely used method to prepare gold catalysts. The presence of the protective layer can have a significant influence on catalyst properties by mediating metal-support and reactantmetal interactions. This paper details the effect of a polyvinyl alcohol (PVA) protecting groups on the activity of a supported gold catalysts as well as its selectivity towards glycerol oxidation.

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

    PubMed

    de Brites-Nóbrega, Fernanda F; Polo, Aldino N B; Benedetti, Angélica M; Leão, Mônica M D; Slusarski-Santana, Veronice; Fernandes-Machado, Nádia R C

    2013-12-15

    This study aimed to evaluate the photocatalytic activity of ZnO and Nb2O5 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 Nb2O5/NaX, Nb2O5/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 2h 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.

  5. The role of acidic sites and the catalytic reaction pathways on the Rh/ZrO2 catalysts for ethanol steam reforming.

    PubMed

    Zhong, Ziyi; Ang, Hanwee; Choong, Catherine; Chen, Luwei; Huang, Lin; Lin, Jianyi

    2009-02-01

    Rh catalysts supported on ZrO(2)-based oxides were studied for ethanol steam reforming (SR) reaction. Pure ZrO(2) as the support resulted in higher H(2) production yield compared to the ZrO(2) oxide decorated with CeO(2), Al(2)O(3), La(2)O(3) or Li(2)O at the reaction temperature of 300 degrees C. Above 450 degrees C, all the catalysts exhibited similar catalytic activity. However, at low reaction temperatures (below 400 degrees C), a significant enhancement in the catalytic activity, selectivity and stability was achieved by replacing the ZrO(2) support prepared by a precipitation method (ZrO(2)-CP) with that prepared by a hydrothermal method (ZrO(2)-HT). A deactivation was observed during the EtOH SR reaction at 300 degrees C on the two catalysts of Rh/ZrO(2)-CP and Rh/ZrO(2)-HT. NH(3)-TPD experiments confirmed that the ZrO(2)-HT support had two types of acidic sites while the ZrO(2)-CP support had only one type of weak acidic sites. DRIFTS studies showed that the absorption of EtOH molecules was strong on the Rh/ZrO(2)-HT catalyst and a number of C(2) oxygenates were accumulated on the catalyst surface. Meanwhile, the EtOH absorption on the Rh/ZrO(2)-CP catalyst was weak and the accumulation of CO, carbonate and CH(x) was observed. It is concluded that the relatively strong Lewis acidic sites in the Rh/ZrO(2)-HT catalyst is responsible for the strong absorption of EtOH molecules, and the subsequent C-H breakage step (formation of acetaldehyde or called as dehydrogenation reaction) is a fast reaction on it; on the Rh/ZrO(2)-CP catalyst, the EtOH adsorption was weak and the C-C breakage was the dominating reaction which led to the accumulation of surface CO, CH(x) and CO(2) species. Therefore, it is believed that, in order to promote the absorption of EtOH molecules and to reduce the formation of metastable carbonaceous species (C(2) oxygenates) during the reaction, the catalyst should be enhanced both with Lewis acidity and with C-C bond breakage function. Also

  6. Identifying active functionalities on few-layered graphene catalysts for oxidative dehydrogenation of isobutane.

    PubMed

    Dathar, Gopi Krishna Phani; Tsai, Yu-Tung; Gierszal, Kamil; Xu, Ye; Liang, Chengdu; Rondinone, Adam J; Overbury, Steven H; Schwartz, Viviane

    2014-02-01

    The general consensus in the studies of nanostructured carbon catalysts for oxidative dehydrogenation (ODH) of alkanes to olefins is that the oxygen functionalities generated during synthesis and reaction are responsible for the catalytic activity of these nanostructured carbons. Identification of the highly active oxygen functionalities would enable engineering of nanocarbons for ODH of alkanes. Few-layered graphenes were used as model catalysts in experiments to synthesize reduced graphene oxide samples with varying oxygen concentrations, to characterize oxygen functionalities, and to measure the activation energies for ODH of isobutane. Periodic density functional theory calculations were performed on graphene nanoribbon models with a variety of oxygen functionalities at the edges to calculate their thermal stability and to model reaction mechanisms for ODH of isobutane. Comparing measured and calculated thermal stability and activation energies leads to the conclusion that dicarbonyls at the zigzag edges and quinones at armchair edges are appropriately balanced for high activity, relative to other model functionalities considered herein. In the ODH of isobutane, both dehydrogenation and regeneration of catalytic sites are relevant at the dicarbonyls, whereas regeneration is facile compared with dehydrogenation at quinones. The catalytic mechanism involves weakly adsorbed isobutane reducing functional oxygen and leaving as isobutene, and O2 in the feed, weakly adsorbed on the hydrogenated functionality, reacting with that hydrogen and regenerating the catalytic sites.

  7. Correlations between mass activity and physicochemical properties of Fe/N/C catalysts for the ORR in PEM fuel cell via 57Fe Mössbauer spectroscopy and other techniques.

    PubMed

    Kramm, Ulrike I; Lefèvre, Michel; Larouche, Nicholas; Schmeisser, Dieter; Dodelet, Jean-Pol

    2014-01-22

    The aim of this work is to clarify the origin of the enhanced PEM-FC performance of catalysts prepared by the procedures described in Science 2009, 324, 71 and Nat. Commun. 2011, 2, 416. Catalysts were characterized after a first heat treatment in argon at 1050 °C (Ar) and a second heat treatment in ammonia at 950 °C (Ar + NH3). For the NC catalysts a variation of the nitrogen precursor was also implemented. (57)Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, neutron activation analysis, and N2 sorption measurements were used to characterize all catalysts. The results were correlated to the mass activity of these catalysts measured at 0.8 V in H2/O2 PEM-FC. It was found that all catalysts contain the same FeN4-like species already found in INRS Standard (Phys. Chem. Chem. Phys. 2012, 14, 11673). Among all FeN4-like species, only D1 sites, assigned to FeN4/C, and D3, assigned to N-FeN2+2 /C sites, were active for the oxygen reduction reaction (ORR). The difference between INRS Standard and the new catalysts is simply that there are many more D1 and D3 sites available in the new catalysts. All (Ar + NH3)-type catalysts have a much larger porosity than Ar-type catalysts, while the maximum number of their active sites is only slightly larger after a second heat treatment in NH3. The large difference in activity between the Ar-type catalysts and the Ar + NH3 ones stems from the availability of the sites to perform ORR, as many sites of the Ar-type catalysts are secluded in the material, while they are available at the surface of the Ar + NH3-type catalysts.

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

    PubMed

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

    2013-07-01

    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.

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

    PubMed

    Severn, John R; Chadwick, John C

    2013-07-01

    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 transition metal. Catalyst productivity is dependent on the balance between activity and stability. Immobilisation can lead to a lower proportion of active species and therefore lower initial polymerisation activity, but nevertheless give higher polymer yields in cases where increased catalyst stability is obtained. Important physical factors are support porosity and the ability of a support to undergo progressive fragmentation during polymerisation, facilitating monomer diffusion through the growing catalyst/polymer particle. This article illustrates the importance of these factors in olefin polymerisation with both early- and late-transition metal catalysts, with particular reference to the use of silica and magnesium chloride supports as well as to effects of immobilisation on polymer structure and properties. PMID:23467461

  10. Support chemistry, surface area, and preparation effects on sulfided NiMo catalyst activity

    SciTech Connect

    Gardner, T.J.; McLaughlin, L.I.; Sandoval, R.S.

    1996-06-01

    Hydrous Metal Oxides (HMOs) are chemically synthesized materials which contain a homogeneous distribution of ion exchangeable alkali cations that provide charge compensation to the metal-oxygen framework. In terms of the major types of inorganic ion exchangers defined by Clearfield, these amorphous HMO materials are similar to both hydrous oxides and layered oxide ion exchangers (e.g., alkali metal titanates). For catalyst applications, the HMO material serves as an ion exchangeable support which facilitates the uniform incorporation of catalyst precursor species. Following catalyst precursor incorporation, an activation step is required to convert the catalyst precursor to the desired active phase. Considerable process development activities at Sandia National Laboratories related to HMO materials have resulted in bulk hydrous titanium oxide (HTO)- and silica-doped hydrous titanium oxide (HTO:Si)-supported NiMo catalysts that are more active in model reactions which simulate direct coal liquefaction (e.g., pyrene hydrogenation) than commercial {gamma}-Al{sub 2}O{sub 3}-supported NiMo catalysts. However, a fundamental explanation does not exist for the enhanced activity of these novel catalyst materials; possible reasons include fundamental differences in support chemistry relative to commercial oxides, high surface area, or catalyst preparation effects (ion exchange vs. incipient wetness impregnation techniques). The goals of this paper are to identify the key factors which control sulfided NiMo catalyst activity, including those characteristics of HTO- and HTO:Si-supported NiMo catalysts which uniquely set them apart from conventional oxide supports.

  11. Highly durable and active non-precious air cathode catalyst for zinc air battery

    NASA Astrophysics Data System (ADS)

    Chen, Zhu; Choi, Ja-Yeon; Wang, Haijiang; Li, Hui; Chen, Zhongwei

    The electrochemical stability of non-precious FeCo-EDA and commercial Pt/C cathode catalysts for zinc air battery have been compared using accelerated degradation test (ADT) in alkaline condition. Outstanding oxygen reduction reaction (ORR) stability of the FeCo-EDA catalyst was observed compared with the commercial Pt/C catalyst. The FeCo-EDA catalyst retained 80% of the initial mass activity for ORR whereas the commercial Pt/C catalyst retained only 32% of the initial mass activity after ADT. Additionally, the FeCo-EDA catalyst exhibited a nearly three times higher mass activity compared to that of the commercial Pt/C catalyst after ADT. Furthermore, single cell test of the FeCo-EDA and Pt/C catalysts was performed where both catalysts exhibited pseudolinear behaviour in the 12-500 mA cm -2 range. In addition, 67% higher peak power density was observed from the FeCo-EDA catalyst compared with commercial Pt/C. Based on the half cell and single cell tests the non-precious FeCo-EDA catalyst is a very promising ORR electrocatalyst for zinc air battery.

  12. Novel, high-activity hydroprocessing catalysts: Iron group phosphides

    NASA Astrophysics Data System (ADS)

    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

  13. State-Sensitive Monitoring of Active and Promoter Sites. Applications to Au/Titania and Pt-Sn/Silica Catalysts by XAFS Combined with X-Ray Fluorescence Spectrometry

    SciTech Connect

    Izumi, Yasuo; Masih, Dilshad; Candy, Jean-Pierre; Yoshitake, Hideaki; Terada, Yasuko; Tanida, Hajime; Uruga, Tomoya

    2007-02-02

    State-sensitive XAFS was enabled combined with high-energy-resolution ({delta}E = 0.3 eV-5.5 keV) X-ray fluorescence spectrometry and applied to Au sites of Au/TiO2 and Sn promoter sites of Pt-Sn/SiO2. Each state of interfacial Au sites located on Ti/O atoms and negatively/positively charged Aun clusters was discriminated. Feasibility of more direct information of on-site catalysis via frontier orbital-sensitive XAFS was demonstrated.

  14. Trimetallic Au/Pt/Rh Nanoparticles as Highly Active Catalysts for Aerobic Glucose Oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Haijun; Cao, Yingnan; Lu, Lilin; Cheng, Zhong; Zhang, Shaowei

    2015-02-01

    This paper reports the findings of an investigation of the correlations between the catalytic activity for aerobic glucose oxidation and the composition of Au/Pt/Rh trimetallic nanoparticles (TNPs) with average diameters of less than 2.0 nm prepared by rapid injection of NaBH4. The prepared TNPs were characterized by UV-Vis, TEM, and HR-TEM. The catalytic activity of the alloy-structured TNPs for aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with nearly the same particle size. The catalytic activities of the TNP catalysts were dependent not only on the composition, but also on the electronic structure. The high catalytic activities of the Au/Pt/Rh TNPs can be ascribed to the formed negative-charged Au atoms due to electron donation of Rh neighboring atoms acting as catalytically active sites for aerobic glucose oxidation.

  15. Remarkable enhancement of O₂ activation on yttrium-stabilized zirconia surface in a dual catalyst bed.

    PubMed

    Richard, Mélissandre; Can, Fabien; Duprez, Daniel; Gil, Sonia; Giroir-Fendler, Anne; Bion, Nicolas

    2014-10-13

    Yttrium-stabilized zirconia (YSZ) has been extensively studied as an electrolyte material for solid oxide fuel cells (SOFC) but its performance in heterogeneous catalysis is also the object of a growing number of publications. In both applications, oxygen activation on the YSZ surface remains the step that hinders utilization at moderate temperature. It was demonstrated by oxygen isotope exchange that a dual catalyst bed system consisting of two successive LaMnO3 and YSZ beds without intimate contact drastically enhances oxygen activation on the YSZ surface at 698 K. It can be concluded that LaMnO3 activates the triplet ground-state of molecular oxygen into a low-lying singlet state, thereby facilitating the activation of the O2 molecule on the YSZ oxygen vacancy sites. This phenomenon is shown to improve the catalytic activity of the LaMnO3-Pd/YSZ system for the partial oxidation of methane.

  16. Understanding Iron-based catalysts with efficient Oxygen reduction activity from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Hafiz, Hasnain; Barbiellini, B.; Jia, Q.; Tylus, U.; Strickland, K.; Bansil, A.; Mukerjee, S.

    2015-03-01

    Catalysts based on Fe/N/C clusters can support the oxygen-reduction reaction (ORR) without the use of expensive metals such as platinum. These systems can also prevent some poisonous species to block the active sites from the reactant. We have performed spin-polarized calculations on various Fe/N/C fragments using the Vienna Ab initio Simulation Package (VASP) code. Some results are compared to similar calculations obtained with the Gaussian code. We investigate the partial density of states (PDOS) of the 3d orbitals near the Fermi level and calculate the binding energies of several ligands. Correlations of the binding energies with the 3d electronic PDOS's are used to propose electronic descriptors of the ORR associated with the 3d states of Fe. We also suggest a structural model for the most active site with a ferrous ion (Fe2+) in the high spin state or the so-called Doublet 3 (D3).

  17. Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts

    PubMed Central

    Mao, Hui; Yu, Hong; Chen, Jing; Liao, Xuepin

    2013-01-01

    In the field of catalysis, it is highly desired to develop novel catalysts that combine the advantages of both homogeneous and heterogeneous catalysts. Here we disclose that the use of plant pholyphenol as amphiphilic large molecule ligand/stabilizer allows for the preparation of noble metal complex and noble metal nanoparticle catalysts. These catalysts are found to be highly selective and active in aqueous-organic biphasic catalysis of cinnamaldehyde and quinoline, and can be reused at least 3 times without significant loss of activity. Moreover, the catalytic activity and reusability of the catalysts can be rationally controlled by simply adjusting the content of polyphenols in the catalysts. Our strategy may be extended to design a wide range of aqueous-organic biphasic catalysis system. PMID:23863916

  18. Activated Carbon Catalysts for the Production of Hydrogen for the Sulfur-Iodine Thermochemical Water Splitting Cycle

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; Harry W. Rollins; Kyle C Burch; Cristina Deiana; Hugo S. Silva; Maria F. Sardella; Dolly Granados

    2009-05-01

    Seven activated carbon catalysts obtained from a variety of raw material sources and preparation methods were examined for their catalytic activity to decompose hydroiodic acid (HI) to produce hydrogen; a key reaction in the sulfur-iodine (S-I) thermochemical water splitting cycle. Activity was examined under a temperature ramp from 473 to 773 K. Within the group of ligno-cellulosic steam-activated carbon catalysts, activity increased with surface area. However, both a mineral-based steam-activated carbon and a ligno-cellulosic chemically-activated carbon displayed activities lower than expected based on their higher surface areas. In general, ash content was detrimental to catalytic activity while total acid sites, as determined by Bohem’s titrations, seemed to favor higher catalytic activity within the group of steam-activated carbons. These results suggest, one more time, that activated carbon raw materials and preparation methods may have played a significant role in the development of surface characteristics that eventually dictated catalyst activity and stability as well.

  19. Regioselective chromatic orthogonality with light-activated metathesis catalysts.

    PubMed

    Levin, Efrat; Mavila, Sudheendran; Eivgi, Or; Tzur, Eyal; Lemcoff, N Gabriel

    2015-10-12

    The ability to selectively guide consecutive chemical processes towards a preferred pathway by using light of different frequencies is an appealing concept. Herein we describe the coupling of two photochemical reactions, one the photoisomerization and consequent activation of a sulfur-chelated latent olefin-metathesis catalyst at 350 nm, and the other the photocleavage of a silyl protecting group at 254 nm. Depending on the steric stress exerted by a photoremovable neighboring chemical substituent, we demonstrate the selective formation of either five- or six-membered-ring frameworks by light-triggered ring-closing metathesis. The orthogonality of these light-induced reactions allows the initiation of these processes independently and in interchangeable order, according to the wavelength of light used to promote them.

  20. Architecture and active site of particulate methane monooxygenase

    PubMed Central

    Culpepper, Megen A.; Rosenzweig, Amy C.

    2012-01-01

    Particulate methane monooxygenase (pMMO) is an integral membrane metalloenzyme that oxidizes methane to methanol in methanotrophic bacteria, organisms that live on methane gas as their sole carbon source. Understanding pMMO function has important implications for bioremediation applications and for the development of new, environmentally friendly catalysts for the direct conversion of methane to methanol. Crystal structures of pMMOs from three different methanotrophs reveal a trimeric architecture, consisting of three copies each of the pmoB, pmoA, and pmoC subunits. There are three distinct metal centers in each protomer of the trimer, mononuclear and dinuclear copper sites in the periplasmic regions of pmoB and a mononuclear site within the membrane that can be occupied by copper or zinc. Various models for the pMMO active site have been proposed within these structural constraints, including dicopper, tricopper, and diiron centers. Biochemical and spectroscopic data on pMMO and recombinant soluble fragments, denoted spmoB proteins, indicate that the active site involves copper and is located at the site of the dicopper center in the pmoB subunit. Initial spectroscopic evidence for O2 binding at this site has been obtained. Despite these findings, questions remain about the active site identity and nuclearity and will be the focus of future studies. PMID:22725967

  1. Design and Preparation of Supported Au Catalyst with Enhanced Catalytic Activities by Rationally Positioning Au Nanoparticles on Anatase.

    PubMed

    Wang, Liang; Wang, Hong; Rice, Andrew E; Zhang, Wei; Li, Xiaokun; Chen, Mingshu; Meng, Xiangju; Lewis, James P; Xiao, Feng-Shou

    2015-06-18

    A synergistic effect between individual components is crucial for increasing the activity of metal/metal oxide catalysts. The greatest challenge is how to control the synergistic effect to obtain enhanced catalytic performance. Through density functional theory calculations of model Au/TiO2 catalysts, it is suggested that there is strong interaction between Au nanoparticles and Ti species at the edge/corner sites of anatase, which is favorable for the formation of stable oxygen vacancies. Motivated by this theoretical analysis, we have rationally prepared Au nanoparticles attached to edge/corner sites of anatase support (Au/TiO2-EC), confirmed by their HR-TEM images. As expected, this strong interaction is well characterized by Raman, UV-visible, and XPS techniques. Very interestingly, compared with conventional Au catalysts, Au/TiO2-EC exhibits superior catalytic activity in the oxidations using O2. Our approach to controlling Au nanoparticle positioning on anatase to obtain enhanced catalytic activity offers an efficient strategy for developing more novel supported metal catalysts.

  2. Design and Preparation of Supported Au Catalyst with Enhanced Catalytic Activities by Rationally Positioning Au Nanoparticles on Anatase.

    PubMed

    Wang, Liang; Wang, Hong; Rice, Andrew E; Zhang, Wei; Li, Xiaokun; Chen, Mingshu; Meng, Xiangju; Lewis, James P; Xiao, Feng-Shou

    2015-06-18

    A synergistic effect between individual components is crucial for increasing the activity of metal/metal oxide catalysts. The greatest challenge is how to control the synergistic effect to obtain enhanced catalytic performance. Through density functional theory calculations of model Au/TiO2 catalysts, it is suggested that there is strong interaction between Au nanoparticles and Ti species at the edge/corner sites of anatase, which is favorable for the formation of stable oxygen vacancies. Motivated by this theoretical analysis, we have rationally prepared Au nanoparticles attached to edge/corner sites of anatase support (Au/TiO2-EC), confirmed by their HR-TEM images. As expected, this strong interaction is well characterized by Raman, UV-visible, and XPS techniques. Very interestingly, compared with conventional Au catalysts, Au/TiO2-EC exhibits superior catalytic activity in the oxidations using O2. Our approach to controlling Au nanoparticle positioning on anatase to obtain enhanced catalytic activity offers an efficient strategy for developing more novel supported metal catalysts. PMID:26266615

  3. Highly active copper-network catalyst for the direct aldol reaction.

    PubMed

    Ohta, Hidetoshi; Uozumi, Yasuhiro; Yamada, Yoichi M A

    2011-09-01

    The development of a highly active solid-phase catechol-copper network catalyst for direct aldol reaction is described. The catalyst was prepared from an alkyl-chain-linked bis(catechol) and a copper(II) complex. The direct aldol reaction between carbonyl compounds (aldehydes and ketones) and methyl isocyanoacetate was carried out using 0.1-1 mol% [Cu] catalyst to give the corresponding oxazolines at yields of up to 99% and a trans/cis ratio of >99:1. The catalyst was reused with no loss of catalytic activity. A plausible reaction pathway is also described. PMID:21751405

  4. Spectroscopic investigation of heterogeneous Ziegler-Natta catalysts: Ti and Mg chloride tetrahydrofuranates, their interaction compound, and the role of the activator.

    PubMed

    Seenivasan, Kalaivani; Sommazzi, Anna; Bonino, Francesca; Bordiga, Silvia; Groppo, Elena

    2011-07-25

    X-ray powder diffraction (XRPD), Infrared, Raman, and UV/Vis spectroscopy have been used to investigate the structural, vibrational, and optical properties of Ti and Mg chloride tetrahydrofuranates as precursors of heterogeneous Ziegler-Natta catalysts for polyethylene production; as well as their interaction compound (pro-catalyst) and the final catalyst obtained after interaction with the AlR(3) activator. Although the structure of the precursors and of the pro-catalyst were well known, that of the catalyst (obtained by reaction of the pro-catalyst with AlR(3)) was not easily obtainable from XRPD data. IR and Raman spectroscopy provided important information on tetrahydrofuran (thf) coordination and on the ν(M-Cl) region; whereas UV/Vis spectroscopy gave the direct proof on both the formal oxidation state and the coordination environment of the active Ti sites. Those presented herein are among the first direct experimental data on the structure of the active Ti sites in Ziegler-Natta catalysts, and can be used to validate the many computational studies that have been increasing exponentially in the last few decades.

  5. Synchronizing Substrate Activation Rates in Multicomponent Reactions with Metal-Organic Framework Catalysts.

    PubMed

    Aguirre-Díaz, Lina María; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles

    2016-05-01

    A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In8 (OH)6 (popha)6 (H2 O)4 ]⋅3 H2 O (InPF-16), [In(popha)(2,2'-bipy)]⋅3 H2 O (InPF-17), [In3 (OH)3 (popha)2 (4,4'-bipy)]⋅4 H2 O (InPF-18), [In2 (popha)2 (4,4'-bipy)2 ]⋅3 H2 O (InPF-19), [In(OH)(Hpopha)]⋅0.5 (1,7-phen) (InPF-20), and [In(popha)(1,10-phen)]⋅4 H2 O (InPF-21) (InPF=indium polymeric framework, H3 popha=5-(4-carboxy-2-nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent-free cyanosilylation of carbonyl compounds, the one pot Passerini 3-component (P-3CR) and the Ugi 4-component (U-4CR) reactions. In addition, InPF-17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α-aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven-coordinated indium framework of the catalyst InPF-17. This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF-based heterogeneous catalyst for multicomponent reactions.

  6. Fischer-Tropsch activity for non-promoted cobalt-on-alumina catalysts

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2001-01-01

    Cobalt catalysts, and processes employing these inventive catalysts, for hydrocarbon synthesis. The inventive catalyst comprises cobalt on an alumina support and is not promoted with any noble or near noble metals. In one aspect of the invention, the alumina support preferably includes a dopant in an amount effective for increasing the activity of the inventive catalyst. The dopant is preferably a titanium dopant. In another aspect of the invention, the cobalt catalyst is preferably reduced in the presence of hydrogen at a water vapor partial pressure effective to increase the activity of the cobalt catalyst for hydrocarbon synthesis. The water vapor partial pressure is preferably in the range of from 0 to about 0.1 atmospheres.

  7. Effect of pretreatment on the activity of a Ru-promoted Co/Al{sub 2}O{sub 3} Fischer-Tropsch catalyst

    SciTech Connect

    Belambe, A.R.; Oukaci, R.; Goodwin, J.G. Jr.

    1997-02-01

    The effect of calcination and reduction temperatures on the activity of a Ru-promoted Co/Al{sub 2}O{sub 3} catalyst for the CO hydrogenation reaction has been studied. The catalyst was prepared by the incipient wetness impregnation method and calcined and reduced at various temperatures. Along with overall steady-state rate analysis, steady-state isotopic transient kinetic analysis was used to investigate the effect of the pretreatment conditions on the intrinsic activity and coverages of surface intermediates. Catalyst characterization techniques such as XRD, TPR, and hydrogen chemisorption were also used. The calcination temperature was found to have a pronounced effect on the overall activity of the catalyst but not on the intrinsic activity of the catalyst sites. On the other hand, the reduction temperature had only a negligible effect on the overall and intrinsic activities. The decrease in rate at high calcination temperatures was caused by a decrease in the number of surface active sites due to a decrease in the reducibility of the catalyst. Neither the reduction nor the calcination conditions had any effect on chain growth probability. Calcination temperature did have, however, a small effect on CH{sub 4} selectivity. 38 refs., 5 figs., 5 tabs.

  8. Highly active gold-based catalyst for the reaction of benzaldehyde with ethyl diazoacetate.

    PubMed

    Fructos, Manuel R; Díaz-Requejo, M Mar; Pérez, Pedro J

    2009-09-14

    The gold complex [IPrAu(NCMe)]BF(4) catalyzes the reaction of ethyl diazoacetate with benzaldehyde to give mixtures of ethyl 3-oxo-3-phenylpropanoate and ethyl 3-hydroxy-2-phenylacrylate in the first example of a group 11 metal-based catalyst for this transformation; the catalyst activity is improved by a factor of 2500 compared to those of previously reported iron-based catalysts.

  9. Pollution Control Meets Sustainability: Structure-Activity Studies on New Iron Oxide-Based CO Oxidation Catalysts.

    PubMed

    Schoch, Roland; Bauer, Matthias

    2016-08-01

    A new class of catalysts for the oxidation of CO based on iron oxide as a biocompatible, earth-abundant and non-toxic metal is presented. The catalytic activities achieved with these catalysts provide promising milestones towards the substitution of noble metals in CO oxidation catalysts. The catalysts can be obtained by using iron core-shell nanoparticle precursors. The metal used for the shell material determines whether the iron core is integrated in or isolated from the support. The active iron site is effectively integrated into the γ-Al2 O3 support if an aluminum shell is present in the core-shell precursor. When the metal used for the shell is different from the support, an isolated structure is formed. Using this directed synthesis approach, different iron oxide species can be obtained and their structural differences are linked to distinct catalytic activities, as demonstrated by combined in-depth analytical studies using XRD, X-ray absorption spectroscopy (XAS), UV/Vis, and Brunauer-Emmett-Teller (BET) analysis. The key species responsible for high catalytic activity is identified as isolated tetrahedrally coordinated Fe(III) centers, whereas aggregation leads to a reduction in activity.

  10. Hierarchical Pd-Sn Alloy Nanosheet Dendrites: An Economical and Highly Active Catalyst for Ethanol Electrooxidation

    PubMed Central

    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. PMID:23383368

  11. Stabilizing a Platinum1 Single-Atom Catalyst on Supported Phosphomolybdic Acid without Compromising Hydrogenation Activity.

    PubMed

    Zhang, Bin; Asakura, Hiroyuki; Zhang, Jia; Zhang, Jiaguang; De, Sudipta; Yan, Ning

    2016-07-11

    In coordination chemistry, catalytically active metal complexes in a zero- or low-valent state often adopt four-coordinate square-planar or tetrahedral geometry. By applying this principle, we have developed a stable Pt1 single-atom catalyst with a high Pt loading (close to 1 wt %) on phosphomolybdic acid(PMA)-modified active carbon. This was achieved by anchoring Pt on the four-fold hollow sites on PMA. Each Pt atom is stabilized by four oxygen atoms in a distorted square-planar geometry, with Pt slightly protruding from the oxygen planar surface. Pt is positively charged, absorbs hydrogen easily, and exhibits excellent performance in the hydrogenation of nitrobenzene and cyclohexanone. It is likely that the system described here can be extended to a number of stable SACs with superior catalytic activities.

  12. Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C

    DOE PAGES

    Hu, J.; Wu, L.; Kuttiyiel, K.; Goodman, K. R.; Zhang, C.; Zhu, Y.; Vukmirovic, M. B.; White, M. G.; Sasaki, K.; Adzic, R. R.

    2016-06-30

    We describe a new class of core-shell nanoparticle catalysts having edges and vertexes covered by refractory metal oxide that preferentially segregates onto these catalyst sites. The monolayer shell is deposited on the oxidefree core atoms. The oxide on edges and vertexes induces high catalyst’s stability and activity. The catalyst and synthesis are exemplified by fabrication of Au nanoparticles doped by Ti atoms that segregate as oxide onto low–coordination sites of edges and vertexes. Pt monolayer shell deposited on Au sites has the mass and specific activities for the oxygen reduction reaction about 13 and 5 times higher than those ofmore » commercial Pt/C catalysts. The durability tests show no activity loss after 10000 potential cycles from 0.6 to 1.0V. The superior activity and durability of the Ti-Au@Pt catalyst originate from protective Ti oxide located at the most dissolution-prone edge and vertex sites, and Au-supported active and stable Pt shell.« less

  13. Study of hydrocarbon adsorption on oxide catalysts by IR spectroscopy: XIX. Propylene adsorption on a Bi-Mo oxide catalyst and the nature of surface sites

    SciTech Connect

    Davydov, A.A.

    1994-07-01

    The nature of surface sites and propylene adsorption on stoichiometric bismuth molybdate are studied by FTIR spectroscopy. Lewis and Broensted acid centers are revealed at the oxidized catalyst surface using IR spectra of adsorbed ammonia. Lewis acid sites are shown to interact with strong electron-donor ligands (NH{sub 3}), but they do not interact with weak ligands (CO, C{sub 2}H{sub 4}, C{sub 3}H{sub 6}). Weak proton acid sites are found only at the surface of the oxidized sample.

  14. Surface site diffusion and reaction on molecular "organizates" and colloidal catalysts: A geometrical perspective.

    PubMed

    Politowicz, P A; Kozak, J J

    1987-12-01

    We study surface-mediated, diffusion-controlled reactive processes on particles whose overall geometry is homeomorphic to a sphere. Rather than assuming that a coreactant can diffuse freely over the surface of the particle to a target site (reaction center), we consider the case where the coreactant can migrate only among N - 1 satellite sites that are networked to the reaction site by means of a number of pathways or reaction channels. Five distinct lattice topologies are considered and we study the reaction efficiency both for the case where the satellite sites are passive and for the case where reaction may occur with finite probability at these sites. The results obtained for this class of surface problems are compared with those obtained by assuming that the reaction-diffusion process takes place on a planar, two-dimensional surface (lattice). The applicability of our results to surface-mediated processes on "organizates" (cells, vesicles, micelles) and on colloidally dispersed catalyst particles is brought out in the Introduction, and the correspondence between the lattice-based, Markovian approach developed here and Fickian models of surface diffusion, particularly with regard to the exponentiality of the decay, is discussed in the concluding section.

  15. CO oxidation on nanoporous gold: A combined TPD and XPS study of active catalysts

    SciTech Connect

    Röhe, Sarah; Frank, Kristian; Schaefer, Andreas; Wittstock, Arne; Zielasek, Volkmar; Rosenauer, Andreas; Bäumer, Marcus

    2012-11-30

    Disks of nanoporous gold (np-Au), produced by leaching of silver from AgAu alloy and prepared as active catalysts for CO oxidation in a continuous-flow reactor, were investigated in detail by x-ray photoelectron spectroscopy and temperature-programmed desorption spectroscopy in ultra-high vacuum. Np-Au exhibits several oxygen species on and in the surface: Chemisorbed oxygen (Oact), probably generated at residual silver sites at the surface, is readily available after np-Au preparation and consumed by CO oxidation. It can be replenished on activated np-Au by exposure to O2. In addition, strongly bound oxygen, probably at subsurface sites, is present as a major species and not consumed by CO oxidation. Pronounced CO desorption at temperatures above 200 K observed after exposing np-Au to CO at 105 K indicates an additional, more stable type of CO binding sites on np-Au as compared to pure gold. Only CO at these binding sites is consumed by oxidation reaction with Oact. In conclusion, we propose that the presence of strongly bound subsurface oxygen stabilizes CO adsorption on np-Au, thereby being as crucial for the observed catalytic activity of np-Au as residual silver.

  16. Design of a high activity and selectivity alcohol catalyst. Eighth quarterly report, May 7, 1992--August 7, 1992

    SciTech Connect

    Foley, H.C.; Mills, G.A.

    1992-07-30

    In methanol dehydration by K-doped Rh-Mo/{gamma}-Al{sub 2}O{sub 3}, while higher K levels reduced the dehydration propensity of the surface, at higher levels the potassium oxide layer formed after doping and calcining the surface interferes detrimentally with the Rh-Mo active metallic sites. Silica- and alumina-supported catalysts with 0.5% Rh loading were synthesized and tested for hydrogenation of CO.

  17. Activity modulation of core and shell in nanozeolite@enzyme bi-functional catalyst for dynamic kinetic resolution.

    PubMed

    Li, Xiang; Yan, Yueer; Wang, Wanlu; Zhang, Yahong; Tang, Yi

    2015-01-15

    A core-shell nanozeolite@enzyme bi-functional catalyst is prepared by using nanozeolite β as acidic core and immobilized Candida antarctica lipase B (CALB) as enzyme shell for the purpose of dynamic kinetic resolution (DKR), and polydiallyldimethylammonium chloride (PDDA) is used as interlayer to compart core and shell. The activities of core and shell in bi-functional catalyst are modulated to achieve the matching between racemization and kinetic resolution (KR) rates in DKR, i.e., a slow racemization rate on core while a fast KR rate on shell. Nanozeolite β with intermediate SiO2/Al2O3 ratio provides proper acid amount for racemization step. A relatively thick layer of PDDA not only improves the activity of CALB by its coverage for surface acidic sites but also limits the accessibility and diffusion of substrate towards the acidic core. The CALB shell with larger immobilized amount and higher enzyme activity offers enhanced driving force of DKR process, leading to higher conversion, selectivity and yield. The preparation and activity modulation of core-shell catalyst provide an ideal method to improve the catalytic performance of bi-functional catalyst.

  18. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion

    PubMed Central

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-01-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones. PMID:26074206

  19. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion.

    PubMed

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-01-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones.

  20. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion

    NASA Astrophysics Data System (ADS)

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-06-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones.

  1. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion.

    PubMed

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-01-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones. PMID:26074206

  2. Aged nano-structured platinum based catalyst: effect of chemical treatment on adsorption and catalytic activity.

    PubMed

    Shim, Wang Geun; Nahm, Seung Won; Park, Hyuk Ryeol; Yun, Hyung Sun; Seo, Seong Gyu; Kim, Sang Chai

    2011-02-01

    To examine the effect of chemical treatment on the adsorption and catalytic activity of nanostructured platinum based catalyst, the aged commercial Pt/AC catalyst was pretreated with sulfuric acid (H2SO4) and a cleaning agent (Hexane). Several reliable methods such as nitrogen adsorption, X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma (ICP) were employed to characterize the aged Pt/AC catalyst and its chemically pretreated Pt/AC catalysts. The catalytic and adsorption activities of nano-structured heterogeneous Pt/AC catalyst were investigated on the basis of toluene oxidation and adsorption isotherm data. In addition, the adsorption isotherms of toluene were used to calculate the adsorption energy distribution functions for the parent catalyst and its pre-treated nano-structured Pt/AC catalysts. It was found that sulfuric acid aqueous treatment can enhance the catalytic performance of aged Pt/AC catalyst toward catalytic oxidation of toluene. It was also shown that a comparative analysis of the energy distribution functions for nano-structured Pt/AC catalysts as well as the pore size distribution provides valuable information about their structural and energetic heterogeneity.

  3. Linking morphology with activity through the lifetime of pretreated PtNi nanostructured thin film catalysts

    DOE PAGES

    Cullen, David A.; Lopez-Haro, Miguel; Bayle-Guillemaud, Pascale; Debe, Mark; Steinbach, Andrew J.; Guetaz, L.

    2015-04-10

    In this study, the nanoscale morphology of highly active Pt3Ni7 nanostructured thin film fuel cell catalysts is linked with catalyst surface area and activity following catalyst pretreatments, conditioning and potential cycling. The significant role of fuel cell conditioning on the structure and composition of these extended surface catalysts is demonstrated by high resolution imaging, elemental mapping and tomography. The dissolution of Ni during fuel cell conditioning leads to highly complex, porous structures which were visualized in 3D by electron tomography. Quantification of the rendered surfaces following catalyst pretreatment, conditioning, and cycling shows the important role pore structure plays in surfacemore » area, activity, and durability.« less

  4. Linking morphology with activity through the lifetime of pretreated PtNi nanostructured thin film catalysts

    SciTech Connect

    Cullen, David A.; Lopez-Haro, Miguel; Bayle-Guillemaud, Pascale; Debe, Mark; Steinbach, Andrew J.; Guetaz, L.

    2015-04-10

    In this study, the nanoscale morphology of highly active Pt3Ni7 nanostructured thin film fuel cell catalysts is linked with catalyst surface area and activity following catalyst pretreatments, conditioning and potential cycling. The significant role of fuel cell conditioning on the structure and composition of these extended surface catalysts is demonstrated by high resolution imaging, elemental mapping and tomography. The dissolution of Ni during fuel cell conditioning leads to highly complex, porous structures which were visualized in 3D by electron tomography. Quantification of the rendered surfaces following catalyst pretreatment, conditioning, and cycling shows the important role pore structure plays in surface area, activity, and durability.

  5. Isolated metal active site concentration and stability control catalytic CO2 reduction selectivity.

    PubMed

    Matsubu, John C; Yang, Vanessa N; Christopher, Phillip

    2015-03-01

    CO2 reduction by H2 on heterogeneous catalysts is an important class of reactions that has been studied for decades. However, atomic scale details of structure-function relationships are still poorly understood. Particularly, it has been suggested that metal particle size plays a unique role in controlling the stability of CO2 hydrogenation catalysts and the distribution of active sites, which dictates reactivity and selectivity. These studies often have not considered the possible role of isolated metal active sites in the observed dependences. Here, we utilize probe molecule diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with known site-specific extinction coefficients to quantify the fraction of Rh sites residing as atomically dispersed isolated sites (Rhiso), as well as Rh sites on the surface of Rh nanoparticles (RhNP) for a series of TiO2 supported Rh catalysts. Strong correlations were observed between the catalytic reverse water gas shift turn over frequency (TOF) and the fraction of Rhiso sites and between catalytic methanation TOF and the fraction of RhNP sites. Furthermore, it was observed that reaction condition-induced disintegration of Rh nanoparticles, forming Rhiso active sites, controls the changing reactivity with time on stream. This work demonstrates that isolated atoms and nanoparticles of the same metal on the same support can exhibit uniquely different catalytic selectivity in competing parallel reaction pathways and that disintegration of nanoparticles under reaction conditions can play a significant role in controlling stability.

  6. Isolated metal active site concentration and stability control catalytic CO2 reduction selectivity.

    PubMed

    Matsubu, John C; Yang, Vanessa N; Christopher, Phillip

    2015-03-01

    CO2 reduction by H2 on heterogeneous catalysts is an important class of reactions that has been studied for decades. However, atomic scale details of structure-function relationships are still poorly understood. Particularly, it has been suggested that metal particle size plays a unique role in controlling the stability of CO2 hydrogenation catalysts and the distribution of active sites, which dictates reactivity and selectivity. These studies often have not considered the possible role of isolated metal active sites in the observed dependences. Here, we utilize probe molecule diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with known site-specific extinction coefficients to quantify the fraction of Rh sites residing as atomically dispersed isolated sites (Rhiso), as well as Rh sites on the surface of Rh nanoparticles (RhNP) for a series of TiO2 supported Rh catalysts. Strong correlations were observed between the catalytic reverse water gas shift turn over frequency (TOF) and the fraction of Rhiso sites and between catalytic methanation TOF and the fraction of RhNP sites. Furthermore, it was observed that reaction condition-induced disintegration of Rh nanoparticles, forming Rhiso active sites, controls the changing reactivity with time on stream. This work demonstrates that isolated atoms and nanoparticles of the same metal on the same support can exhibit uniquely different catalytic selectivity in competing parallel reaction pathways and that disintegration of nanoparticles under reaction conditions can play a significant role in controlling stability. PMID:25671686

  7. Photogeneration of active formate decomposition catalysts to produce hydrogen from formate and water

    DOEpatents

    King, Jr., Allen D.; King, Robert B.; Sailers, III, Earl L.

    1983-02-08

    A process for producing hydrogen from formate and water by photogenerating an active formate decomposition catalyst from transition metal carbonyl precursor catalysts at relatively low temperatures and otherwise mild conditions is disclosed. Additionally, this process may be expanded to include the generation of formate from carbon monoxide and hydroxide such that the result is the water gas shift reaction.

  8. On the Importance of Metal–Oxide Interface Sites for the Water–Gas Shift Reaction Over Pt/CeO2 Catalysts

    SciTech Connect

    Aranifard, Sara; Ammal, Salai Cheettu; Heyden, Andreas

    2014-01-01

    The mechanism of water–gas shift reaction at the three-phase boundary of Pt/CeO2 catalysts has been investigated using density functional theory and microkinetic modeling to better understand the importance of metal–oxide interface sites in heterogeneous catalysis. Analysis of a microkinetic model based on parameters obtained from first principles suggests that both the “Redox pathway” and the “Associative carboxyl pathway with redox regeneration” could operate on Pt/CeO2 catalysts. Although (1) only few interfacial Pt atoms are found to be catalytically active at low temperatures due to strong adsorption of CO and (2) interfacial O–H bond breakage is difficult due to the high reducibility of ceria, interface sites are 2–3 orders of magnitude more active than Pt (1 1 1) and stepped Pt surface sites and therefore effectively determine the overall activity of Pt/CeO2. The high activity of Pt/CeO2 interface sites originates from a significantly enhanced water activation and dissociation at interfacial oxygen vacancies.

  9. Turning aluminium into a noble-metal-like catalyst for low-temperature activation of molecular hydrogen.

    PubMed

    Chopra, Irinder S; Chaudhuri, Santanu; Veyan, Jean François; Chabal, Yves J

    2011-11-01

    Activation of molecular hydrogen is the first step in producing many important industrial chemicals that have so far required expensive noble-metal catalysts and thermal activation. We demonstrate here that aluminium doped with very small amounts of titanium can activate molecular hydrogen at temperatures as low as 90 K. Using an approach that uses CO as a probe molecule, we identify the atomistic arrangement of the catalytically active sites containing Ti on Al(111) surfaces, combining infrared reflection-absorption spectroscopy and first-principles modelling. CO molecules, selectively adsorbed on catalytically active sites, form a complex with activated hydrogen that is removed at remarkably low temperatures (115 K; possibly as a molecule). These results provide the first direct evidence that Ti-doped Al can carry out the essential first step of molecular hydrogen activation under nearly barrierless conditions, thereby challenging the monopoly of noble metals in hydrogen activation. PMID:21946610

  10. Electrolyte-dependent electrosynthesis and activity of cobalt-based water oxidation catalysts.

    PubMed

    Surendranath, Yogesh; Dinca, Mircea; Nocera, Daniel G

    2009-02-25

    Electrolysis of Co(2+) in phosphate, methylphosphonate, and borate electrolytes effects the electrodeposition of an amorphous highly active water oxidation catalyst as a thin film on an inert anode. Electrodeposition of a catalytically competent species immediately follows oxidation of Co(2+) to Co(3+) in solution. Methylphosphonate and borate electrolytes support catalyst activity comparable to that observed for phosphate. Catalytic activity for O(2) generation in aqueous solutions containing 0.5 M NaCl is retained for catalysts grown from phosphate electrolyte.

  11. Synthesis of supported bimetallic nanoparticles with controlled size and composition distributions for active site elucidation

    SciTech Connect

    Hakim, Sikander H.; Sener, Canan; Alba Rubio, Ana C.; Gostanian, Thomas M.; O'neill, Brandon J; Ribeiro, Fabio H.; Miller, Jeffrey T.; Dumesic, James A

    2015-08-01

    Elucidation of active sites in supported bimetallic catalysts is complicated by the high level of dispersity in the nanoparticle size and composition that is inherent in conventional methods of catalyst preparation. We present a synthesis strategy that leads to highly dispersed, bimetallic nanoparticles with uniform particle size and composition by means of controlled surface reactions. We demonstrate the synthesis of three systems, RhMo, PtMo, and RhRe, consisting of a highly reducible metal with an oxophilic promoter. These catalysts are characterized by FTIR, CO chemisorption, STEM/EDS, TPR, and XAS analysis. The catalytic properties of these bimetallic nanoparticles were probed for the selective CO hydrogenolysis of (hydroxymethyl)tetrahydropyran to produce 1,6 hexanediol. Based on the characterization results and reactivity trends, the active sites in the hydrogenolysis reaction are identified to be small ensembles of the more noble metal (Rh, Pt) adjacent to highly reduced moieties of the more oxophilic metal (Mo, Re).

  12. Copper catalyst activation driven by photoinduced electron transfer: a prototype photolatent click catalyst.

    PubMed

    Harmand, Lydie; Cadet, Sarah; Kauffmann, Brice; Scarpantonio, Luca; Batat, Pinar; Jonusauskas, Gediminas; McClenaghan, Nathan D; Lastécouères, Dominique; Vincent, Jean-Marc

    2012-07-16

    PET cat. While the copper(II) tren ketoprofenate precatalyst 1 (see picture) is inactive at room temperature in methanol, it is quantitatively and rapidly reduced to its cuprous state upon light irradiation to provide a highly reactive click catalyst. By simply introducing air into the reaction medium the catalysis can be switched off and then switched on again by bubbling argon followed by irradiation. PMID:22777953

  13. Driving electrocatalytic activity by interface electronic structure control in a metalloprotein hybrid catalyst for efficient hydrogen evolution.

    PubMed

    Behera, Sushant Kumar; Deb, Pritam; Ghosh, Arghya

    2016-08-17

    The rational design of metalloprotein hybrid structures and precise calculations for understanding the role of the interfacial electronic structure in regulating the HER activity of water splitting sites and their microscopic effect for obtaining robust hydrogen evolution possess great promise for developing highly efficient nano-bio hybrid HER catalysts. Here, we employ high-accuracy linear-scaling density functional theory calculations using a near-complete basis set and a minimal parameter implicit solvent model within the self-consistent calculations, on silver (Ag) ions assimilated on bacteriorhodopsin (bR) at specific binding sites. Geometry optimization indicates the formation of active sites at the interface of the metalloprotein complex and the density of states reflects the metallic nature of the active sites. The reduced value of the canonical orbital gap indicates the state of dynamic nature after Ag ion assimilation on active sites and smooth electron transfer. These incorporated active protein sites are more efficient in electrolytic splitting of water than pristine sites due to their low value of Gibbs free energy for the HER in terms of hydrogen coverages. Volcano plot analysis and the free energy diagram are compared for understanding the hydrogen evolution efficiency. Moreover, the essential role of the interfacial electronic properties in regulating the HER catalytic activity of water splitting sites and enhancing the efficiency is elucidated.

  14. Driving electrocatalytic activity by interface electronic structure control in a metalloprotein hybrid catalyst for efficient hydrogen evolution.

    PubMed

    Behera, Sushant Kumar; Deb, Pritam; Ghosh, Arghya

    2016-08-17

    The rational design of metalloprotein hybrid structures and precise calculations for understanding the role of the interfacial electronic structure in regulating the HER activity of water splitting sites and their microscopic effect for obtaining robust hydrogen evolution possess great promise for developing highly efficient nano-bio hybrid HER catalysts. Here, we employ high-accuracy linear-scaling density functional theory calculations using a near-complete basis set and a minimal parameter implicit solvent model within the self-consistent calculations, on silver (Ag) ions assimilated on bacteriorhodopsin (bR) at specific binding sites. Geometry optimization indicates the formation of active sites at the interface of the metalloprotein complex and the density of states reflects the metallic nature of the active sites. The reduced value of the canonical orbital gap indicates the state of dynamic nature after Ag ion assimilation on active sites and smooth electron transfer. These incorporated active protein sites are more efficient in electrolytic splitting of water than pristine sites due to their low value of Gibbs free energy for the HER in terms of hydrogen coverages. Volcano plot analysis and the free energy diagram are compared for understanding the hydrogen evolution efficiency. Moreover, the essential role of the interfacial electronic properties in regulating the HER catalytic activity of water splitting sites and enhancing the efficiency is elucidated. PMID:27499158

  15. Boron-doped graphene as promising support for platinum catalyst with superior activity towards the methanol electrooxidation reaction

    NASA Astrophysics Data System (ADS)

    Sun, Yongrong; Du, Chunyu; An, Meichen; Du, Lei; Tan, Qiang; Liu, Chuntao; Gao, Yunzhi; Yin, Geping

    2015-12-01

    We report the synthesis of boron-doped graphene by thermally annealing the mixture of graphene oxide and boric acid, and its usage as the support of Pt catalyst towards the methanol oxidation reaction. The composition, structure and morphology of boron-doped graphene and its supported Pt nanoparticles (Pt/BG) are characterized by transmission electron microscopy, inductively coupled plasma mass spectrometry, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. It is revealed that boron atoms are doped into graphene network in the form of BC2O and BCO2 bonds, which lead to the increase in defect sites and facilitate the subsequent deposition of Pt nanoparticles. Therefore, the Pt/BG catalyst presents smaller particle size and narrower size distribution than the graphene supported Pt (Pt/G) catalyst. When evaluated as the electrocatalyst for the methanol oxidation reaction, the Pt/BG catalyst exhibits excellent electrochemical activity and stability demonstrated by cyclic voltammetry and chronoamperometry tests. The enhanced activity is mainly ascribed to the electronic interaction between boron-doped graphene and Pt nanoparticles, which lowers the d-band center of Pt and thus weakens the absorption of the poisoning intermediate CO. Our work provides an alternative approach of improving the reaction kinetics for the oxidation of small organic molecules.

  16. A-site-deficiency facilitated in situ growth of bimetallic Ni-Fe nano-alloys: a novel coking-tolerant fuel cell anode catalyst

    NASA Astrophysics Data System (ADS)

    Sun, Yi-Fei; Li, Jian-Hui; Cui, Lin; Hua, Bin; Cui, Shao-Hua; Li, Jian; Luo, Jing-Li

    2015-06-01

    To date, most investigations of Ni-Fe bimetallic catalysts for solid oxide fuel cells (SOFCs) have focused on materials with micro-scale particle sizes, which severely restrict their catalytic activity. In this study, we fabricated a Ni- and/or Fe-doped A-site-deficient LaSrCrO3 perovskite (A-LSC) bimetallic anode material on which the in situ exsolution of uniformly dispersed nano Ni, Fe and Ni-Fe alloy with an average particle size of 25 to 30 nm was facilitated by the introduction of A-site deficiency under a reducing atmosphere. The dopants were shown to significantly enhance the electrical conductivity of the material by many orders of magnitude. Further characterization of the bimetallic material showed that the addition of Fe changed the reduction behavior and increased the amount of oxygen vacancies in the material. Fuel cell performance tests demonstrated that the prepared bimetallic anode catalyst with a highly catalytically active nano Ni-Fe alloy promoted the electrochemical performance in 5000 ppm H2S-syngas and improved the carbon deposition resistance compared to a monometallic anode catalyst.

  17. Synergistic "ping-pong" energy transfer for efficient light activation in a chromophore-catalyst dyad.

    PubMed

    Quaranta, Annamaria; Charalambidis, Georgios; Herrero, Christian; Margiola, Sofia; Leibl, Winfried; Coutsolelos, Athanassios; Aukauloo, Ally

    2015-10-01

    The synthesis of a porphyrin-Ru(II) polypyridine complex where the porphyrin acts as a photoactive unit and the Ru(II) polypyridine as a catalytic precursor is described. Comparatively, the free base porphyrin was found to outperform the ruthenium based chromophore in the yield of light induced electron transfer. Mechanistic insights indicate the occurrence of a ping-pong energy transfer from the (1)LC excited state of the porphyrin chromophore to the (3)MCLT state of the catalyst and back to the (3)LC excited state of the porphyrin unit. The latter, triplet-triplet energy transfer back to the chromophore, efficiently competes with fast radiationless deactivation of the excited state at the catalyst site. The energy thus recovered by the chromophore allows improved yield of formation of the oxidized form of the chromophore and concomitantly of the oxidation of the catalytic unit by intramolecular charge transfer. The presented results are among the rare examples where a porphyrin chromophore is successfully used to drive an oxidative activation process where reductive processes prevail in the literature.

  18. Mimicking enzymatic active sites on surfaces for energy conversion chemistry.

    PubMed

    Gutzler, Rico; Stepanow, Sebastian; Grumelli, Doris; Lingenfelder, Magalí; Kern, Klaus

    2015-07-21

    Metal-organic supramolecular chemistry on surfaces has matured to a point where its underlying growth mechanisms are well understood and structures of defined coordination environments of metal atoms can be synthesized in a controlled and reproducible procedure. With surface-confined molecular self-assembly, scientists have a tool box at hand which can be used to prepare structures with desired properties, as for example a defined oxidation number and spin state of the transition metal atoms within the organic matrix. From a structural point of view, these coordination sites in the supramolecular structure resemble the catalytically active sites of metallo-enzymes, both characterized by metal centers coordinated to organic ligands. Several chemical reactions take place at these embedded metal ions in enzymes and the question arises whether these reactions also take place using metal-organic networks as catalysts. Mimicking the active site of metal atoms and organic ligands of enzymes in artificial systems is the key to understanding the selectivity and efficiency of enzymatic reactions. Their catalytic activity depends on various parameters including the charge and spin configuration in the metal ion, but also on the organic environment, which can stabilize intermediate reaction products, inhibits catalytic deactivation, and serves mostly as a transport channel for the reactants and products and therefore ensures the selectivity of the enzyme. Charge and spin on the transition metal in enzymes depend on the one hand on the specific metal element, and on the other hand on its organic coordination environment. These two parameters can carefully be adjusted in surface confined metal-organic networks, which can be synthesized by virtue of combinatorial mixing of building synthons. Different organic ligands with varying functional groups can be combined with several transition metals and spontaneously assemble into ordered networks. The catalytically active metal

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

    NASA Technical Reports Server (NTRS)

    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.

  20. Microwave and Beam Activation of Nanostructured Catalysts for Environmentally Friendly, Energy Efficient Heavy Crude Oil Processing

    SciTech Connect

    2009-03-01

    This factsheet describes a study whose goal is initial evaluation and development of energy efficient processes which take advantage of the benefits offered by nanostructured catalysts which can be activated by microwave, RF, or radiation beams.

  1. Catalytic activity of bimetallic catalysts highly sensitive to the atomic composition and phase structure at the nanoscale

    NASA Astrophysics Data System (ADS)

    Shan, Shiyao; Petkov, Valeri; Prasai, Binay; Wu, Jinfang; Joseph, Pharrah; Skeete, Zakiya; Kim, Eunjoo; Mott, Derrick; Malis, Oana; Luo, Jin; Zhong, Chuan-Jian

    2015-11-01

    The ability to determine the atomic arrangement in nanoalloy catalysts and reveal the detailed structural features responsible for the catalytically active sites is essential for understanding the correlation between the atomic structure and catalytic properties, enabling the preparation of efficient nanoalloy catalysts by design. Herein we describe a study of CO oxidation over PdCu nanoalloy catalysts focusing on gaining insights into the correlation between the atomic structures and catalytic activity of nanoalloys. PdCu nanoalloys of different bimetallic compositions are synthesized as a model system and are activated by a controlled thermochemical treatment for assessing their catalytic activity. The results show that the catalytic synergy of Pd and Cu species evolves with both the bimetallic nanoalloy composition and temperature of the thermochemical treatment reaching a maximum at a Pd : Cu ratio close to 50 : 50. The nanoalloys are characterized structurally by ex situ and in situ synchrotron X-ray diffraction, including atomic pair distribution function analysis. The structural data show that, depending on the bimetallic composition and treatment temperature, PdCu nanoalloys adopt two different structure types. One features a chemically ordered, body centered cubic (B2) type alloy consisting of two interpenetrating simple cubic lattices, each occupied with Pd or Cu species alone, and the other structure type features a chemically disordered, face-centered cubic (fcc) type of alloy wherein Pd and Cu species are intermixed at random. The catalytic activity for CO oxidation is strongly influenced by the structural features. In particular, it is revealed that the prevalence of chemical disorder in nanoalloys with a Pd : Cu ratio close to 50 : 50 makes them superior catalysts for CO oxidation in comparison with the same nanoalloys of other bimetallic compositions. However, the catalytic synergy can be diminished if the Pd50Cu50 nanoalloys undergo phase

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

    SciTech Connect

    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.

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

    SciTech Connect

    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.

  4. Catalyst patterning for nanowire devices

    NASA Technical Reports Server (NTRS)

    Li, Jun (Inventor); Cassell, Alan M. (Inventor); Han, Jie (Inventor)

    2004-01-01

    Nanowire devices may be provided that are based on carbon nanotubes or single-crystal semiconductor nanowires. The nanowire devices may be formed on a substrate. Catalyst sites may be formed on the substrate. The catalyst sites may be formed using lithography, thin metal layers that form individual catalyst sites when heated, collapsible porous catalyst-filled microscopic spheres, microscopic spheres that serve as masks for catalyst deposition, electrochemical deposition techniques, and catalyst inks. Nanowires may be grown from the catalyst sites.

  5. Morphology-dependent bactericidal activities of Ag/CeO2 catalysts against Escherichia coli.

    PubMed

    Wang, Lian; He, Hong; Yu, Yunbo; Sun, Li; Liu, Sijin; Zhang, Changbin; He, Lian

    2014-06-01

    Silver-loaded CeO2 nanomaterials (Ag/CeO2) including Ag/CeO2 nanorods, nanocubes, nanoparticles were prepared with hydrothermal and impregnation methods. Catalytic inactivation of Escherichia coli with Ag/CeO2 catalysts through the formation of reactive oxygen species (ROS) was investigated. For comparison purposes, the bactericidal activities of CeO2 nanorods, nanocubes and nanoparticles were also studied. There was a 3-4 log order improvement in the inactivation of E. coli with Ag/CeO2 catalysts compared with CeO2 catalysts. Temperature-programmed reduction of H2 showed that Ag/CeO2 catalysts had higher catalytic oxidation ability than CeO2 catalysts, which was the reason for that Ag/CeO2 catalysts exhibited stronger bactericidal activities than CeO2 catalysts. Further, the bactericidal activities of CeO2 and Ag/CeO2 depend on their shapes. Results of 5,5-dimethyl-1-pyrroline-N-oxide spin-trapping measurements by electron spin resonance and addition of catalase as a scavenger indicated the formation of OH, O2(-), and H2O2, which caused the obvious bactericidal activity of catalysts. The stronger chemical bond between Ag and CeO2 nanorods led to lower Ag(+) elution concentrations. The toxicity of Ag(+) eluted from the catalysts did not play an important role during the bactericidal process. Experimental results also indicated that Ag/CeO2 induced the production of intracellular ROS and disruption of the cell wall and cell membrane. A possible production mechanism of ROS and bactericidal mechanism of catalytic oxidation were proposed.

  6. Highly active PtAu alloy nanoparticle catalysts for the reduction of 4-nitrophenol.

    PubMed

    Zhang, Jianming; Chen, Guozhu; Guay, Daniel; Chaker, Mohamed; Ma, Dongling

    2014-02-21

    To enhance the catalytic activity of gold nanoparticles (AuNPs) for the hydrogenation of nitro-aromatic chemicals, Pt was introduced into AuNPs to form "bare" PtAu alloy NPs using a physical approach, pulsed laser ablation in liquid (PLAL), on single metal-mixture targets. These PLAL-NPs are deemed to favor catalysis due to the absence of any surfactant molecules on their unique "bare and clean" surface. The PLAL-NPs were facilely assembled onto CeO2 nanotubes (NTs) by simply mixing them without conducting any surface functionalization, representing another advantage of these NPs. Their catalytic activity was assessed in 4-nitrophenol (4-NP) hydrogenation. The reaction catalyzed by alloy-NP/CeO2-NT catalysts demonstrates a remarkably higher reaction rate in comparison with that catalyzed by pure Au and Pt NPs, and other similar Au and Pt containing catalysts reported recently. A "volcano-like" catalytic activity dependence of the alloy NPs on their chemical composition suggests a strong synergistic effect between Au and Pt in the 4-NP reduction, far beyond the simple sum of their individual contributions. It leads to the significantly enhanced catalytic activity of Pt30Au70 and Pt50Au50 alloy NPs, outperforming not only each single constituent, but also their physical mixtures and most recently reported AuNP based nanocatalysts. The favorable d-band center shift of Pt after alloying, and co-operative actions between Pt clusters and nearby Au (or mixed PtAu) sites were proposed as possible mechanisms to explain such a strong synergistic effect on catalysis.

  7. Single-Face/All-cis Arene Hydrogenation by a Supported Single-Site d(0) Organozirconium Catalyst.

    PubMed

    Stalzer, Madelyn Marie; Nicholas, Christopher P; Bhattacharyya, Alak; Motta, Alessandro; Delferro, Massimiliano; Marks, Tobin J

    2016-04-18

    The single-site supported organozirconium catalyst Cp*ZrBz2 /ZrS (Cp*=Me5 C5 , Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single-face/all-cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all-cis-cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H2 delivery to a single catalyst-bound arene face, versus any competing intramolecular arene π-face interchange.

  8. Causes of Activation and Deactivation of Modified Nanogold Catalysts during Prolonged Storage and Redox Treatments.

    PubMed

    Kolobova, Ekaterina; Kotolevich, Yulia; Pakrieva, Ekaterina; Mamontov, Grigory; Farías, Mario H; Bogdanchikova, Nina; Cortés Corberán, Vicente; Pestryakov, Alexey

    2016-01-01

    The catalytic properties of modified Au/TiO₂ catalysts for low-temperature CO oxidation are affected by deactivation and reactivation after long-term storage and by redox treatments. The effect of these phenomena on the catalysts was studied by HRTEM, BET, SEM, FTIR CO, XPS and H₂ TPR methods. The main cause for the deactivation and reactivation of catalytic properties is the variation in the electronic state of the supported gold, mainly, the proportion of singly charged ions Au⁺. The most active samples are those with the highest proportion of singly charged gold ions, while catalysts with a high content of trivalent gold ions are inactive at low-temperatures. Active states of gold, resistant to changes caused by the reaction process and storage conditions, can be stabilized by modification of the titanium oxide support with transition metals oxides. The catalyst modified with lanthanum oxide shows the highest stability and activity. PMID:27089310

  9. Causes of Activation and Deactivation of Modified Nanogold Catalysts during Prolonged Storage and Redox Treatments.

    PubMed

    Kolobova, Ekaterina; Kotolevich, Yulia; Pakrieva, Ekaterina; Mamontov, Grigory; Farías, Mario H; Bogdanchikova, Nina; Cortés Corberán, Vicente; Pestryakov, Alexey

    2016-04-13

    The catalytic properties of modified Au/TiO₂ catalysts for low-temperature CO oxidation are affected by deactivation and reactivation after long-term storage and by redox treatments. The effect of these phenomena on the catalysts was studied by HRTEM, BET, SEM, FTIR CO, XPS and H₂ TPR methods. The main cause for the deactivation and reactivation of catalytic properties is the variation in the electronic state of the supported gold, mainly, the proportion of singly charged ions Au⁺. The most active samples are those with the highest proportion of singly charged gold ions, while catalysts with a high content of trivalent gold ions are inactive at low-temperatures. Active states of gold, resistant to changes caused by the reaction process and storage conditions, can be stabilized by modification of the titanium oxide support with transition metals oxides. The catalyst modified with lanthanum oxide shows the highest stability and activity.

  10. Effect of Support on the Activity of Ag-based Catalysts for Formaldehyde Oxidation

    PubMed Central

    Zhang, Jianghao; Li, Yaobin; Zhang, Yan; Chen, Min; Wang, Lian; Zhang, Changbin; He, Hong

    2015-01-01

    Ag-based catalysts with different supports (TiO2, Al2O3 and CeO2) were prepared by impregnation method and subsequently tested for the catalytic oxidation of formaldehyde (HCHO) at low temperature. The Ag/TiO2 catalyst showed the distinctive catalytic performance, achieving the complete HCHO conversion at around 95 °C. In contrast, the Ag/Al2O3 and Ag/CeO2 catalysts displayed much lower activity and the 100% conversion was reached at 110 °C and higher than 125 °C, respectively. The Ag-based catalysts were next characterized by several methods. The characterization results revealed that supports have the dramatic influence on the Ag particle sizes and dispersion. Kinetic tests showed that the Ag based catalyst on the TiO2, Al2O3 or CeO2 supports have the similar apparent activation energy of 65 kJ mol−1, indicating that the catalytic mechanism keep immutability over these three catalysts. Therefore, Ag particle size and dispersion was confirmed to be the main factor affecting the catalytic performance for HCHO oxidation. The Ag/TiO2 catalyst has the highest Ag dispersion and the smallest Ag particle size, accordingly presenting the best catalytic performance for HCHO oxidation. PMID:26263506

  11. Surface state and catalytic activity and selectivity of nickel catalysts in hydrogenation reactions. III. Electronic and catalytic properties of nickel catalysts

    SciTech Connect

    Okamoto, Y.; Nitta, Y.; Imanaka, T.; Teranishi, S.

    1980-08-01

    Various nickel catalysts (nickle-boride, nickel-phosphide, Raney-nickel, Urushibara-nickel, and decomposed-nickel) were investigated to examine the relationships between catalytic and electronic properties of nickel catalysts modified by component elements (boron, phosphorus, aluminum, and zinc) in the catalysts. Based on the x-ray photoelectron spectroscopic results, a parameter ..delta..q was tentatively proposed to characterize the electronic properties of the catalysts. The specific activity (activity per surface area of nickel metal) for hydrogenation reaction, the adsorption equilibrium constant of acetophenone, the resistivity against poisoning, and the characteristic selectivities in hydrogenation of 1,2-butylene oxide were found to be summarized in terms of the parameter ..delta..q. It is suggested that a useful parameter to reflect the electronic properties of the nickel catalysts.

  12. Acidic Properties and Structure-Activity Correlations of Solid Acid Catalysts Revealed by Solid-State NMR Spectroscopy.

    PubMed

    Zheng, Anmin; Li, Shenhui; Liu, Shang-Bin; Deng, Feng

    2016-04-19

    Solid acid materials with tunable structural and acidic properties are promising heterogeneous catalysts for manipulating and/or emulating the activity and selectivity of industrially important catalytic reactions. On the other hand, the performances of acid-catalyzed reactions are mostly dictated by the acidic features, namely, type (Brønsted vs Lewis acidity), amount, strength, and local environment of acid sites. The latter is relevant to their location (intra- vs extracrystalline), and possible confinement and Brønsted-Lewis acid synergy effects that may strongly affect the host-guest interactions, reaction mechanism, and shape selectivity of the catalytic system. This account aims to highlight some important applications of state-of-the-art solid-state NMR (SSNMR) techniques for exploring the structural and acidic properties of solid acid catalysts as well as their catalytic performances and relevant reaction pathway invoked. In addition, density functional theory (DFT) calculations may be exploited in conjunction with experimental SSNMR studies to verify the structure-activity correlations of the catalytic system at a microscopic scale. We describe in this Account the developments and applications of advanced ex situ and/or in situ SSNMR techniques, such as two-dimensional (2D) double-quantum magic-angle spinning (DQ MAS) homonuclear correlation spectroscopy for structural investigation of solid acids as well as study of their acidic properties. Moreover, the energies and electronic structures of the catalysts and detailed catalytic reaction processes, including the identification of reaction species, elucidation of reaction mechanism, and verification of structure-activity correlations, made available by DFT theoretical calculations were also discussed. Relevant discussions will focus primarily on results obtained from our laboratories in the past decade, including (i) quantitative and qualitative acidity characterization utilizing assorted probe molecules

  13. Catalysts possessing augmented C-O and C-N hydrogenolysis activity. Preliminary progress report, August-September 1983

    SciTech Connect

    Massoth, F.E.; Shabtai, J.S.

    1983-10-31

    The aim of the proposed research is to synthesize and investigate new sulfided catalyst systems having higher carbon-heteroatom hydrogenolysis activity as compared to ring hydrogenation activity. A fundamental approach is planned to gain understanding of the basic catalytic properties which relate to hydrogenolysis, hydrogenation and cracking functions of the catalysts. This will involve preparation of new catalysts, characterization of their properties and model compound reactivity studies. In another part of the project, selected catalysts will be applied in studies of more complex O- and N-containing model compounds with the objective of providing fundamental data on the stereochemistry of HDO and HDN reactions. These data will be used to develop steric surface-reactant models for sulfided catalysts. These new catalysts should be of particular importance for upgrading of coal-derived liquids and solids, as well as other heavy feedstocks. The research is divided into four tasks: (1) catalyst preparation and activity testing; (2) catalyst characterization; (2) study of catalyst activity under hydroprocessing conditions; and (4) stereochemical studies. This report covers a period of only one month. Work was initiated on catalyst preparation. A brief literature search was made to ascertain what different preparation methods can be applied to supported sulfide catalysts besides the standard wetness method. Several Cr/Al/sub 2/O/sub 3/ catalysts containing Co or Ni were prepared by the standard impregnation method. 3 references.

  14. Method of treating intermetallic alloy hydrogenation/oxidation catalysts for improved impurity poisoning resistance, regeneration and increased activity

    DOEpatents

    Wright, Randy B.

    1992-01-01

    Alternate, successive high temperature oxidation and reduction treatments, in either order, of intermetallic alloy hydrogenation and intermetallic alloy oxidation catalysts unexpectedly improves the impurity poisoning resistance, regeneration capacity and/or activity of the catalysts. The particular alloy, and the final high temperature treatment given alloy (oxidation or reduction) will be chosen to correspond to the function of the catalyst (oxidation or hydrogenation).

  15. Methanol Synthesis over Cu/ZnO/Al2O3: The Active Site in Industrial Catalysis

    SciTech Connect

    Behrens, Malte

    2012-03-28

    Unlike homogeneous catalysts, heterogeneous catalysts that have been optimized through decades are typically so complex and hard to characterize that the nature of the catalytically active site is not known. This is one of the main stumbling blocks in developing rational catalyst design strategies in heterogeneous catalysis. We show here how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst. Using a combination of experimental evidence from bulk-, surface-sensitive and imaging methods collected on real high-performance catalytic systems in combination with DFT calculations. We show that the active site consists of Cu steps peppered with Zn atoms, all stabilized by a series of well defined bulk defects and surface species that need jointly to be present for the system to work.

  16. An alternative approach to PEPPSI catalysts: from palladium isonitriles to highly active unsymmetrically substituted PEPPSI catalysts.

    PubMed

    Zeiler, Anna; Rudolph, Matthias; Rominger, Frank; Hashmi, A Stephen K

    2015-07-27

    A series of new pyridine-enhanced precatalyst preparation, stabilization, and initiation (PEPPSI)-type complexes bearing different types of carbene ligands was prepared by the modular and convergent template synthesis strategy. Nitrogen acyclic carbenes, saturated and unsaturated five-membered NHC, saturated six-membered NHCs, and five-membered N-heterocyclic oxo-carbene (NHOC) ligands on palladium were prepared this way. These new organometallic compounds then were tested in Suzuki and Negishi cross-coupling reactions by using substrates with one or two substituents in ortho-position of the new CC bond being formed. Both aryl chlorides and bromides were tested as coupling partners. In some cases, the new ligands gave results similar to Organ's successful IPr-based and IPent-based PEPPSI derivatives, with aryl bromides 0.05 mol % catalyst load still gave satisfactory results, with aryl chlorides 0.5 mol % were needed. PMID:26096141

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

    NASA Technical Reports Server (NTRS)

    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.

  18. Shape-selective catalysts for Fischer-Tropsch chemistry : atomic layer deposition of active catalytic metals. Activity report : January 1, 2005 - September 30, 2005.

    SciTech Connect

    Cronauer, D. C.

    2011-04-15

    Argonne National Laboratory is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry - specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. The broad goal is to produce diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. Originally the goal was to prepare shape-selective catalysts that would limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' Such catalysts were prepared with silica-containing fractal cages. The activity was essentially the same as that of catalysts without the cages. We are currently awaiting follow-up experiments to determine the attrition strength of these catalysts. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for complete monolayer coverage. In addition, there was likely to be significant variation in the Fe and Ru loading among the membranes due to difficulties in nucleating these materials on the aluminum oxide surfaces. The first

  19. Renewable phenols production by catalytic microwave pyrolysis of Douglas fir sawdust pellets with activated carbon catalysts.

    PubMed

    Bu, Quan; Lei, Hanwu; Wang, Lu; Wei, Yi; Zhu, Lei; Liu, Yupeng; Liang, Jing; Tang, Juming

    2013-08-01

    The effects of different activated carbon (AC) catalysts based on various carbon sources on products yield and chemical compositions of upgraded pyrolysis oils were investigated using microwave pyrolysis of Douglas fir sawdust pellets. Results showed that high amounts of phenols were obtained (74.61% and 74.77% in the upgraded bio-oils by DARCO MRX (wood based) and DARCO 830 (lignite coal based) activated carbons, respectively). The catalysts recycling test of the selected catalysts indicated that the carbon catalysts can be reused for at least 3-4 times and produced high concentrations of phenol and phenolic compounds. The chemical reaction mechanism for phenolics production during microwave pyrolysis of biomass was analyzed. PMID:23765005

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

    SciTech Connect

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

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of the catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

  1. Renewable phenols production by catalytic microwave pyrolysis of Douglas fir sawdust pellets with activated carbon catalysts.

    PubMed

    Bu, Quan; Lei, Hanwu; Wang, Lu; Wei, Yi; Zhu, Lei; Liu, Yupeng; Liang, Jing; Tang, Juming

    2013-08-01

    The effects of different activated carbon (AC) catalysts based on various carbon sources on products yield and chemical compositions of upgraded pyrolysis oils were investigated using microwave pyrolysis of Douglas fir sawdust pellets. Results showed that high amounts of phenols were obtained (74.61% and 74.77% in the upgraded bio-oils by DARCO MRX (wood based) and DARCO 830 (lignite coal based) activated carbons, respectively). The catalysts recycling test of the selected catalysts indicated that the carbon catalysts can be reused for at least 3-4 times and produced high concentrations of phenol and phenolic compounds. The chemical reaction mechanism for phenolics production during microwave pyrolysis of biomass was analyzed.

  2. Graphene nanosheets-polypyrrole hybrid material as a highly active catalyst support for formic acid electro-oxidation.

    PubMed

    Yang, Sudong; Shen, Chengmin; Liang, Yanyu; Tong, Hao; He, Wei; Shi, Xuezhao; Zhang, Xiaogang; Gao, Hong-jun

    2011-08-01

    A novel electrode material based on graphene oxide (GO)-polypyrrole (PPy) composites was synthesized by in situ chemical oxidation polymerization. Palladium nanoparticles (NPs) with a diameter of 4.0 nm were loaded on the reduced graphene oxide(RGO)-PPy composites by a microwave-assisted polyol process. Microstructure analysis showed that a layer of coated PPy film with monodisperse Pd NPs is present on the RGO surface. The Pd/RGO-PPy catalysts exhibit excellent catalytic activity and stability for formic acid electro-oxidation when the weight feed ratio of GO to pyrrole monomer is 2:1. The superior performance of Pd/RGO-PPy catalysts may arise from utilization of heterogeneous nucleation sites for NPs and the greatly increased electronic conductivity of the supports.

  3. Graphene nanosheets-polypyrrole hybrid material as a highly active catalyst support for formic acid electro-oxidation.

    PubMed

    Yang, Sudong; Shen, Chengmin; Liang, Yanyu; Tong, Hao; He, Wei; Shi, Xuezhao; Zhang, Xiaogang; Gao, Hong-jun

    2011-08-01

    A novel electrode material based on graphene oxide (GO)-polypyrrole (PPy) composites was synthesized by in situ chemical oxidation polymerization. Palladium nanoparticles (NPs) with a diameter of 4.0 nm were loaded on the reduced graphene oxide(RGO)-PPy composites by a microwave-assisted polyol process. Microstructure analysis showed that a layer of coated PPy film with monodisperse Pd NPs is present on the RGO surface. The Pd/RGO-PPy catalysts exhibit excellent catalytic activity and stability for formic acid electro-oxidation when the weight feed ratio of GO to pyrrole monomer is 2:1. The superior performance of Pd/RGO-PPy catalysts may arise from utilization of heterogeneous nucleation sites for NPs and the greatly increased electronic conductivity of the supports. PMID:21713273

  4. XAFS Study of the Photo-Active Site of Mo/MCM-41

    NASA Astrophysics Data System (ADS)

    Miyamoto, Daisuke; Ichikuni, Nobuyuki; Shimazu, Shogo

    2007-02-01

    An Mo/MCM-41 catalyst was prepared and used for study of propene and 1-butene photo-metathesis reactions. XAFS analysis revealed that hydrogen reduction leads to a decreased role for the Mo=O site. The Mo-O site plays an important role for the olefin photo-metathesis reaction on the H2 reduced Mo/MCM-41. From EXAFS analysis, the active site of photo-metathesis reaction is the Mo=O part for oxidized Mo/MCM-41, whereas it is the Mo-O site for reduced Mo/MCM-41.

  5. Single-Site Heterogeneous Catalysts for Olefin Polymerization Enabled by Cation Exchange in a Metal-Organic Framework.

    PubMed

    Comito, Robert J; Fritzsching, Keith J; Sundell, Benjamin J; Schmidt-Rohr, Klaus; Dincă, Mircea

    2016-08-17

    The manufacture of advanced polyolefins has been critically enabled by the development of single-site heterogeneous catalysts. Metal-organic frameworks (MOFs) show great potential as heterogeneous catalysts that may be designed and tuned on the molecular level. In this work, exchange of zinc ions in Zn5Cl4(BTDD)3, H2BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin) (MFU-4l) with reactive metals serves to establish a general platform for selective olefin polymerization in a high surface area solid promising for industrial catalysis. Characterization of polyethylene produced by these materials demonstrates both molecular and morphological control. Notably, reactivity approaches single-site catalysis, as evidenced by low polydispersity indices, and good molecular weight control. We further show that these new catalysts copolymerize ethylene and propylene. Uniform growth of the polymer around the catalyst particles provides a mechanism for controlling the polymer morphology, a relevant metric for continuous flow processes.

  6. Nitrogen-doped carbon nanotubes as a highly active metal-free catalyst for selective oxidation.

    PubMed

    Chizari, Kambiz; Deneuve, Adrien; Ersen, Ovidiu; Florea, Ileana; Liu, Yu; Edouard, David; Janowska, Izabela; Begin, Dominique; Pham-Huu, Cuong

    2012-01-01

    Catalytic reactions are generally carried out on supported metals or oxides, which act as an active phase and require impregnation and thermal treatment steps. During tests, the metal or oxide nanoparticles could be further sintered, which would induces deactivation. Direct incorporation of the active phase into the matrix of a support could be an elegant alternative to prevent catalyst deactivation. Here, we report that nitrogen-doped carbon nanotubes (N-CNTs) can be efficiently employed as a metal-free catalyst for oxidative reactions that allow the selective transformation of the harmful, gaseous H(2)S into solid sulfur. The catalyst exhibits a high stability during the test at high space velocity. The macroscopic shaping of the catalyst on the silicon carbide foam also increases its catalytic activity by improving the contact between the reactants and the catalyst. Such macroscopic shaping allows the avoidance of problems linked with transport and handling of nanoscopic materials and also reduces the pressure drop across the catalyst bed to a large extent.

  7. ALTERNATIVE ROUTES FOR CATALYST PREPARATION: USE OF ULTRASOUND AND MICROWAVE IRRADIATION FOR THE PREPARATION OF VANADIUM PHOSPHORUS OXIDE CATALYST AND THEIR ACTIVITY FOR HYDROCARBON OXIDATION

    EPA Science Inventory

    Vanadium phosphorus oxide (VPO) has been prepared using ultrasound and microwave irradiation methods and compared with the catalyst prepared by conventional method for both the phase composition and activity for hydrocarbon oxidation. It is found that ultrasound irradiation metho...

  8. Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions.

    PubMed

    Parapat, Riny Y; Wijaya, Muliany; Schwarze, Michael; Selve, Sören; Willinger, Marc; Schomäcker, Reinhard

    2013-01-21

    We recently introduced a new method to synthesize an active and stable Pt catalyst, namely thermo-destabilization of microemulsions (see R. Y. Parapat, V. Parwoto, M. Schwarze, B. Zhang, D. S. Su and R. Schomäcker, J. Mater. Chem., 2012, 22 (23), 11605-11614). We are able to produce Pt nanocrystals with a small size (2.5 nm) of an isotropic structure i.e. truncated octahedral and deposit them well on support materials. Although we have obtained good results, the performance of the catalyst still needed to be improved and optimized. We followed the strategy to retain the small size but change the shape to an anisotropic structure of Pt nanocrystals which produces more active sites by means of a weaker reducing agent. We found that our catalysts are more active than those we reported before and even show the potential to be applied in a challenging reaction such as hydrogenation of levulinic acid. PMID:23235742

  9. A facile reflux procedure to increase active surface sites form highly active and durable supported palladium@platinum bimetallic nanodendrites

    NASA Astrophysics Data System (ADS)

    Wang, Qin; Li, Yingjun; Liu, Baocang; Xu, Guangran; Zhang, Geng; Zhao, Qi; Zhang, Jun

    2015-11-01

    A series of well-dispersed bimetallic Pd@Pt nanodendrites uniformly supported on XC-72 carbon black are fabricated by using different capping agents. These capping agents are essential for the branched morphology control. However, the surfactant adsorbed on the nanodendrites surface blocks the access of reactant molecules to the active surface sites, and the catalytic activities of these bimetallic nanodendrites are significantly restricted. Herein, a facile reflux procedure to effectively remove the capping agent molecules without significantly affecting their sizes is reported for activating supported nanocatalysts. More significantly, the structure and morphology of the nanodendrites can also be retained, enhancing the numbers of active surface sites, catalytic activity and stability toward methanol and ethanol electro-oxidation reactions. The as-obtained hot water reflux-treated Pd@Pt/C catalyst manifests superior catalytic activity and stability both in terms of surface and mass specific activities, as compared to the untreated catalysts and the commercial Pt/C and Pd/C catalysts. We anticipate that this effective and facile removal method has more general applicability to highly active nanocatalysts prepared with various surfactants, and should lead to improvements in environmental protection and energy production.

  10. Structure-Activity Relationship Studies of Cyclopropenimines as Enantioselective Brønsted Base Catalysts

    PubMed Central

    Bandar, Jeffrey S.; Barthelme, Alexandre P.; Mazori, Alon Y.; Lambert, Tristan H.

    2015-01-01

    We recently demonstrated that chiral cyclopropenimines are viable Brønsted base catalysts in enantioselective Michael and Mannich reactions. Herein, we describe a series of structure-activity relationship studies that provide an enhanced understanding of the effectiveness of certain cyclopropenimines as enantioselective Brønsted base catalysts. These studies underscore the crucial importance of dicyclohexylamino substituents in mediating both reaction rate and enantioselectivity. In addition, an unusual catalyst CH···O interaction, which provides both ground state and transition state organization, is discussed. Cyclopropenimine stability studies have led to the identification of new catalysts with greatly improved stability. Finally, additional demonstrations of substrate scope and current limitations are provided herein. PMID:26504512

  11. The effect of catalyst preparation on catalytic activity: Final report, December 1, 1983-November 31, 1986

    SciTech Connect

    Schwarz, J.A.

    1986-12-01

    The performance of catalysts has been shown to be strongly dependent on their methods of preparation. The objective of our research has been to examine the effect of preparation procedures including metal concentration and pH of the impregnation solution on the catalytic properties of supported-metal catalyst systems. Design parameters have been identified for Ni/Al/sub 2/O/sub 3/ catalysts propared by incipient wetness and wet impregnation from nickel nitrate solution in contact with a ..gamma..-Al/sub 2/O/sub 3/ support. The metal dispersion, activity for C/sub 1/, C/sub 2/, and C/sub 3/ formation under synthesis conditions, and the carbon deposited during reaction have been shown to be predictable based solely on the properties of the electrolytes from which these catalysts were formed.

  12. TiO2 nanotubes supported NiW hydrodesulphurization catalysts: Characterization and activity

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

    High surface area TiO2 nanotubes (Ti-NT) synthesized by alkali hydrothermal method were used as a support for NiW hydrodesulphurization catalyst. Nickel salt of 12-tungstophosphoric acid - Ni3/2PW12O40 was applied as oxide precursor of the active components. The catalyst was characterized by SBET, 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.

  13. Identification of active sites in gold-catalyzed hydrogenation of acrolein.

    PubMed

    Mohr, Christian; Hofmeister, Herbert; Radnik, Jörg; Claus, Peter

    2003-02-19

    The active sites of supported gold catalysts, favoring the adsorption of C=O groups of acrolein and subsequent reaction to allyl alcohol, have been identified as edges of gold nanoparticles. After our recent finding that this reaction preferentially occurs on single crystalline particles rather than multiply twinned ones, this paper reports on a new approach to distinguish different features of the gold particle morphology. Elucidation of the active site issue cannot be simply done by varying the size of gold particles, since the effects of faceting and multiply twinned particles may interfere. Therefore, modification of the gold particle surface by indium has been used to vary the active site characteristics of a suitable catalyst, and a selective decoration of gold particle faces has been observed, leaving edges free. This is in contradiction to theoretical predictions, suggesting a preferred occupation of the low-coordinated edges of the gold particles. On the bimetallic catalyst, the desired allyl alcohol is the main product (selectivity 63%; temperature 593 K, total pressure p(total) = 2 MPa). From the experimentally proven correlation between surface structure and catalytic behavior, the edges of single crystalline gold particles have been identified as active sites for the preferred C=O hydrogenation. PMID:12580618

  14. Site-Selective Ribosylation of Fluorescent Nucleobase Analogs Using Purine-Nucleoside Phosphorylase as a Catalyst: Effects of Point Mutations.

    PubMed

    Stachelska-Wierzchowska, Alicja; Wierzchowski, Jacek; Bzowska, Agnieszka; Wielgus-Kutrowska, Beata

    2015-12-28

    Enzymatic ribosylation of fluorescent 8-azapurine derivatives, like 8-azaguanine and 2,6-diamino-8-azapurine, with purine-nucleoside phosphorylase (PNP) as a catalyst, leads to N9, N8, and N7-ribosides. The final proportion of the products may be modulated by point mutations in the enzyme active site. As an example, ribosylation of the latter substrate by wild-type calf PNP gives N7- and N8-ribosides, while the N243D mutant directs the ribosyl substitution at N9- and N7-positions. The same mutant allows synthesis of the fluorescent N7-β-d-ribosyl-8-azaguanine. The mutated form of the E. coli PNP, D204N, can be utilized to obtain non-typical ribosides of 8-azaadenine and 2,6-diamino-8-azapurine as well. The N7- and N8-ribosides of the 8-azapurines can be analytically useful, as illustrated by N7-β-d-ribosyl-2,6-diamino-8-azapurine, which is a good fluorogenic substrate for mammalian forms of PNP, including human blood PNP, while the N8-riboside is selective to the E. coli enzyme.

  15. Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation

    NASA Astrophysics Data System (ADS)

    He, Qian; Freakley, Simon J.; Edwards, Jennifer K.; Carley, Albert F.; Borisevich, Albina Y.; Mineo, Yuki; Haruta, Masatake; Hutchings, Graham J.; Kiely, Christopher J.

    2016-09-01

    The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviours after heat treatment of Au/FeOx materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed to reveal the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. Correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeOx catalyst.

  16. Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation

    PubMed Central

    He, Qian; Freakley, Simon J.; Edwards, Jennifer K.; Carley, Albert F.; Borisevich, Albina Y.; Mineo, Yuki; Haruta, Masatake; Hutchings, Graham J.; Kiely, Christopher J.

    2016-01-01

    The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviours after heat treatment of Au/FeOx materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed to reveal the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. Correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeOx catalyst. PMID:27671143

  17. Modification of Pd-CeO 2 catalyst by different treatments: Effect on the structure and CO oxidation activity

    NASA Astrophysics Data System (ADS)

    Wang, Bin; Weng, Duan; Wu, Xiaodong; Ran, Rui

    2011-02-01

    To investigate the interaction between noble metal and CeO2, a Pd-doped CeO2 catalyst was prepared by sol-gel method, and the catalyst was then treated in static air and a H2/O2 alternating flow at 800 °C, respectively. It is found by step-scanning XRD that Pd ions migrate out of the ceria lattice during the redox treatment, while the exudation of Pd is not so obvious after the oxidative treatment. For the CO oxidation activity, the redox treated catalyst is seriously weakened compared with the oxidative-treated one. This difference is ascribed to the encapsulation of Pd crystallites by the CeO2 support during the redox treatment, which is confirmed by XPS and CO-TPR. Based on the activity and FTIR results, it is proposed that, CO oxidation at low temperatures proceeds mainly via the reaction between the adsorbed CO on Pd sites and the lattice oxygen of surface CeO2 at the Pd-Ce interface.

  18. Enhancing catalytic activity by narrowing local energy gaps--X-ray studies of a manganese water oxidation catalyst.

    PubMed

    Xiao, Jie; Khan, Munirah; Singh, Archana; Suljoti, Edlira; Spiccia, Leone; Aziz, Emad F

    2015-03-01

    Changes in the local electronic structure of the Mn 3d orbitals of a Mn catalyst derived from a dinuclear Mn(III) complex during the water oxidation cycle were investigated ex situ by X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) analyses. Detailed information about the Mn 3d orbitals, especially the local HOMO-LUMO gap on Mn sites revealed by RIXS analyses, indicated that the enhancement in catalytic activity (water oxidation) originated from the narrowing of the local HOMO-LUMO gap when electrical voltage and visible light illumination were applied simultaneously to the Mn catalytic system.

  19. Nanoscaled palladium catalysts on activated carbon support "Sibunit" for fine organic synthesis

    NASA Astrophysics Data System (ADS)

    Simakova, I.; Koskin, A.; Deliy, I.; Simakov, A.

    2005-08-01

    The application of nanosized palladium catalysts has gained growing importance over the last few years. Palladiumbased catalytic methods for fine organic synthesis permits the replacement of traditional labor-consuming techniques in multi-step organic syntheses and provides an improvement from the standpoint of cost and environmental impact. The use of activated carbon "Sibunit" as a substrate for catalysts has been fostered by the substrate's high surface area, chemical inertness both in acidic and basic media, and at the same time by the absence of very strong acidic centers on its surface which could promote undesirable side reactions during the catalytic run. A conversion of alpha-pinene derivatives to commercial biologically active compounds and fragrances as well as sun screens with ultra violet filtering properties, involves a catalytic hydrogenation as a key intermediate step. The aim of the present work is to clarify the factors favoring the dispersion of Pd metal on carbon. The effect of reduction temperature and pretreatment of the carbon surface on metal size during preparation of Pd on "Sibunit" catalysts for selective verbenol conversion was studied. The electron microscopy method (TEM) was used to show the influence on Pd metal dispersion of carbon surface oxidation by the oxidant H2O2, HNO3. The catalytic activity of Pd/C catalyst samples in verbenol hydrogenation reaction was determined. Kinetic peculiarities of verbenol hydrogenation over the most active catalyst sample were obtained.

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

    DOE PAGES

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

    2015-09-16

    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 inmore » 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. As a result, 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.« less

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

    SciTech Connect

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

    2015-09-16

    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. As a result, 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.

  2. Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts.

    PubMed

    Yue, Lin; He, Chi; Hao, Zhengping; Wang, Shunbing; Wang, Hailin

    2014-03-01

    Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption-desorption, X-ray fluorescence (XRF), H2 temperature programmed reduction (H2-TPR), and NH3 temperature programmed desorption (NH3-TPD). Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2-methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from isomerization and protolysis reactions. PMID:25079284

  3. Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts.

    PubMed

    Yue, Lin; He, Chi; Hao, Zhengping; Wang, Shunbing; Wang, Hailin

    2014-03-01

    Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption-desorption, X-ray fluorescence (XRF), H2 temperature programmed reduction (H2-TPR), and NH3 temperature programmed desorption (NH3-TPD). Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2-methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from isomerization and protolysis reactions.

  4. Copper on responsive polymer microgels: a recyclable catalyst exhibiting tunable catalytic activity.

    PubMed

    Wu, Qingshi; Cheng, Han; Chang, Aiping; Bai, Xue; Lu, Fan; Wu, Weitai

    2014-11-25

    Copper has been immobilized on a chitosan-based responsive polymer microgel by simply stirring the microgel dispersion with copper sulfate. The ensuing catalyst is highly active for a model azide-alkyne [3+2]-cycloaddition reaction, and can be recycled at least 5 times; the catalytic activity can be tuned via swelling-deswelling transitions of the polymer gels. PMID:25283806

  5. Design of a high activity and selectivity alcohol catalyst

    SciTech Connect

    Foley, H.C.; Mills, G.A.

    1993-02-17

    Preliminary investigations of these manganese oxide materials show that the different oxides exhibit different selectivity toward methanol and other products. It seems that there is a correlation between the initial O/Mn ratio of the oxide and methanol selectivity. These conclusions are supported by the results displayed in Figures 1 and 2. The main product of the manganese oxide-catalyzed CO hydrogenation is methanol except on Mao, which shows the lowest methanol selectivity, but the highest CO[sub 2] yield. Preliminarily, the results suggest that the higher the O/Mn ratio of the precursor oxide, the higher will be the methanol selectivity, while the CO[sub 2] and methane selectivities will be lower. The higher CO[sub 2] and C[sub 2], C[sub 3] and C[sub 4] hydrocarbon selectivities over the Mao catalyst compared to the other manganese oxides tested, indicates that Mao acts more like a water-gas shift and Fischer-Tropsch catalyst.

  6. Microcrystalline Zinc Coordination Polymers as Single-site Heterogeneous Catalysts for the Selective Synthesis of Mono-oxazolines from Amino Alcohol and Dinitriles.

    PubMed

    Wang, Junning; Huang, Chao; Gao, Kuan; Wang, Xiaolu; Liu, Mengjia; Ma, Haoran; Wu, Jie; Hou, Hongwei

    2016-06-21

    In our effort to develop coordination polymers (CPs)-based single-site catalysts for the selective synthesis of mono-oxazolines, two Zn-based CPs, [{Zn6 (idbt)4 (phen)4 } ⋅3 H2 O]n  (1) and [{Zn3 (idbt)2 (H2 O)4 }⋅2 H2 O]n  (2) (H3 idbt= 5,5'-(1H-imidazole-4,5-diyl)-bis-(2H-tetrazole), phen=1,10-phenanthroline) have been synthesized. They exhibit two-dimensional structure and contain isolated and accessible catalytically active sites, mimicking the site isolation of many catalytic enzymes. Micro CPs 1 and 2 are obtained by using surfactant-mediated hydrothermal methods, and an investigation is conducted to explore how different surfactants affect their morphologies and particle sizes. Furthermore, micro 1 and 2 have shown to be effective heterogeneous catalysts for the reaction of amino alcohols and aromatic dinitriles, and exerted a significant influence on the selectivity of the catalytic reactions, yielding mono-oxazolines as the major reaction product. PMID:27136746

  7. Fe/S doped granular activated carbon as a highly active heterogeneous persulfate catalyst toward the degradation of Orange G and diethyl phthalate.

    PubMed

    Pu, Mengjie; Ma, Yongwen; Wan, Jinquan; Wang, Yan; Huang, Mingzhi; Chen, Yangmei

    2014-03-15

    Fe/S doped granular activated carbon (Fe/SGAC) was synthesized with ferric nitrate, Na2S2O3 and (NH4)2S2O8 via an impregnation-precipitation, reduction-oxidation combining with aqueous-phase synthesis method treatment. Surface density of functional groups, surface area changes as well as the chemical state inside Fe/SGAC catalyst were studied by Boehm titration, N2 adsorption and X-ray photoelectron spectroscopy (XPS). The reactivity of the catalysts was tested by degrading Orange G (OG) and diethyl phthalate (DEP). The Fe/SGAC catalysts could significantly enhance the removal rate of OG as compared to persulfate alone and PS/GAC. And the catalytic capacity was also enhanced by S doping. But the degradation of DEP under the similar condition was inhibited by adsorption process because of the different hydrophobicities of OG and DEP molecule. Fe2O3/FeOOH (Fe(3+)) (represents ferrihydrite) together with FeO/Fe3O4 (Fe(2+)) and Fe2O3-satellite, which provide the new active site for persulfate catalyst was found to be the major components of iron element in Fe/SGAC catalyst; the existence of FeS2(S(-)) for sulfur element verified the assumption that the doped S element promoted the electron transfer between the persulfate species and iron oxide at the interface. COD removal experiment further confirmed that mostly contaminant removal was owed to the Fe/SGAC catalytic persulfate oxidation process. PMID:24461853

  8. Characterization and CO oxidation activity of Cu/Cr/Al{sub 2}O{sub 3} catalysts

    SciTech Connect

    Park, P.W.; Ledford, J.S.

    1998-03-01

    X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) have been used to characterize a series of Cu/Cr/Al{sub 2}O{sub 3} catalysts prepared by stepwise incipient wetness impregnation of first chromium followed by copper (designated CuCry). The copper loading was held constant at 8 wt% CuO, and chromium loadings were varied from 0 to 20 wt% Cr{sub 2}O{sub 3}. The information obtained from surface and bulk characterization has been correlated with the CO oxidation activity of the catalysts. XPS and XRD results of analogous Cry indicated that the Cr dispersion decreased and the concentration of Cr{sup 3+} species increased with increasing Cr content. The decrease in Cu dispersion of CuCry with increasing Cr content has been attributed to the formation of large crystalline CuO and CuCr{sub 2}O{sub 4}. Copper addition decreased the Cr dispersion by reacting selectively with a dispersed Cr{sup 3+} species to form CuCr{sub 2}O{sub 4} species. However, the Cu addition did not affect the Cr oxidation state distribution compared to that of Cry. For low Cr loading CuCry catalysts (Cr/Al {le} 0.027), the CO oxidation activity increased with increasing Cr content due to the formation of crystalline CuO on the Cr-modified alumina. This has been attributed to the inhibition of Cu ion diffusion into alumina lattice vacancies by highly dispersed chromium species. The CuCry catalyst of Cr/Al = 0.054 showed the highest CO oxidation activity due to the formation of CuCr{sub 2}O{sub 4} which was more active than the CuO phase. For Cr-rich catalysts (Cr/Al {ge} 0.080), the decrease in CO oxidation activity has been ascribed to the encapsulation of the active site with Cr{sub 2}O{sub 3} species.

  9. High-activity PtRuPd/C catalyst for direct dimethyl ether fuel cells.

    PubMed

    Li, Qing; Wen, Xiaodong; Wu, Gang; Chung, Hoon T; Gao, Rui; Zelenay, Piotr

    2015-06-22

    Dimethyl ether (DME) has been considered as a promising alternative fuel for direct-feed fuel cells but lack of an efficient DME oxidation electrocatalyst has remained the challenge for the commercialization of the direct DME fuel cell. The commonly studied binary PtRu catalyst shows much lower activity in DME than methanol oxidation. In this work, guided by density functional theory (DFT) calculation, a ternary carbon-supported PtRuPd catalyst was designed and synthesized for DME electrooxidation. DFT calculations indicated that Pd in the ternary PtRuPd catalyst is capable of significantly decreasing the activation energy of the CO and CH bond scission during the oxidation process. As evidenced by both electrochemical measurements in an aqueous electrolyte and polymer-electrolyte fuel cell testing, the ternary catalyst shows much higher activity (two-fold enhancement at 0.5 V in fuel cells) than the state-of-the-art binary Pt50 Ru50 /C catalyst (HiSPEC 12100).

  10. The role of surface reactions on the active and selective catalyst design for bioethanol steam reforming

    NASA Astrophysics Data System (ADS)

    Benito, M.; Padilla, R.; Serrano-Lotina, A.; Rodríguez, L.; Brey, J. J.; Daza, L.

    In order to study the role of surface reactions involved in bioethanol steam reforming mechanism, a very active and selective catalyst for hydrogen production was analysed. The highest activity was obtained at 700 °C, temperature at which the catalyst achieved an ethanol conversion of 100% and a selectivity to hydrogen close to 70%. It also exhibited a very high hydrogen production efficiency, higher than 4.5 mol H 2 per mol of EtOH fed. The catalyst was operated at a steam to carbon ratio (S/C) of 4.8, at 700 °C and atmospheric pressure. No by-products, such as ethylene or acetaldehyde were observed. In order to consider a further application in an ethanol processor, a long-term stability test was performed under the conditions previously reported. After 750 h, the catalyst still exhibited a high stability and selectivity to hydrogen production. Based on the intermediate products detected by temperature programmed desorption and reaction (TPD and TPR) experiments, a reaction pathway was proposed. Firstly, the adsorbed ethanol is dehydrogenated to acetaldehyde producing hydrogen. Secondly, the adsorbed acetaldehyde is transformed into acetone via acetic acid formation. Finally, acetone is reformed to produce hydrogen and carbon dioxide, which were the final reaction products. The promotion of such reaction sequence is the key to develop an active, selective and stable catalyst, which is the technical barrier for hydrogen production by ethanol reforming.

  11. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    SciTech Connect

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang Gao, Ziwei

    2015-01-15

    A successive anchoring of Ti(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 silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.

  12. Catalytic activity of bimetallic catalysts highly sensitive to the atomic composition and phase structure at the nanoscale.

    PubMed

    Shan, Shiyao; Petkov, Valeri; Prasai, Binay; Wu, Jinfang; Joseph, Pharrah; Skeete, Zakiya; Kim, Eunjoo; Mott, Derrick; Malis, Oana; Luo, Jin; Zhong, Chuan-Jian

    2015-12-01

    The ability to determine the atomic arrangement in nanoalloy catalysts and reveal the detailed structural features responsible for the catalytically active sites is essential for understanding the correlation between the atomic structure and catalytic properties, enabling the preparation of efficient nanoalloy catalysts by design. Herein we describe a study of CO oxidation over PdCu nanoalloy catalysts focusing on gaining insights into the correlation between the atomic structures and catalytic activity of nanoalloys. PdCu nanoalloys of different bimetallic compositions are synthesized as a model system and are activated by a controlled thermochemical treatment for assessing their catalytic activity. The results show that the catalytic synergy of Pd and Cu species evolves with both the bimetallic nanoalloy composition and temperature of the thermochemical treatment reaching a maximum at a Pd : Cu ratio close to 50 : 50. The nanoalloys are characterized structurally by ex situ and in situ synchrotron X-ray diffraction, including atomic pair distribution function analysis. The structural data show that, depending on the bimetallic composition and treatment temperature, PdCu nanoalloys adopt two different structure types. One features a chemically ordered, body centered cubic (B2) type alloy consisting of two interpenetrating simple cubic lattices, each occupied with Pd or Cu species alone, and the other structure type features a chemically disordered, face-centered cubic (fcc) type of alloy wherein Pd and Cu species are intermixed at random. The catalytic activity for CO oxidation is strongly influenced by the structural features. In particular, it is revealed that the prevalence of chemical disorder in nanoalloys with a Pd : Cu ratio close to 50 : 50 makes them superior catalysts for CO oxidation in comparison with the same nanoalloys of other bimetallic compositions. However, the catalytic synergy can be diminished if the Pd50Cu50 nanoalloys undergo

  13. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts.

    PubMed

    Santos, Vera P; Wezendonk, Tim A; Jaén, Juan José Delgado; Dugulan, A Iulian; Nasalevich, Maxim A; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A; Koeken, Ard C J; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-05

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  14. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts

    NASA Astrophysics Data System (ADS)

    Santos, Vera P.; Wezendonk, Tim A.; Jaén, Juan José Delgado; Dugulan, A. Iulian; Nasalevich, Maxim A.; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A.; Koeken, Ard C. J.; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R.; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-01

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  15. NOx reduction Activity over Phosphate-supported Platinum Catalysts with Hydrogen under Oxygen-rich Condition

    NASA Astrophysics Data System (ADS)

    Itoh, M.; Takehara, M.; Saito, M.; Machida, K.

    2011-10-01

    The phosphate supported Pt catalysts (Pt/AlPO4, Pt/CePO4, Pt/CeP2O7, Pt/SnP2O7, Pt/TiP2O7, Pt/Zn3(PO4)2) were prepared by a conventional impregnation method to evaluate their selective catalytic reduction activity of NOx under excess oxygen condition. Among them, good NOx reduction activity was obtained on the Pt/AlPO4 catalyst. Specific adsorption species during the NOx reduction were checked by a diffuse reflectance infrared Fourier transform spectrum (DRIFTs) measurement to examine the reaction mechanism. Also NH3 temperature programmed desorption measurements were performed for all catalysts and their catalytic properties were discussed from the viewpoints of solid acidity.

  16. Enhanced Oxygen Reduction Activity In Acid By Tin-Oxide Supported Au Nanoparticle Catalysts

    SciTech Connect

    Baker,W.; Pietron, J.; Teliska, M.; Bouwman, P.; Ramaker, D.; Swider-Lyons, K.

    2006-01-01

    Gold nanoparticles supported on hydrous tin-oxide (Au-SnO{sub x}) are active for the four-electron oxygen reduction reaction in an acid electrolyte. The unique electrocatalytic of the Au-SnO is confirmed by the low amount of peroxide detected with rotating ring-disk electrode voltammetry and Koutecky-Levich analysis. In comparison, 10 wt % Au supported on Vulcan carbon and SnO{sub x} catalysts both produce significant peroxide in the acid electrolyte, indicating only a two-electron reduction reaction. Characterization of the Au-SnO{sub x} catalyst reveals a high-surface area, amorphous support with 1.7 nm gold metal particles. The high catalytic activity of the Au-SnO is attributed to metal support interactions. The results demonstrate a possible path to non-Pt catalysts for proton exchange membrane fuel cell cathodes.

  17. Kinetics studies of d-glucose hydrogenation over activated charcoal supported platinum catalyst

    NASA Astrophysics Data System (ADS)

    Ahmed, Muthanna J.

    2012-02-01

    The kinetics of the catalytic hydrogenation of d-glucose to produce d-sorbitol was studied in a three-phase laboratory scale reactor. The hydrogenation reactions were performed on activated charcoal supported platinum catalyst in the temperature range 25-65°C and in a constant pressure of 1 atm. The kinetic data were modeled by zero, first and second-order reaction equations. In the operating regimes studied, the results show that the hydrogenation reaction was of a first order with respect to d-glucose concentration. Also the activation energy of the reaction was determined, and found to be 12.33 kJ mole-1. A set of experiment was carried out to test the deactivation of the catalyst, and the results show that the deactivation is slow with the ability of using the catalyst for several times with a small decrease in product yield.

  18. Air Oxidation of Activated Carbon to Synthesize a Biomimetic Catalyst for Hydrolysis of Cellulose.

    PubMed

    Shrotri, Abhijit; Kobayashi, Hirokazu; Fukuoka, Atsushi

    2016-06-01

    Oxygenated carbon catalyzes the hydrolysis of cellulose present in lignocellulosic biomass by utilizing the weakly acidic functional groups on its surface. Here we report the synthesis of a biomimetic carbon catalyst by simple and economical air-oxidation of a commercially available activated carbon. Air- oxidation at 450-500 °C introduced 2000-2400 μmol g(-1) of oxygenated functional groups on the material with minor changes in the textural properties. Selectivity towards the formation of carboxylic groups on the catalyst surface increased with the increase in oxidation temperature. The degree of oxidation on carbon catalyst was found to be proportional to its activity for hydrolysis of cellulose. The hydrolysis of eucalyptus in the presence of carbon oxidized at 475 °C afforded glucose yield of 77 % and xylose yield of 67 %.

  19. Catalysts possessing augmented C-O and C-N hydrogenolysis activity. Progress report No. 3, April-June 1984

    SciTech Connect

    Massoth, F.E.; Shabtai, J.S.

    1984-07-01

    The aim this research project is to synthesize and investigate new sulfided catalyst systems having higher carbon-heteroatom hydrogenolysis activity as compared with ring hydrogenation activity. A fundamental approach is being applied to gain understanding of the basic catalytic properties which relate to hydrogenolysis, hydrogenation and cracking functions of the catalysts. This involves preparation of new catalysts, characterization of their properties and model compound reactivity studies. In another part of the project, selected catalysts are being applied in studies of more complex O- and N- containing model compounds with the objective of providing fundamental data on the stereochemistry of HDO and HDN reactions. These data will be used to develop steric surface-reactant models for sulfided catalysts. Supported noble metal catalysts containing Rh and Pd were prepared by incipient wetness impregnation of ..gamma..-Al/sub 2/O/sub 3/ using nitrate solutions. Catalysts containing also Co and Cr were similarly prepared. Catalyst activities for HDO and HDN were evaluated using the model compounds dibenzofuran and indole. Characterization work by ESCA and oxygen chemisorption, of CoMo catalysts, and stereochemical studies with several catalysts were also initiated. 15 references, 1 figure, 3 tables.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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. PMID:26878237

  2. Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue

    DOEpatents

    Sharp, David W.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered for the particles by contacting or washing them with an aqueous solution containing calcium or magnesium ions in an alkali metal recovery zone at a low temperature, preferably below about 249.degree. F. During the washing or leaching process, the calcium or magnesium ions displace alkali metal ions held by ion exchange sites in the particles thereby liberating the ions and producing an aqueous effluent containing alkali metal constituents. The aqueous effluent from the alkali metal recovery zone is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  3. Nanocrystalline Ferrihydrite-Based Catalysts for Fischer-Tropsch Synthesis: Part II. Effects of Activation Gases on the Catalytic Performance.

    PubMed

    Rhim, Geun Bae; Hong, Seok Yong; Park, Ji Chan; Jung, Heon; Rhee, Young Woo; Chun, Dong Hyun

    2016-02-01

    Fischer-Tropsch synthesis (FTS) was carried out over nanocrystalline ferrihydrite-based (Fe9O2(OH)23) catalysts activated by different reducing agents: syngas (H2+CO), CO, and H2. The syngas activation successfully changed the ferrihydrite-based catalysts into an active and stable catalytic structure with chi-carbide (Fe2.5 C) and epsilon'-carbide (Fe2.2 C). The crystal structure of the catalysts obtained by syngas activation was similar to the structure obtained by CO activation; this similarity was probably due to the peculiar reduction behavior of the ferrihydrite-based catalysts, which exhibit much greater reducibility in CO atmosphere than in H2 atmosphere. The performance of the catalysts activated by syngas was much higher than the performance of the catalysts activated by H2 and was comparable to the performance of the catalysts activated by CO. This strongly demonstrates that the ferrihydrite-based catalysts are advantageous for industrial FTS processes because syngas can be commonly used for both activation pre-treatment and subsequent reaction.

  4. Nanocrystalline Ferrihydrite-Based Catalysts for Fischer-Tropsch Synthesis: Part II. Effects of Activation Gases on the Catalytic Performance.

    PubMed

    Rhim, Geun Bae; Hong, Seok Yong; Park, Ji Chan; Jung, Heon; Rhee, Young Woo; Chun, Dong Hyun

    2016-02-01

    Fischer-Tropsch synthesis (FTS) was carried out over nanocrystalline ferrihydrite-based (Fe9O2(OH)23) catalysts activated by different reducing agents: syngas (H2+CO), CO, and H2. The syngas activation successfully changed the ferrihydrite-based catalysts into an active and stable catalytic structure with chi-carbide (Fe2.5 C) and epsilon'-carbide (Fe2.2 C). The crystal structure of the catalysts obtained by syngas activation was similar to the structure obtained by CO activation; this similarity was probably due to the peculiar reduction behavior of the ferrihydrite-based catalysts, which exhibit much greater reducibility in CO atmosphere than in H2 atmosphere. The performance of the catalysts activated by syngas was much higher than the performance of the catalysts activated by H2 and was comparable to the performance of the catalysts activated by CO. This strongly demonstrates that the ferrihydrite-based catalysts are advantageous for industrial FTS processes because syngas can be commonly used for both activation pre-treatment and subsequent reaction. PMID:27433672

  5. Relation between hydrodesulfurization activity and the state of promoters in precursor calcined Ni-Co-Mo/Al/sub 2/O/sub 3/ catalysts

    SciTech Connect

    Caceres, C.; Fierro, J.L.G.; Agudo, A.L.; Severino, F.; Laine, J.

    1986-01-01

    Two series of NiCo-Mo/Al/sub 2/O/sub 3/ hydrodesulfurization (HDS) catalysts prepared by different procedures were investigated. In each series the Mo loading and the total content of promoters (Co + Ni) were kept constant but the Co/(Co + Ni) atomic ratio was varied from 0 to 1. The two series of catalysts were prepared by a sequential wet impregnation technique. In series I, the impregnations of both Mo and promoters were carried out at the pH of the impregnating aqueous solutions, employing an intermediate calcination; in series II, Mo was impregnated at pH 10, while the promoters were added in aqueous ethanol solutions without intermediate calcination. Catalysts in their calcined state were characterized by reduction in H/sub 2/ at 500/sup 0/C, O/sub 2/ chemisorption, and infrared spectroscopy of adsorbed NO. The HDS activity and the optimum Co/(Co + Ni) atomic ratio were different for the two series, in agreement with the previous studies, HDS activity being generally higher for series II than for series I. Dispersion of Mo (as estimated from O/sub 2/ chemisorption) and NO adsorption on Mo in reduced catalysts (as judged from the intensity of the band at about 1705 cm/sup -1/) were not substantially different for the two series of catalysts and did not correlate with HDS activity. However, adsorbed NO on promoters in oxidized catalysts (bands at about 1880 and 1800 cm/sup -1/) followed roughly the same trend as HDS activity, suggesting that the active sites may be related to the Co and Ni atoms adsorbing NO. Possible reasons for the differences between HDS activity of the two series are considered.

  6. Commercial runs show TiO/sub 2/ Claus catalyst retains activity

    SciTech Connect

    Nougayrede, J.; Philippe, A.; Quesmerel, E.; Vermeersch, R.

    1987-08-10

    Commercial data are given for the CRS 31 Claus catalyst, jointly developed by Rhone Poulenc and Societe Nationale Elf Aquitane (Production) (SNEA). The data confirm laboratory results that show the catalyst's ability to deliver more complete hydrolysis in the first reactor of Claus sulfur recovery plants, and its ability to maintain activity in the second and third reactors. The most important losses in sulfur yields in Claus plants generally come from COS and CS/sub 2/ formed in the thermal steps of the process in the first reactor, and from the low Claus activity of alumina-based catalysts in the second and third reactors. In the first reactor, loaded with alumina-based catalyst, hydrolysis is only partial. Low Claus activity in second and third reactors is caused by the inevitable sulfation of the alumina. Catalytic-activity decrease of aluminas is caused particularly by the presence of oxygen, even in trace amounts, in the Claus gases. Therefore, in the first reactor, the CS/sub 2/ hydrolysis rate is lowered in the subsequent reactors, the H/sub 2/ + SO/sub 2/ conversion significantly drops. The chemical composition of CRS 31, TiO/sub 2/ only, in the same operating conditions, causes a significant improvement in activity because of its increased resistance to sulfation. The economics of the process are given.

  7. The Significance of Lewis Acid Sites for the Selective Catalytic Reduction of Nitric Oxide on Vanadium-Based Catalysts.

    PubMed

    Marberger, Adrian; Ferri, Davide; Elsener, Martin; Kröcher, Oliver

    2016-09-19

    The long debated reaction mechanisms of the selective catalytic reduction (SCR) of nitric oxide with ammonia (NH3 ) on vanadium-based catalysts rely on the involvement of Brønsted or Lewis acid sites. This issue has been clearly elucidated using a combination of transient perturbations of the catalyst environment with operando time-resolved spectroscopy to obtain unique molecular level insights. Nitric oxide reacts predominantly with NH3 coordinated to Lewis sites on vanadia on tungsta-titania (V2 O5 -WO3 -TiO2 ), while Brønsted sites are not involved in the catalytic cycle. The Lewis site is a mono-oxo vanadyl group that reduces only in the presence of both nitric oxide and NH3 . We were also able to verify the formation of the nitrosamide (NH2 NO) intermediate, which forms in tandem with vanadium reduction, and thus the entire mechanism of SCR. Our experimental approach, demonstrated in the specific case of SCR, promises to progress the understanding of chemical reactions of technological relevance.

  8. The Significance of Lewis Acid Sites for the Selective Catalytic Reduction of Nitric Oxide on Vanadium-Based Catalysts.

    PubMed

    Marberger, Adrian; Ferri, Davide; Elsener, Martin; Kröcher, Oliver

    2016-09-19

    The long debated reaction mechanisms of the selective catalytic reduction (SCR) of nitric oxide with ammonia (NH3 ) on vanadium-based catalysts rely on the involvement of Brønsted or Lewis acid sites. This issue has been clearly elucidated using a combination of transient perturbations of the catalyst environment with operando time-resolved spectroscopy to obtain unique molecular level insights. Nitric oxide reacts predominantly with NH3 coordinated to Lewis sites on vanadia on tungsta-titania (V2 O5 -WO3 -TiO2 ), while Brønsted sites are not involved in the catalytic cycle. The Lewis site is a mono-oxo vanadyl group that reduces only in the presence of both nitric oxide and NH3 . We were also able to verify the formation of the nitrosamide (NH2 NO) intermediate, which forms in tandem with vanadium reduction, and thus the entire mechanism of SCR. Our experimental approach, demonstrated in the specific case of SCR, promises to progress the understanding of chemical reactions of technological relevance. PMID:27553251

  9. Bifunctional enhancement of oxygen reduction reaction activity on Ag catalysts due to water activation on LaMnO3 supports in alkaline media.

    PubMed

    Park, Shin-Ae; Lee, Eun-Kyung; Song, Hannah; Kim, Yong-Tae

    2015-08-27

    Ag is considered to be one of the best candidates for oxygen reduction reaction electrocatalysts in alkaline media for application in various electrochemical energy devices. In this study, we demonstrate that water activation is a key factor in enhancing the ORR activity in alkaline media, unlike in acid environments. Ag supported on LaMnO3 having a high oxophilicity showed a markedly higher ORR activity than that on carbon with inert surfaces. Through various electrochemical tests, it was revealed that the origin of the enhanced ORR activity of Ag/LaMnO3 is the bifunctional effect mainly due to the water activation at the interface between Ag and LaMnO3. Furthermore, the ligand effect due to the charge transfer from Mn to Ag leads to the enhancement of both oxygen activation on Ag and water activation on Mn sites, and hence, an improvement in the ORR activity of Ag/LaMnO3. On the other hand, the strain effect based on the fine structure variation in the lattice was negligible. We therefore suggest that the employment of a co-catalyst or support with highly oxophilic nature and the maximization of the interface between catalyst and support should be considered in the design of electrocatalysts for the ORR in alkaline media.

  10. Highly Active Carbon Supported Pd-Ag Nanofacets Catalysts for Hydrogen Production from HCOOH.

    PubMed

    Wang, Wenhui; He, Ting; Liu, Xuehua; He, Weina; Cong, Hengjiang; Shen, Yangbin; Yan, Liuming; Zhang, Xuetong; Zhang, Jinping; Zhou, Xiaochun

    2016-08-17

    Hydrogen is regarded as a future sustainable and clean energy carrier. Formic acid is a safe and sustainable hydrogen storage medium with many advantages, including high hydrogen content, nontoxicity, and low cost. In this work, a series of highly active catalysts for hydrogen production from formic acid are successfully synthesized by controllably depositing Pd onto Ag nanoplates with different Ag nanofacets, such as Ag{111}, Ag{100}, and the nanofacet on hexagonal close packing Ag crystal (Ag{hcp}). Then, the Pd-Ag nanoplate catalysts are supported on Vulcan XC-72 carbon black to prevent the aggregation of the catalysts. The research reveals that the high activity is attributed to the formation of Pd-Ag alloy nanofacets, such as Pd-Ag{111}, Pd-Ag{100}, and Pd-Ag{hcp}. The activity order of these Pd-decorated Ag nanofacets is Pd-Ag{hcp} > Pd-Ag{111} > Pd-Ag{100}. Particularly, the activity of Pd-Ag{hcp} is up to an extremely high value, i.e., TOF{hcp} = 19 000 ± 1630 h(-1) at 90 °C (lower limit value), which is more than 800 times higher than our previous quasi-spherical Pd-Ag alloy nanocatalyst. The initial activity of Pd-Ag{hcp} even reaches (3.13 ± 0.19) × 10(6) h(-1) at 90 °C. This research not only presents highly active catalysts for hydrogen generation but also shows that the facet on the hcp Ag crystal can act as a potentially highly active catalyst. PMID:27454194

  11. Highly Active Carbon Supported Pd-Ag Nanofacets Catalysts for Hydrogen Production from HCOOH.

    PubMed

    Wang, Wenhui; He, Ting; Liu, Xuehua; He, Weina; Cong, Hengjiang; Shen, Yangbin; Yan, Liuming; Zhang, Xuetong; Zhang, Jinping; Zhou, Xiaochun

    2016-08-17

    Hydrogen is regarded as a future sustainable and clean energy carrier. Formic acid is a safe and sustainable hydrogen storage medium with many advantages, including high hydrogen content, nontoxicity, and low cost. In this work, a series of highly active catalysts for hydrogen production from formic acid are successfully synthesized by controllably depositing Pd onto Ag nanoplates with different Ag nanofacets, such as Ag{111}, Ag{100}, and the nanofacet on hexagonal close packing Ag crystal (Ag{hcp}). Then, the Pd-Ag nanoplate catalysts are supported on Vulcan XC-72 carbon black to prevent the aggregation of the catalysts. The research reveals that the high activity is attributed to the formation of Pd-Ag alloy nanofacets, such as Pd-Ag{111}, Pd-Ag{100}, and Pd-Ag{hcp}. The activity order of these Pd-decorated Ag nanofacets is Pd-Ag{hcp} > Pd-Ag{111} > Pd-Ag{100}. Particularly, the activity of Pd-Ag{hcp} is up to an extremely high value, i.e., TOF{hcp} = 19 000 ± 1630 h(-1) at 90 °C (lower limit value), which is more than 800 times higher than our previous quasi-spherical Pd-Ag alloy nanocatalyst. The initial activity of Pd-Ag{hcp} even reaches (3.13 ± 0.19) × 10(6) h(-1) at 90 °C. This research not only presents highly active catalysts for hydrogen generation but also shows that the facet on the hcp Ag crystal can act as a potentially highly active catalyst.

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

    SciTech Connect

    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.

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

    PubMed

    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. PMID:27240245

  14. Mesoporous carbon-supported Pd nanoparticles with high specific surface area for cyclohexene hydrogenation: Outstanding catalytic activity of NaOH-treated catalysts

    NASA Astrophysics Data System (ADS)

    Puskás, R.; Varga, T.; Grósz, A.; Sápi, A.; Oszkó, A.; Kukovecz, Á.; Kónya, Z.

    2016-06-01

    Extremely high specific surface area mesoporous carbon-supported Pd nanoparticle catalysts were prepared with both impregnation and polyol-based sol methods. The silica template used for the synthesis of mesoporous carbon was removed by both NaOH and HF etching. Pd/mesoporous carbon catalysts synthesized with the impregnation method has as high specific surface area as 2250 m2/g. In case of NaOH-etched impregnated samples, the turnover frequency of cyclohexene hydrogenation to cyclohexane at 313 K was obtained ~ 14 molecules • site- 1 • s- 1. The specific surface area of HF-etched samples was higher compared to NaOH-etched samples. However, catalytic activity was ~ 3-6 times higher on NaOH-etched samples compared to HF-etched samples, which can be attributed to the presence of sodium and surface hydroxylgroups of the catalysts etched with NaOH solution.

  15. Ligand-free Heck reaction: Pd(OAc)2 as an active catalyst revisited.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Yang, Zhi

    2003-09-19

    Palladium acetate was shown to be an extremely active catalyst for the Heck reaction of aryl bromides. Both the base and the solvent were found to have a fundamental influence on the efficiency of the reaction, with K(3)PO(4) and N,N-dimethylacetamide being the optimal base and solvent, respectively. PMID:12968913

  16. Ligand-free Heck reaction: Pd(OAc)2 as an active catalyst revisited.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Yang, Zhi

    2003-09-19

    Palladium acetate was shown to be an extremely active catalyst for the Heck reaction of aryl bromides. Both the base and the solvent were found to have a fundamental influence on the efficiency of the reaction, with K(3)PO(4) and N,N-dimethylacetamide being the optimal base and solvent, respectively.

  17. PREPARATION, CHARACTERIZATION AND ACTIVITY OF AL2O3-SUPPORTED V2O5 CATALYSTS

    EPA Science Inventory

    A series of activated alumina supported vanadium oxide catalysts with various V2O5 loadings ranging from 5 to 25 wt% has been prepared by wet impregnation technique. A combination of various physico-chemical techniques such as BET surface areas, oxygen chemisorption, X-ray diffra...

  18. Alkene Isomerization Using a Solid Acid as Activator and Support for a Homogeneous Catalyst

    ERIC Educational Resources Information Center

    Seen, Andrew J.

    2004-01-01

    An upper-level undergraduate experiment that, in addition to introducing students to catalysis using an air sensitive transition-metal complex, introduces the use of a solid acid as an activator and support for the catalyst is developed. The increased stability acquired in the course of the process affords the opportunity to characterize the…

  19. Graphene-supported hemin as a highly active biomimetic oxidation catalyst.

    PubMed

    Xue, Teng; Jiang, Shan; Qu, Yongquan; Su, Qiao; Cheng, Rui; Dubin, Sergey; Chiu, Chin-Yi; Kaner, Richard; Huang, Yu; Duan, Xiangfeng

    2012-04-16

    Well supported: stable hemin-graphene conjugates formed by immobilization of monomeric hemin on graphene, showed excellent catalytic activity, more than 10 times better than that of the recently developed hemin-hydrogel system and 100 times better than that of unsupported hemin. The catalysts also showed excellent binding affinities and catalytic efficiencies approaching that of natural enzymes. PMID:22368046

  20. Preparation, characterization, and activity of α-Ti(HPO4)2 supported metallocene catalysts

    NASA Astrophysics Data System (ADS)

    Shi, Yasai; Yuan, Yuan; Xu, Qinghong; Yi, Jianjun

    2016-10-01

    A series of heterogeneous catalysts by loading metallocenes on surface of α-Ti(HPO4)2, a kind of solid acid, has been synthesized. Polymerization of alkenes, including ethylene and propylene, based on participation of the heterogeneous catalysts were studied and the results were compared to metallocenes supported on silica gel, α-Zr(HPO4)2 and clay. Higher catalytic activity, larger polymer molecular weight and narrow distribution of polymer molecular weight were obtained. Acidic strength of the support and its influence to metallocenes were studied to discover intrinsic factors in the polymerizations.

  1. Method for preparing high activity silica supported hydrotreating catalysts

    SciTech Connect

    Thompson, M.S.

    1986-03-04

    A method is described for preparing a silica supported hydrotreating catalyst containing from about 10-25%w molybdenum and from about 1-5%w nickel and/or cobalt as hydrogenation metals. The method consists of: (a) reacting a mixture of MoCl/sub 5/ and a compound selected from the group consisting of Ni(H/sub 2/O)/sub 6/Cl/sub 2/, Co(H/sub 2/O)/sub 6/Cl/sub 2/ and mixutres in amounts to provide a desired catalytic metals concentration of the support in the presence of a solubilizing amount of acetonitrile; (b) heating the mixture to between about 25/sup 0/ and 80/sup 0/C until most of the metal compounds have reacted and/or dissolved; (c) removing any undissolved solids from the solution; (d) impregnating the dried silica support with the hydrogenation metals-containing solution in one or more steps; and (e) drying the impregnated silica support at elevated temperature.

  2. Highly active cobalt phosphate and borate based oxygen evolving catalysts operating in neutral and natural waters

    SciTech Connect

    Esswein, AJ; Surendranath, Y; Reece, SY; Nocera, DG

    2011-02-01

    A high surface area electrode is functionalized with cobalt-based oxygen evolving catalysts (Co-OEC = electrodeposited from pH 7 phosphate, Pi, pH 8.5 methylphosphonate, MePi, and pH 9.2 borate electrolyte, Bi). Co-OEC prepared from MePi and operated in Pi and Bi achieves a current density of 100 mA cm(-2) for water oxidation at 442 and 363 mV overpotential, respectively. The catalyst retains activity in near-neutral pH buffered electrolyte in natural waters such as those from the Charles River (Cambridge, MA) and seawater (Woods Hole, MA). The efficacy and ease of operation of anodes functionalized with Co-OEC at appreciable current density together with its ability to operate in near neutral pH buffered natural water sources bodes well for the translation of this catalyst to a viable renewable energy storage technology.

  3. Method of treating intermetallic alloy hydrogenation/oxidation catalysts for improved impurity poisoning resistance, regeneration and increased activity

    DOEpatents

    Wright, R.B.

    1992-01-14

    Alternate, successive high temperature oxidation and reduction treatments, in either order, of intermetallic alloy hydrogenation and intermetallic alloy oxidation catalysts unexpectedly improves the impurity poisoning resistance, regeneration capacity and/or activity of the catalysts. The particular alloy, and the final high temperature treatment given alloy (oxidation or reduction) will be chosen to correspond to the function of the catalyst (oxidation or hydrogenation). 23 figs.

  4. Pt5Gd as a highly active and stable catalyst for oxygen electroreduction.

    PubMed

    Escudero-Escribano, María; Verdaguer-Casadevall, Arnau; Malacrida, Paolo; Grønbjerg, Ulrik; Knudsen, Brian P; Jepsen, Anders K; Rossmeisl, Jan; Stephens, Ifan E L; Chorkendorff, Ib

    2012-10-10

    The activity and stability of Pt(5)Gd for the oxygen reduction reaction (ORR) have been studied, using a combination of electrochemical measurements, angle-resolved X-ray photoelectron spectroscopy (AR-XPS), and density functional theory calculations. Sputter-cleaned, polycrystalline Pt(5)Gd shows a 5-fold increase in ORR activity, relative to pure Pt at 0.9 V, approaching the most active in the literature for catalysts prepared in this way. AR-XPS profiles after electrochemical measurements in 0.1 M HClO(4) show the formation of a thick Pt overlayer on the bulk Pt(5)Gd, and the enhanced ORR activity can be explained by means of compressive strain effects. Furthermore, these novel bimetallic electrocatalysts are highly stable, which, in combination with their enhanced activity, makes them very promising for the development of new cathode catalysts for fuel cells. PMID:22998588

  5. Synthesis, characterization and catalytic activity of carbon-silica hybrid catalyst from rice straw

    NASA Astrophysics Data System (ADS)

    Janaun, J.; Safie, N. N.; Siambun, N. J.

    2016-07-01

    The hybrid-carbon catalyst has been studied because of its promising potential to have high porosity and surface area to be used in biodiesel production. Silica has been used as the support to produce hybrid carbon catalyst due to its mesoporous structure and high surface area properties. The chemical synthesis of silica-carbon hybrid is expensive and involves more complicated preparation steps. The presence of natural silica in rice plants especially rice husk has received much attention in research because of the potential as a source for solid acid catalyst synthesis. But study on rice straw, which is available abundantly as agricultural waste is limited. In this study, rice straw undergone pyrolysis and functionalized using fuming sulphuric acid to anchor -SO3H groups. The presence of silica and the physiochemical properties of the catalyst produced were studied before and after sulphonation. The catalytic activity of hybrid carbon silica acid catalyst, (H-CSAC) in esterification of oleic acid with methanol was also studied. The results showed the presence of silica-carbon which had amorphous structure and highly porous. The carbon surface consisted of higher silica composition, had lower S element detected as compared to the surface that had high carbon content but lower silica composition. This was likely due to the fact that Si element which was bonded to oxygen was highly stable and unlikely to break the bond and react with -SO3H ions. H-CSAC conversions were 23.04 %, 35.52 % and 34.2 7% at 333.15 K, 343.15 K and 353.15 K, respectively. From this research, rice straw can be used as carbon precursor to produce hybrid carbon-silica catalyst and has shown catalytic activity in biodiesel production. Rate equation obtained is also presented.

  6. Structure-activity correlations in a nickel-borate oxygen evolution catalyst.

    PubMed

    Bediako, D Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh; Yano, Junko; Yachandra, Vittal K; Nocera, Daniel G

    2012-04-18

    An oxygen evolution catalyst that forms as a thin film from Ni(aq)(2+) solutions containing borate electrolyte (Ni-B(i)) has been studied by in situ X-ray absorption spectroscopy. A dramatic increase in catalytic rate, induced by anodic activation of the electrodeposited films, is accompanied by structure and oxidation state changes. Coulometric measurements correlated with X-ray absorption near-edge structure spectra of the active catalyst show that the nickel centers in activated films possess an average oxidation state of +3.6, indicating that a substantial proportion of nickel centers exist in a formal oxidation state of Ni(IV). In contrast, nickel centers in nonactivated films exist predominantly as Ni(III). Extended X-ray absorption fine structure reveals that activated catalyst films comprise bis-oxo/hydroxo-bridged nickel centers organized into sheets of edge-sharing NiO(6) octahedra. Diminished long-range ordering in catalyst films is due to their ostensibly amorphous nature. Nonactivated films display a similar oxidic nature but exhibit a distortion in the local coordination geometry about nickel centers, characteristic of Jahn-Teller distorted Ni(III) centers. Our findings indicate that the increase in catalytic activity of films is accompanied by changes in oxidation state and structure that are reminiscent of those observed for conversion of β-NiOOH to γ-NiOOH and consequently challenge the long-held notion that the β-NiOOH phase is a more efficient oxygen-evolving catalyst. PMID:22417283

  7. Steam gasification of carbon: Catalyst properties

    SciTech Connect

    Falconer, J.L.

    1991-12-13

    This research uses several techniques to measure the concentration of catalyst sites and determine their stoichiometry for the catalyzed gasification of carbon. Both alkali and alkaline earth oxides are effective catalysts for accelerating the gasification rate of coal chars, but only a fraction of the catalyst appears to be in a form that is effective for gasification, and the composition of that catalyst is not established. Transient techniques with {sup 13}C labeling, are being used to study the surface processes, to measure the concentration of active sites, and to determine the specific reaction rates. We have used secondary ion mass spectrometry (SIMS) for both high surface area samples of carbon/alkali carbonate mixtures and for model carbon surfaces with deposited alkali atoms. SIMS provides a direct measure of surface composition. The combination of these results can provide knowledge of catalyst dispersion and composition, and thus indicate the way to optimally utilize carbon gasification catalysts.

  8. Highly active trialkoxymolybdenum(VI) alkylidyne catalysts synthesized by a reductive recycle strategy.

    PubMed

    Zhang, Wei; Kraft, Stefan; Moore, Jeffrey S

    2004-01-14

    A systematic study of alkyne metathesis catalyzed by trialkoxymolybdenum(VI) alkylidyne complexes is reported, in which substrate functional groups, alkynyl substituents, and catalyst ligands are varied. Sterically hindered trisamidomolybdenum(VI) propylidyne complex 5 was prepared conveniently through a previously communicated reductive recycle strategy. Alcoholysis of 5 with various phenols/alcohols provides a set of active catalysts for alkyne metathesis at room temperature, among which the catalyst with p-nitrophenol as ligand shows the highest catalytic activity and is compatible with a variety of functional groups and solvents. A key finding that enabled the use of highly active molybdenum(VI) catalysts is replacement of the commonly used propynyl substituents on the starting alkyne substrates with butynyl groups. Under reduced pressure using 1,2,4-trichlorobenzene as an involatile solvent, the alkyne metathesis of butynyl substituted compounds proceeds well at 30 degrees C providing high yields (83%-97%) of dimers. Rationalization of the special role played by butynyl substrates is discussed.

  9. Enhanced activity of urea electrooxidation on nickel catalysts supported on tungsten carbides/carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Wang, Lu; Du, Tingting; Cheng, Jin; Xie, Xing; Yang, Bolun; Li, Mingtao

    2015-04-01

    Nickel nanoparticles with tungsten carbides supported on the multi-walled carbon nanotubes, noted as Ni-WC/MWCNT catalyst, is prepared through an impregnation method and used for the electrooxidation of urea in alkaline conditions. The micro-morphology and composition of the Ni-WC/MWCNT particles are determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. The electrooxidation activity and conductivity of the catalyst are investigated by cyclic voltammetry and electrochemical impedance spectroscopy, respectively. Characterization results indicate that the Ni nanoparticles are uniformly distributed on the WC/MWCNT framework, and the Ni-WC/MWCNT catalyst shows an improved activity for the urea electrooxidation. The current densities of Ni-WC/MWCNT are over 3 times and 15 times higher than those of the Ni-WC/C and Ni/C catalysts, respectively, and the electrochemical impedance also decreases markedly. The higher activity on Ni-WC/MWCNT is attributed to the support effect of MWCNT as well as the synergistic effect between Ni and WC.

  10. Active Sites Environmental Monitoring Program: Action levels

    SciTech Connect

    Ashwood, J.S.; Ashwood, T.L.

    1991-10-01

    The Active Sites Environmental Monitoring Program (ASEMP) was established at Oak Ridge National Laboratory to provide for early leak detection and to monitor performance of the active low-level waste disposal facilities in Solid Waste Storage Area (SWSA) 6 and the transuranic waste storage areas in SWSA 5 North. Early leak detection is accomplished by sampling runoff, groundwater, and perched water in burial trenches. Sample results are compared to action levels that represent background contamination by naturally occurring and fallout-derived radionuclides. 15 refs., 3 figs., 12 tabs.

  11. An investigation of active and selective oxygen in vanadium phosphorus oxide catalysts for n-butane conversion to maleic anhydride

    SciTech Connect

    Lashier, M.E.

    1990-01-01

    The role of lattice oxygens in two model catalysts, {beta}-VOPO{sub 4} and (VO){sub 2}P{sub 2}O{sub 7}, was investigated for the selective and nonselective oxidation of C{sub 4} hydrocarbons to maleic anhydride and combustion products. Specific catalytic oxygen sites in each model catalyst were labeled with specific amounts of {sup 18}O. Labeled sites were identified by laser Raman spectroscopy and Fourier transform infrared spectroscopy. The level of {sup 18}O enrichment in each site was estimated from the laser Raman spectra and the stoichiometry of reactions involved in the synthesis of the labeled catalysts. Products of the anaerobic C{sub 4} hydrocarbon oxidation and, in the case of (VO){sub 2}P{sub 2}O{sub 7}, alternating pulses of oxygen with pulses of hydrocarbon, over labeled catalysts were monitored by quadrupole mass spectrometry. 146 refs., 51 figs., 7 tabs.

  12. Activity of platinum/carbon and palladium/carbon catalysts promoted by Ni2 P in direct ethanol fuel cells.

    PubMed

    Li, Guoqiang; Feng, Ligang; Chang, Jinfa; Wickman, Björn; Grönbeck, Henrik; Liu, Changpeng; Xing, Wei

    2014-12-01

    Ethanol is an alternative fuel for direct alcohol fuel cells, in which the electrode materials are commonly based on Pt or Pd. Owing to the excellent promotion effect of Ni2 P that was found in methanol oxidation, we extended the catalyst system of Pt or Pd modified by Ni2 P in direct ethanol fuel cells. The Ni2 P-promoted catalysts were compared to commercial catalysts as well as to reference catalysts promoted with only Ni or only P. Among the studied catalysts, Pt/C and Pd/C modified by Ni2 P (30 wt %) showed both the highest activity and stability. Upon integration into the anode of a homemade direct ethanol fuel cell, the Pt-Ni2 P/C-30 % catalyst showed a maximum power density of 21 mW cm(-2) , which is approximately two times higher than that of a commercial Pt/C catalyst. The Pd-Ni2 P/C-30 % catalyst exhibited a maximum power density of 90 mW cm(-2) . This is approximately 1.5 times higher than that of a commercial Pd/C catalyst. The discharge stability on both two catalysts was also greatly improved over a 12 h discharge operation.

  13. ``Greener Shade of Ruthenium'': New Concepts of Activation, Immobilization, and Recovery of Ruthenium Catalysts For Green Olefin Metathesis

    NASA Astrophysics Data System (ADS)

    Michrowska, Anna; Gulajski, Lukasz; Grela, Karol

    The results described herewith demonstrate that the activity of ruthenium (Ru) metathesis catalysts can be enhanced by introduction of electron-withdrawing groups (EWGs) without detriment to catalysts stability. This principle can be used not only to increase the catalyst activity, but also to alter its physical-chemical properties, such as solubility in given medium or affinity to silica gel. An example of novel immobilisation strategy, based on this concept is presented. The ammonium-tagged Hoveyda-type catalysts can be successfully applied in aqueous media as well as in ionic liquids (IL). Substitution of a benzylidene fragment can be used not only to immobilize the organometallic complex in such media, but also to increase its catalytic activity by electronic activation. The high stability and good application profiles of such modified catalysts in conjunction with their facile removal from organic products can be expected to offer new opportunities in green applications of olefin metathesis.

  14. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    NASA Astrophysics Data System (ADS)

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

    2015-01-01

    A successive anchoring of Ti(NMe2)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 silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands.

  15. Characterizing Surface Acidic Sites in Mesoporous-Silica-Supported Tungsten Oxide Catalysts Using Solid State NMR and Quantum Chemistry Calculations

    SciTech Connect

    Hu, Jian Z.; Kwak, Ja Hun; Wang, Yong; Hu, Mary Y.; Turcu, Romulus VF; Peden, Charles HF

    2011-10-18

    The acidic sites in dispersed tungsten oxide supported on SBA-15 mesoporous silica were investigated using a combination of pyridine titration, both fast-, and slow-MAS {sup 15}N NMR, static {sup 2}H NMR, and quantum chemistry calculations. It is found that the bridged acidic -OH groups in surface adsorbed tungsten dimers (i.e., W-OH-W) are the Broensted acid sites. The unusually strong acidity of these Broensted acid sites is confirmed by quantum chemistry calculations. In contrast, terminal W-OH sites are very stable and only weakly acidic as are terminal Si-OH sites. Furthermore, molecular interactions between pyridine molecules and the dimer Broensted and terminal W-OH sites for dispersed tungsten oxide species is strong. This results in restricted molecular motion for the interacting pyridine molecules even at room temperature, i.e., a reorientation mainly about the molecular 2-fold axis. This restricted reorientation makes it possible to estimate the relative ratio of the Broensted (tungsten dimer) to the weakly acidic terminal W-OH sites in the catalyst using the slow-MAS {sup 1}H-{sup 15}N CP PASS method.

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

    NASA Astrophysics Data System (ADS)

    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

  17. In situ generated highly active copper oxide catalysts for the oxygen evolution reaction at low overpotential in alkaline solutions.

    PubMed

    Liu, Xiang; Cui, Shengsheng; Qian, Manman; Sun, Zijun; Du, Pingwu

    2016-04-25

    Developing efficient water oxidation catalysts made up of earth-abundant elements has attracted much attention as a step toward for future clean energy production. Herein we report a simple one-step method to generate a low cost copper oxide catalyst film in situ from a copper(ii) ethylenediamine complex. The resulting catalyst has excellent activity toward the oxygen evolution reaction in alkaline solutions. A catalytic current density of 1.0 mA cm(-2) and 10 mA cm(-2) for the catalyst film requires the overpotentials of only ∼370 mV and ∼475 mV in 1.0 M KOH, respectively. This catalytic performance shows that the new catalyst is one of the best Cu-based heterogeneous OER catalysts to date. PMID:27020763

  18. Low-temperature catalyst activator: mechanism of dense carbon nanotube forest growth studied using synchrotron radiation

    PubMed Central

    Takashima, Akito; Izumi, Yudai; Ikenaga, Eiji; Ohkochi, Takuo; Kotsugi, Masato; Matsushita, Tomohiro; Muro, Takayuki; Kawabata, Akio; Murakami, Tomo; Nihei, Mizuhisa; Yokoyama, Naoki

    2014-01-01

    The mechanism of the one-order-of-magnitude increase in the density of vertically aligned carbon nanotubes (CNTs) achieved by a recently developed thermal chemical vapor deposition process was studied using synchrotron radiation spectroscopic techniques. In the developed process, a Ti film is used as the underlayer for an Fe catalyst film. A characteristic point of this process is that C2H2 feeding for the catalyst starts at a low temperature of 450°C, whereas conventional feeding temperatures are ∼800°C. Photoemission spectroscopy using soft and hard X-rays revealed that the Ti underlayer reduced the initially oxidized Fe layer at 450°C. A photoemission intensity analysis also suggested that the oxidized Ti layer at 450°C behaved as a support for nanoparticle formation of the reduced Fe, which is required for dense CNT growth. In fact, a CNT growth experiment, where the catalyst chemical state was monitored in situ by X-ray absorption spectroscopy, showed that the reduced Fe yielded a CNT forest at 450°C. Contrarily, an Fe layer without the Ti underlayer did not yield such a CNT forest at 450°C. Photoemission electron microscopy showed that catalyst annealing at the conventional feeding temperature of 800°C caused excess catalyst agglomeration, which should lead to sparse CNTs. In conclusion, in the developed growth process, the low-temperature catalyst activation by the Ti underlayer before the excess Fe agglomeration realised the CNT densification. PMID:25075343

  19. Influence of liquid medium on the activity of a low-alpha Fischer-Tropsch catalyst

    SciTech Connect

    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.

  20. Catalyst suppliers consolidate further, offer more catalysts

    SciTech Connect

    Rhodes, A.K.

    1995-10-02

    The list of suppliers of catalysts to the petroleum refining industry has decreased by five since Oil and Gas Journal`s survey of refining catalysts and catalytic additives was last published. Despite the consolidation, the list of catalyst designations has grown to about 950 in this latest survey, compared to 820 listed in 1993. The table divides the catalysts by use and gives data on their primary differentiating characteristics, feedstock, products, form, bulk density,catalyst support, active agents, availability, and manufactures.

  1. In Situ Observation of Active Oxygen Species in Fe-Containing Ni-Based Oxygen Evolution Catalysts: The Effect of pH on Electrochemical Activity.

    PubMed

    Trześniewski, Bartek J; Diaz-Morales, Oscar; Vermaas, David A; Longo, Alessandro; Bras, Wim; Koper, Marc T M; Smith, Wilson A

    2015-12-01

    Ni-based oxygen evolution catalysts (OECs) are cost-effective and very active materials that can be potentially used for efficient solar-to-fuel conversion process toward sustainable energy generation. We present a systematic spectroelectrochemical characterization of two Fe-containing Ni-based OECs, namely nickel borate (Ni(Fe)-B(i)) and nickel oxyhydroxide (Ni(Fe)OOH). Our Raman and X-ray absorption spectroscopy results show that both OECs are chemically similar, and that the borate anions do not play an apparent role in the catalytic process at pH 13. Furthermore, we show spectroscopic evidence for the generation of negatively charged sites in both OECs (NiOO(-)), which can be described as adsorbed "active oxygen". Our data conclusively links the OER activity of the Ni-based OECs with the generation of those sites on the surface of the OECs. The OER activity of both OECs is strongly pH dependent, which can be attributed to a deprotonation process of the Ni-based OECs, leading to the formation of the negatively charged surface sites that act as OER precursors. This work emphasizes the relevance of the electrolyte effect to obtain catalytically active phases in Ni-based OECs, in addition to the key role of the Fe impurities. This effect should be carefully considered in the development of Ni-based compounds meant to catalyze the OER at moderate pHs. Complementarily, UV-vis spectroscopy measurements show strong darkening of those catalysts in the catalytically active state. This coloration effect is directly related to the oxidation of nickel and can be an important factor limiting the efficiency of solar-driven devices utilizing Ni-based OECs.

  2. Investigation of the active sites of rhodium sulfide for hydrogen evolution/oxidation using carbon monoxide as a probe.

    PubMed

    Singh, Nirala; Upham, David C; Liu, Ru-Fen; Burk, Jonathan; Economou, Nick; Buratto, Steven; Metiu, Horia; McFarland, Eric W

    2014-05-20

    Carbon monoxide (CO) was observed to decrease the activity for hydrogen evolution, hydrogen oxidation, and H2-D2 exchange on rhodium sulfide, platinum, and rhodium metal. The temperature at which the CO was desorbed from the catalyst surface (detected by recovery in the H2-D2 exchange activity of the catalyst) was used as a descriptor for the CO binding energy to the active site. The differences in the CO desorption temperature between the different catalysts showed that the rhodium sulfide active site is not metallic rhodium. Using density functional theory, the binding energy of CO to the Rh sites in rhodium sulfide is found comparable to the binding energy on Pt. Coupled with experiment this supports the proposition that rhodium rather than sulfur atoms in the rhodium sulfide are the active site for the hydrogen reaction. This would indicate the active sites for hydrogen evolution/oxidation as well as oxygen reduction (determined by other groups using X-ray absorption spectroscopy) may be the same.

  3. N-Butyl-2,4-dinitro-anilinium p-toluenesulfonate as a highly active and selective esterification catalyst

    PubMed Central

    Sattenapally, Narsimha; Wang, Wei; Liu, Huimin; Gao, Yong

    2013-01-01

    N-Butyl-2,4-dinitro-anilinium p-toluenesulfonate (1) was found to be a very active esterification catalyst that promotes condensation of equal mole amount of carboxylic acids and alcohols under mild conditions. This catalyst is also highly selective towards carboxylic acid and alcohol substrates at ambient temperature. PMID:24357885

  4. N-Butyl-2,4-dinitro-anilinium p-toluenesulfonate as a highly active and selective esterification catalyst.

    PubMed

    Sattenapally, Narsimha; Wang, Wei; Liu, Huimin; Gao, Yong

    2013-11-27

    N-Butyl-2,4-dinitro-anilinium p-toluenesulfonate (1) was found to be a very active esterification catalyst that promotes condensation of equal mole amount of carboxylic acids and alcohols under mild conditions. This catalyst is also highly selective towards carboxylic acid and alcohol substrates at ambient temperature.

  5. A Highly Active Magnetically Recoverable Nano Ferrite-Glutathione-Copper (Nano-FGT-Cu) Catalyst for Huisgen 1, 3-Dipolar Cycloadditions

    EPA Science Inventory

    A homogeneous catalyst, where the catalyst is in the same phase as the reactants, is generally accepted by chemists.1 One attractive property is that all catalytic sites are accessible because the catalyst is generally a soluble metal complex where it is possible to tune the chem...

  6. Promoting effect of vanadium on catalytic activity of Pt/Ce-Zr-O diesel oxidation catalysts.

    PubMed

    Huang, Haifeng; Jiang, Bo; Gu, Lei; Qi, Zhonghua; Lu, Hanfeng

    2015-07-01

    A series of Pt-V/Ce-Zr-O diesel oxidation catalysts was prepared using the impregnation method. The catalytic activity and sulfur resistance of Pt-V/Ce-Zr-O were investigated in the presence of simulated diesel exhaust. The effect of vanadium on the structure and redox properties of the catalysts was also investigated using the Brunauer-Emmett-Teller method, X-ray diffraction, H2 temperature-programmed reduction, CO temperature-programmed desorption, X-ray photoelectron spectroscopy, and Energy Dispersive Spectroscopy. Results showed that the Pt particles were well dispersed on the Ce-Zr-O carrier through the vanadium isolation effect, which significantly improved the oxidation activity toward CO and hydrocarbons. An electron-withdrawing phenomenon occurred from V to Pt, resulting in an increase in the metallic nature of platinum, which was beneficial to hydrocarbon molecular activation.

  7. Evidence of alloy formation during the activation of graphite-supported palladium-cobalt catalysts

    SciTech Connect

    Noronha, F.B.; Schmal, M.; Frety, R.; Bergeret, G.; Moraweck, B.

    1999-08-15

    Magnetism, XRD, and EXAFS analyses were used to study the formation of a solid solution on Pd-Co/G catalysts during reduction treatment. After reduction at 773 K, magnetic measurements revealed the formation of a Pd-Co alloy. XRD analysis in situ allowed one to follow the alloy process during the increase of the reduction temperature. The XRD results showed the presence of a heterogeneous solid solution after reduction at 773 K. Pd and Co K-edge EXAFS analysis confirmed that bimetallic particles with a palladium- and cobalt-rich phase were formed. The formation of a solid solution decreased the adsorption strength of 1,3-butadiene on new Pd sites modified by Co. Palladium-cobalt catalysts are useful for methanol and ethanol formation from synthesis gas at high pressure.

  8. Key structure-activity relationships in the vanadium phosphorus oxide catalyst system

    SciTech Connect

    Thompson, M.R. ); Ebner, J.R. )

    1990-04-01

    The crystal structure of vanadyl pyrophosphate has been redetermined using single crystals obtained from a near solidified melt of a microcrystalline catalyst sample. Crystals that index as vanadyl pyrophosphate obtained from this melt are variable in color. Crystallographic refinement of the single crystal x-ray diffraction data indicates that structural differences among these materials can be described in terms of crystal defects associated with linear disorder of the vanadium atoms. The importance of the disorder is outlined in the context of its effect on the proposed surface topology parallel to (1,0,0). Models of the surface topology simply and intuitively account for the non-stoichometric surface atomic P/V ratio exhibited by selective catalysts of this phase. These models also point to the possible role of the excess phosphorus in providing site isolation of reactive centers at the surface. 33 refs., 7 figs.

  9. Design of highly active binary catalyst systems for CO2/epoxide copolymerization: polymer selectivity, enantioselectivity, and stereochemistry control.

    PubMed

    Lu, Xiao-Bing; Shi, Lei; Wang, Yi-Ming; Zhang, Rong; Zhang, Ying-Ju; Peng, Xiao-Jun; Zhang, Zhi-Chao; Li, Bo

    2006-02-01

    Asymmetric, regio- and stereoselective alternating copolymerization of CO(2) and racemic aliphatic epoxides proceeds effectively under mild temperature and pressure by using a binary catalyst system of a chiral tetradentate Schiff base cobalt complex [SalenCo(III)X] as the electrophile in conjunction with an ionic organic ammonium salt or a sterically hindered strong organic base as the nucleophile. The substituent groups on the aromatic rings, chiral diamine backbone, and axial X group of the electrophile, as well as the nucleophilicity, leaving ability, and coordination ability of the nucleophile, all significantly affect the catalyst activity, polymer selectivity, enantioselectivity, and stereochemistry. A bulky chiral cyclohexenediimine backbone complex [SalcyCo(III)X] with an axial X group of poor leaving ability as the electrophile, combined with a bulky nuclephile with poor leaving ability and low coordination ability, is an ideal binary catalyst system for the copolymerization of CO(2) and a racemic aliphatic epoxide to selectively produce polycarbonates with relatively high enantioselectivity, >95% head-to-tail connectivity, and >99% carbonate linkages. A fast copolymerization of CO(2) and epoxides was observed when the concentration of the electrophile or/and the nucleophile was increased, and the number of polycarbonate chains was proportional to the concentration of the nucleophile. Electrospray ionization mass spectrometry, in combination with a kinetic study, showed that the copolymerization involved the coordination activation of the monomer by the electrophile and polymer chain growth predominately occurring in the nucleophile. Both the enantiomorphic site effect resulting from the chiral electrophile and the polymer chain end effect mainly from the bulky nucleophile cooperatively control the stereochemistry of the CO(2)/epoxide copolymerization.

  10. Candida antarctica Lipase B Chemically Immobilized on Epoxy-Activate Micro- and Nanobeads: Catalysts for Polyester Synthesis

    SciTech Connect

    Chen,B.; Hu, J.; Miller, E.; Xie, W.; Cai, M.; Gross, R.

    2008-01-01

    Candida antarctica Lipase B (CALB) was covalently immobilized onto epoxy-activated macroporous poly(methyl methacrylate) Amberzyme beads (235 {mu}m particle size, 220 Angstroms pore size) and nanoparticles (nanoPSG, diameter 68 nm) with a poly(glycidyl methacrylate) outer region. Amberzyme beads allowed CALB loading up to 0.16 g of enzyme per gram of support. IR microspectroscopy generated images of Amberzyme-CALB beads showed CALB is localized within a 50 {mu}m thick loading front. IR microspectroscopy images, recorded prior to and after treatment of Amberzyme-CALB with DMSO/aqueous Triton X-100, are similar, confirming that CALB is largely chemically linked to Amberzyme. The activity of CALB immobilized on Amberzyme, Lewatit (i.e., Novozym 435 catalyst), and nanoPSG was assessed for lactone ring-opening and step-condensation polymerizations. For example, the percent conversion of -caprolactone using the same amount of enzyme catalyzed by Amberzym-CALB, Novozym 435, and nanoPSG-CALB for 20 min was 7.0, 16, and 65%, respectively. Differences in CALB reactivity were discussed based on resin physical parameters and availability of active sites determined by active site titrations. Regardless of the matrix used and chemical versus physical immobilization, -CL ring-opening polymerizations occur by a chain growth mechanism without chain termination. To test Amberzyme-CALB stability, the catalyst was reused over three reaction cycles for -CL ring-opening polymerization (70 C, 70 min reactions) and glycerol/1, 8-octanediol/adipic acid polycondensation reactions (90 C, 64 h). Amberzyme-CALB was found to have far better stability for reuse relative to Novozym 435 for the polycondensation reaction.

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

    PubMed

    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.

  12. Highly active non-PGM catalysts prepared from metal organic frameworks

    SciTech Connect

    Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; Xu, Tao; Liu, Di -Jia

    2015-06-11

    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.

  13. Highly active non-PGM catalysts prepared from metal organic frameworks

    DOE PAGES

    Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; Xu, Tao; Liu, Di -Jia

    2015-06-11

    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 demonstratedmore » 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.« less

  14. The fluxional amine gold(III) complex as an excellent catalyst and precursor of biologically active acyclic carbenes.

    PubMed

    Montanel-Pérez, Sara; Herrera, Raquel P; Laguna, Antonio; Villacampa, M Dolores; Gimeno, M Concepción

    2015-05-21

    A new amine gold(III) complex [Au(C6F5)2(DPA)]ClO4 with the di-(2-picolyl)amine (DPA) ligand has been synthesised. In the solid state the complex has a chiral amine nitrogen because the ligand coordinates to the gold centre through one nitrogen atom from a pyridine and through the NH moiety, whereas in solution it shows a fluxional behaviour with a rapid exchange between the pyridine sites. This complex can be used as an excellent synton to prepare new gold(III) carbene complexes by the reaction with isocyanide CNR. The resulting gold(III) derivatives have unprecedented bidentate C^N acyclic carbene ligands. All the complexes have been spectroscopically and structurally characterized. Taking advantage of the fluxional behaviour of the amine complex, its catalytic properties have been tested in several reactions with the formation of C-C and C-N bonds. The complex showed excellent activity with total conversion, without the presence of a co-catalyst, and with a catalyst loading as low as 0.1%. These complexes also present biological properties, and cytotoxicity studies have been performed in vitro against three tumour human cell lines, Jurkat (T-cell leukaemia), MiaPaca2 (pancreatic carcinoma) and A549 (lung carcinoma). Some of them showed excellent cytotoxic activity compared with the reference cisplatin.

  15. Catalysts possessing augmented C-O and C-N hydrogenolysis activity. Progress report No. 1, October-December 1983

    SciTech Connect

    Massoth, F.E.; Shabtai, J.S.

    1984-01-09

    The aim of the proposed research is to synthesize and investigate new sulfided catalyst systems having higher carbon-heteroatom hydrogenolysis activity as compared to ring hydrogenation activity. A fundamental approach is planned to gain understanding of the basic catalytic properties which relate to hydrogenolysis, hydrogenation and cracking functions of the catalysts. This will involve preparation of new catalysts, characterization of their properties and model compound reactivity studies. In another part of the project, selected catalysts will be applied in studies of more complex O- and N- containing model compounds with the objective of providing fundamental data on the stereochemistry of HDO and HDN reactions. These data will be used to develop steric surface-reactant models for sulfided catalysts. During this quarter additional catalysts were prepared by incipient wetness impregnation using solutions at various pH levels. Catalysts prepared by this method included: 3% and 6% Co, or 3% and 6% Ni with either 8% Mo or with 4.5% Cr supported on ..gamma.. alumina. Five catalysts were tested for hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) activity using model compounds indole and dibenzofuran. 5 references, 5 figures, 1 table.

  16. ALTERNATIVE ROUTES FOR CATALYST PREPARATION: USE OF ULTRASOUND AND MICROWAVE IRRADIATION FOR THE PREPARATION OF VANADIUM PHOSPHORUS OXIDE CATALYST AND ITS ACTIVITY FOR HYDROCARBON OXIDATION

    EPA Science Inventory

    Vanadium phosphorus oxide (VPO) is a well-known catalyst used for the vapor phase n-butane oxidation to maleic anhydride. It is prepared by a variety of methods, all of which, however, eventually result in the same active phase. The two main methods for the preparation of its pr...

  17. Structure-activity relationship of Cr/Ti-PILC catalysts using a pre-modification method for NO oxidation and their surface species study.

    PubMed

    Zhong, Lei; Yu, Yang; Cai, Wei; Geng, Xinxin; Zhong, Qin

    2015-06-14

    The performances of Cr/Ti-PILC catalysts, which were prepared by the pre-modification method, are studied for the selective catalytic oxidation of NO. The aim of this paper is to elucidate the detailed relationship between physical nanoparticle structure and chemical properties. The maximum NO conversion over the Cr-HP(3)/TP catalyst reached 71.4% at 280 °C. The catalysts were characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction of H2 (H2-TPR), temperature-programmed desorption (TPD) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) techniques. The characterization results demonstrated that the enhanced catalytic activity was ascribed to several beneficial effects, which were caused by the pre-modification such as the inhibition of crystallite size, improvement of Cr species dispersion and increase of the amount of active sites. XPS and FTIR experiments indicated that two Cr(VI) species, oxidized state CrO3 and chromate species with the anionic form, were generated via pre-modification, which played different roles in the catalytic reaction. In addition, the TPR and TPD results suggest that the increased active sites (Cr(VI) species) were conducive for the preferential adsorption and activation of NO. Furthermore, DRIFTS results revealed that the intermediates, NO(+) and nitrates, interacted quickly to generate gaseous NO2.

  18. Comparative dimerization of 1-butene with a variety of metal catalysts, and the investigation of a new catalyst for C=H bond activation.

    PubMed

    Small, Brooke L; Schmidt, Roland

    2004-02-20

    Catalytic dimerization of 1-butene by a variety of catalysts is carried out, and the products are analyzed by gas chromatography and mass spectrometry. Catalysts based on cobalt and iron can produce highly linear dimers, with the cobalt-based dimers exceeding 97 % linearity. Catalysts based on vanadium and aluminum prefer to make branched dimers, which are most often methyl-heptenes in the case of vanadium and almost exclusively 2-ethyl-1-butene in the case of aluminum. The vanadium catalyst also produces substantial amounts of dienes and alkanes, suggesting a competing hydrogenation/dehydrogenation pathway that appears to involve vinyl Cbond;H bond activation. Nickel catalysts are generally less selective than those based on iron or cobalt for making linear dimers, but they can make dimers with 60 % linearity. The major by-products for the nickel systems are trisubstituted internal olefins. An important side reaction that must be considered for dimerization reactions is 1-butene isomerization to 2-butene, which makes recycling the butene difficult for a linear dimerization process. Aluminum, iron, and vanadium systems promote very little isomerization, but nickel and cobalt systems tend to isomerize the undimerized substrate heavily. PMID:14978828

  19. Activation and regeneration of a NiMo/Al[sub 2]O[sub 3] hydrotreatment catalyst

    SciTech Connect

    Teixeira da Silva, V.L.S.; Schmal, M. ); Frety, R. . Inst. de Reserches sur la Catalyse)

    1994-07-01

    Activation and regeneration procedures applied to a nickel-molybdenum on alumina catalyst, both fresh and spent, were tested by the hydrodesulfurization of thiophene. Characterization techniques used included temperature programmed reduction and oxidation (TPR,TPO), diffuse reflectance spectroscopy (DRS), and X-ray diffraction (XRD). The fresh catalyst was treated by sulfiding, reoxidation, and resulfiding. This sequence was found to be more effective than one sulfiding step, possibly because of the formation of a nickel molybdate phase during reoxidation. The spent catalyst could not be regenerated completely although its original surface properties were attained. The loss of activity of the spent catalysts was alluded by TPO to result from nickel-molybdenum segregation which probably happened because of the excessive heat from burning the coke present on the catalyst.

  20. The effect of H2O and pretreatment on the activity of a Pt/SnO2 catalyst

    NASA Technical Reports Server (NTRS)

    Vannorman, John D.; Brown, Kenneth G.; Schryer, Jacqueline; Schryer, David R.; Upchurch, Billy T.; Sidney, Barry D.

    1990-01-01

    CO oxidation catalysts with high activity at 25 C to 100 C are important for long-life, closed-cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 has been shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment or no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady-state yield is attained. This dip has been found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.

  1. Operando and in situ Raman studies of alumina-supported vanadium phosphate catalysts in propane ammoxidation reaction: activity, selectivity and active phase formation.

    PubMed

    Mikolajska, Ewelina; Rasmussen, Søren B; Lewandowska, Anna E; Bañares, Miguel A

    2012-02-21

    Alumina-supported VPO materials are efficient catalysts for acrylonitrile production by the propane ammoxidation reaction. In order to understand the structure-activity relationship and the nature of active sites, operando Raman-GC analyses follow the states of vanadium and phosphorous species on an alumina support during ammoxidation. These oxides were supported on γ-alumina by incipient wetness impregnation at a total V + P loading of two monolayers, which led to incipient formation of nanoscaled VPO crystallites possessing a high surface-to-volume ratio. Since catalysis occurs at the catalyst surface, which is related to the surface and outermost layers, this approach allows studying surface species phase transformations near the surface, and relates changes in activity and selectivity to variations in composition and structure. Dispersed surface V(5+) species appear selective to acetonitrile and V(4+) species would promote selectivity to acrylonitrile. This study suggests that V(3+) is probably involved in redox processes during propane ammoxidation and that the balance between these vanadium species would be determined by activation process. PMID:21993840

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    A successive anchoring of Zr(NMe2)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, 13C 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.

  3. Zirconia supported catalysts for bioethanol steam reforming: Effect of active phase and zirconia structure

    NASA Astrophysics Data System (ADS)

    Benito, M.; Padilla, R.; Rodríguez, L.; Sanz, J. L.; Daza, L.

    Three new catalysts have been prepared in order to study the active phase influence in ethanol steam reforming reaction. Nickel, cobalt and copper were the active phases selected and were supported on zirconia with monoclinic and tetragonal structure, respectively. To characterize the behaviour of the catalysts in reaction conditions a study of catalytic activity with temperature was performed. The highest activity values were obtained at 973 K where nickel and cobalt based catalysts achieved an ethanol conversion of 100% and a selectivity to hydrogen close to 70%. Nickel supported on tetragonal zirconia exhibited the highest hydrogen production efficiency, higher than 4.5 mol H 2/mol EtOH fed. The influence of steam/carbon (S/C) ratio on product distribution was another parameter studied between the range 3.2-6.5. Nickel supported on tetragonal zirconia at S/C = 3.2 operated at 973 K without by-product production such as ethylene or acetaldehyde. In order to consider a further application in an ethanol processor, a long-term reaction experiment was performed at 973 K, S/C = 3.2 and atmospheric pressure. After 60 h, nickel supported on tetragonal zirconia exhibited high stability and selectivity to hydrogen production.

  4. Cationic tungsten-oxo-alkylidene-N-heterocyclic carbene complexes: highly active olefin metathesis catalysts.

    PubMed

    Schowner, Roman; Frey, Wolfgang; Buchmeiser, Michael R

    2015-05-20

    The synthesis, structure, and olefin metathesis activity of the first neutral and cationic W-oxo-alkylidene-N-heterocyclic carbene (NHC) catalysts are reported. Neutral W-oxo-alkylidene-NHC catalysts can be prepared in up to 90% isolated yield. Depending on the ligands used, they possess either an octahedral (Oh) or trigonal bipyramidal ligand sphere. They can be activated with excess AlCl3 to form cationic olefin metathesis-active W-complexes; however, these readily convert into neutral chloro-complexes. Well-defined, stable cationic species can be prepared by stoichiometric substitution of one chloro ligand in the parent, neutral W-oxo-alkylidene-NHC complexes with Ag(MeCN)2B(Ar(F))4 or NaB(Ar(F))4; B(Ar(F))4 = B(3,5-(CF3)2-C6H3)4. They are highly active olefin metathesis catalysts, allowing for turnover numbers up to 10,000 in various olefin metathesis reactions including alkenes bearing nitrile, sec-amine, and thioether groups. PMID:25938340

  5. Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation

    DOE PAGES

    He, Qian; Freakley, Simon J.; Edwards, Jennifer K.; Carley, Albert F.; Borisevich, Albina Y.; Mineo, Yuki; Haruta, Masatake; Hutchings, Graham J.; Kiely, Christopher J.

    2016-09-27

    The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviors after heat treatment of Au/FeOx materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed to revealmore » the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. As a result, correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeOx catalyst.« less

  6. Cationic tungsten-oxo-alkylidene-N-heterocyclic carbene complexes: highly active olefin metathesis catalysts.

    PubMed

    Schowner, Roman; Frey, Wolfgang; Buchmeiser, Michael R

    2015-05-20

    The synthesis, structure, and olefin metathesis activity of the first neutral and cationic W-oxo-alkylidene-N-heterocyclic carbene (NHC) catalysts are reported. Neutral W-oxo-alkylidene-NHC catalysts can be prepared in up to 90% isolated yield. Depending on the ligands used, they possess either an octahedral (Oh) or trigonal bipyramidal ligand sphere. They can be activated with excess AlCl3 to form cationic olefin metathesis-active W-complexes; however, these readily convert into neutral chloro-complexes. Well-defined, stable cationic species can be prepared by stoichiometric substitution of one chloro ligand in the parent, neutral W-oxo-alkylidene-NHC complexes with Ag(MeCN)2B(Ar(F))4 or NaB(Ar(F))4; B(Ar(F))4 = B(3,5-(CF3)2-C6H3)4. They are highly active olefin metathesis catalysts, allowing for turnover numbers up to 10,000 in various olefin metathesis reactions including alkenes bearing nitrile, sec-amine, and thioether groups.

  7. Active site of ribulosebisphosphate carboxylase/oxygenase

    SciTech Connect

    Hartman, F.C.; Stringer, C.D.; Milanez, S.; Lee, E.H.

    1985-01-01

    Previous affinity labeling studies and comparative sequence analyses have identified two different lysines at the active site of ribulosebisphosphate carboxylase/oxygenase and have suggested their essentiality to function. The essential lysines occupy positions 166 and 329 in the Rhodospirillum rubrum enzyme and positions 175 and 334 in the spinach enzyme. Based on the pH-dependencies of inactivations of the two enzymes by trinitrobenzene sulfonate, Lys-166 (R. rubrum enzyme) exhibits a pK/sub a/ of 7.9 and Lys-334 (spinach enzyme) exhibits a pK/sub a/ of 9.0. These low pK/sub a/ values as well as the enhanced nucleophilicities of the lysyl residues argue that both are important to catalysis rather than to substrate binding. Lys-166 may correspond to the essential base that initiates catalysis and that displays a pK/sub a/ of 7.5 in the pH-curve for V/sub max//K/sub m/. Cross-linking experiments with 4,4'-diisothiocyano-2,2'-disulfonate stilbene demonstrate that the two active-site lysines are within 12 A. 50 refs., 7 figs., 1 tab.

  8. Catalytically Active and Spectator Ce(3+) in Ceria-Supported Metal Catalysts.

    PubMed

    Kopelent, René; van Bokhoven, Jeroen A; Szlachetko, Jakub; Edebeli, Jacinta; Paun, Cristina; Nachtegaal, Maarten; Safonova, Olga V

    2015-07-20

    Identification of active species and the rate-determining reaction steps are crucial for optimizing the performance of oxygen-storage materials, which play an important role in catalysts lowering automotive emissions, as electrode materials for fuel cells, and as antioxidants in biomedicine. We demonstrated that active Ce(3+) species in a ceria-supported platinum catalyst during CO oxidation are short-lived and therefore cannot be observed under steady-state conditions. Using time-resolved resonant X-ray emission spectroscopy, we quantitatively correlated the initial rate of Ce(3+) formation under transient conditions to the overall rate of CO oxidation under steady-state conditions and showed that ceria reduction is a kinetically relevant step in CO oxidation, whereas a fraction of Ce(3+) was present as spectators. This approach can be applied to various catalytic processes involving oxygen-storage materials and reducible oxides to distinguish between redox and nonredox catalytic mechanisms.

  9. Conformational Change in the Active Site of Streptococcal Unsaturated Glucuronyl Hydrolase Through Site-Directed Mutagenesis at Asp-115.

    PubMed

    Nakamichi, Yusuke; Oiki, Sayoko; Mikami, Bunzo; Murata, Kousaku; Hashimoto, Wataru

    2016-08-01

    Bacterial unsaturated glucuronyl hydrolase (UGL) degrades unsaturated disaccharides generated from mammalian extracellular matrices, glycosaminoglycans, by polysaccharide lyases. Two Asp residues, Asp-115 and Asp-175 of Streptococcus agalactiae UGL (SagUGL), are completely conserved in other bacterial UGLs, one of which (Asp-175 of SagUGL) acts as a general acid and base catalyst. The other Asp (Asp-115 of SagUGL) also affects the enzyme activity, although its role in the enzyme reaction has not been well understood. Here, we show substitution of Asp-115 in SagUGL with Asn caused a conformational change in the active site. Tertiary structures of SagUGL mutants D115N and D115N/K370S with negligible enzyme activity were determined at 2.00 and 1.79 Å resolution, respectively, by X-ray crystallography. The side chain of Asn-115 is drastically shifted in both mutants owing to the interaction with several residues, including Asp-175, by formation of hydrogen bonds. This interaction between Asn-115 and Asp-175 probably prevents the mutants from triggering the enzyme reaction using Asp-175 as an acid catalyst.

  10. Active Sites Environmental Monitoring Program: Program plan

    SciTech Connect

    Ashwood, T.L.; Wickliff, D.S.; Morrissey, C.M.

    1992-02-01

    The Active Sites Environmental Monitoring Program (ASEMP), initiated in 1989, provides early detection and performance monitoring of transuranic (TRU) waste and active low-level waste (LLW) facilities at Oak Ridge National Laboratory (ORNL) in accordance with US Department of Energy (DOE) Order 5820.2A. Active LLW facilities in Solid Waste Storage Area (SWSA) 6 include Tumulus I and Tumulus II, the Interim Waste Management Facility (IWMF), LLW silos, high-range wells, asbestos silos, and fissile wells. The tumulus pads and IWMF are aboveground, high-strength concrete pads on which concrete vaults containing metal boxes of LLW are placed; the void space between the boxes and vaults is filled with grout. Eventually, these pads and vaults will be covered by an engineered multilayered cap. All other LLW facilities in SWSA 6 are below ground. In addition, this plan includes monitoring of the Hillcut Disposal Test Facility (HDTF) in SWSA 6, even though this facility was completed prior to the data of the DOE order. In SWSA 5 North, the TRU facilities include below-grade engineered caves, high-range wells, and unlined trenches. All samples from SWSA 6 are screened for alpha and beta activity, counted for gamma-emitting isotopes, and analyzed for tritium. In addition to these analytes, samples from SWSA 5 North are analyzed for specific transuranic elements.

  11. A General Method for Multimetallic Platinum Alloy Nanowires as Highly Active and Stable Oxygen Reduction Catalysts.

    PubMed

    Bu, Lingzheng; Ding, Jiabao; Guo, Shaojun; Zhang, Xu; Su, Dong; Zhu, Xing; Yao, Jianlin; Guo, Jun; Lu, Gang; Huang, Xiaoqing

    2015-11-25

    An unconventional class of high-performance Pt alloy multimetallic nanowires (NWs) is produced by a general method. The obtained PtNi NWs exhibit amazingly specific and mass oxygen reduction reaction (ORR) activities with improvement factors of 51.1 and 34.6 over commercial Pt/C catalysts, respectively, and are also stable in ORR conditions, making them among the most efficient electrocatalysts for ORR.

  12. Reductive alkylation of active methylene compounds with carbonyl derivatives, calcium hydride and a heterogeneous catalyst.

    PubMed

    Guyon, Carole; Duclos, Marie-Christine; Sutter, Marc; Métay, Estelle; Lemaire, Marc

    2015-07-01

    A one-pot two-step reaction (Knoevenagel condensation - reduction of the double bond) has been developed using calcium hydride as a reductant in the presence of a supported noble metal catalyst. The reaction between carbonyl compounds and active methylene compounds such as methylcyanoacetate, 1,3-dimethylbarbituric acid, dimedone and the more challenging dimethylmalonate, affords the corresponding monoalkylated products in moderate to good yields (up to 83%) with minimal reduction of the starting carbonyl compounds. PMID:26053131

  13. CATALYST ACTIVITY MAINTENANCE FOR THE LIQUID PHASE SYNTHESIS GAS-TO-DIMETHYL ETHER PROCESS PART II: DEVELOPMENT OF ALUMINUM PHOSPHATE AS THE DEHYDRATION CATALYST FOR THE SINGLE-STEP LIQUID PHASE SYNGAS-TO-DME PROCESS

    SciTech Connect

    Xiang-Dong Peng

    2002-05-01

    At the heart of the single-step liquid phase syngas-to-DME process (LPDME{trademark}) is a catalyst system that can be active as well as stable. In the Alternative Fuels I program, a dual-catalyst system containing a Cu-based commercial methanol synthesis catalyst (BASF S3-86) and a commercial dehydration material ({gamma}-alumina) was demonstrated. It provided the productivity and selectivity expected from the LPDME process. However, the catalyst system deactivated too rapidly to warrant a viable commercial process [1]. The mechanistic investigation in the early part of the DOE's Alternative Fuels II program revealed that the accelerated catalyst deactivation under LPDME conditions is due to detrimental interaction between the methanol synthesis catalyst and methanol dehydration catalyst [2,3]. The interaction was attributed to migration of Cu- and/or Zn-containing species from the synthesis catalyst to the dehydration catalyst. Identification of a dehydration catalyst that did not lead to this detrimental interaction while retaining adequate dehydration activity was elusive. Twenty-nine different dehydration materials were tested, but none showed the desired performance [2]. The search came to a turning point when aluminum phosphate was tested. This amorphous material is prepared by precipitating a solution containing Al(NO{sub 3}){sub 3} and H{sub 3}PO{sub 4} with NH{sub 4}OH, followed by washing, drying and calcination. The aluminum phosphate catalyst has adequate dehydration activity and good stability. It can co-exist with the Cu-based methanol synthesis catalyst without negatively affecting the latter catalyst's stability. This report documents the details of the development of this catalyst. These include initial leads, efforts in improving activity and stability, investigation and development of the best preparation parameters and procedures, mechanistic understanding and resulting preparation guidelines, and the accomplishments of this work.

  14. Oxyhydrochlorination catalyst

    DOEpatents

    Taylor, Charles E.; Noceti, Richard P.

    1992-01-01

    An improved catalyst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HCl and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

  15. Direct evidence of active surface reconstruction during oxidative dehydrogenation of propane over VMgO catalyst

    SciTech Connect

    Pantazidis, A.; Mirodatos, C.; Burrows, A.; Kiely, C.J.

    1998-07-25

    This paper presents a thorough investigation of an optimized VMgO catalyst (14 wt% V) for the oxidative dehydrogenation of propane, carried out in order to elucidate the nature and behavior of the active surface. The catalyst morphology and the surface composition are studied by means of HREM, XPS, UV-vis, XRD, and in-situ electrical conductivity techniques, as a function of the gaseous environments of the catalyst. The active surface is shown to be essentially a monolayer of amorphous VO{sub 4}{sup 3{minus}} units scattered over the magnesia as isolated and polymeric species. These surface vanadia units are found to stabilize an unusual polar (111) orientation of MgO up to temperatures of 800 C. A direct and outstanding evidence of a totally reversible phenomenon of order/disorder restructuration of this V overlayer is provided in conjunction with the redox state of the surface depending on the properties of the surrounding atmosphere (reductive or oxidative). These fast surface phenomena are assumed to determine the elementary steps of propane activation within the overall oxidative dehydrogenation of propane (ODHP) process.

  16. Redox-Active Nitroxide Radical Polymers: From Green Catalysts to Energy Storage Devices

    NASA Astrophysics Data System (ADS)

    Waskitoaji, Wihatmoko; Suga, Takeo; Nishide, Hiroyuki

    2009-09-01

    Robust but redox-active radical polymers bearing 2, 2, 6, 6-tetramethylpiperidin-N-oxy (TEMPO) were investigated as a metal-free, green mediator/catalyst for the oxidation of alcohol derivatives, and as a new electrode-active and charge-storage material. The TEMPO-mediated oxidation of the primary alcohol group of the natural cellulose improved the water-dispersivity of cellulose, and the polymer-supported catalysts or redox resins allow facile removal of catalysts from products by simple filtration. Other radical molecule (e.g. galvinoxyl) was also used as a mediator, which is coupled with the molecular oxygen. A reversible one-electron redox reaction of TEMPO allowed its application as an electrode-active material featuring high cyclability (>500 cycles), relatively high battery electrode capacity (100-135 mAh/g), and fast electrode kinetics, leading to the high power rate capability of the battery. The radical polymer-based electrodes also provided good processability and shape flexibility, which promised the paper-like and wearable energy-storage devices.

  17. Heterogeneous copper-silica catalyst from agricultural biomass and its catalytic activity

    NASA Astrophysics Data System (ADS)

    Andas, Jeyashelly; Adam, Farook; Rahman, Ismail Ab.

    2013-11-01

    A series of highly mesoporous copper catalysts (5-20 wt.%) supported on silica rice husk were synthesized via sol-gel route at room temperature. The FT-IR and 29Si MAS NMR spectroscopic studies revealed the successful substitution of copper into the silica matrix. Copper in the +2 oxidation state was evidenced from the DR/UV-vis and XPS analyses. Introduction of copper up to 10 wt.% (RH-10Cu) results in a progressive enhancement in the BET surface area. The activity of the copper catalysts was studied in the liquid-phase oxidation of phenol with H2O2 yielding catechol (CAT) and hydroquinone (HQ). Phenol conversion was influenced by various experimental conditions such as temperature, catalyst dosage, molar ratio of reactants, nature of solvent and percentage metal loading. Excellent activity was achieved when 10 wt.% copper was used and decreased with further increase in the copper loading. RH-10Cu could be regenerated several times without significant loss in the catalytic activity.

  18. Activity and selectivity of palladium catalysts during the liquid-phase hydrogenation of phenol. Influence of temperature and pressure

    SciTech Connect

    Gonzalez-Velasco, J.R.; Gonzalez-Marcos, M.P.; Arnaiz, S.; Gutierrez-Ortiz, J.I.; Gutierrez-Ortiz, M.A.

    1995-04-01

    Two series of highly dispersed palladium catalysts supported on alumina have been prepared by adsorption from solution, with palladium contents varying from 0.25 to 2.0 wt %. The first series was calcined at 773 K for 4 h in air, whereas the second series was just heated at 423 K for 1 h in nitrogen, before reduction. Complete dispersion of the metal has been found for the calcined catalysts, and metal dispersion was favored with low palladium contents for the noncalcined catalysts. The kinetic behavior of the catalysts has been analyzed for the liquid-phase hydrogenation of phenol in a stirred tank reactor, ensuring a chemically controlled regime for stirring speed above 750 rpm and catalyst particle below 0.08--0.16 mm in the studied conditions. Despite their higher metallic dispersion, the calcined catalysts presented lower activity than their corresponding noncalcined catalysts. The influence of hydrogen partial pressure on activity showed a reaction order of 2. The apparent activation energy resulted in 56.8 kJ/mol. Selectivity to cyclohexanone was found to be very high for all experiments. Some conclusions on the kinetic reaction rate equations and the apparent activation energies of phenol to cyclohexanone and cyclohexanone to cyclohexanol are given.

  19. Regeneration of field-spent activated carbon catalysts for low-temperature selective catalytic reduction of NOx with NH3

    SciTech Connect

    Jeon, Jong Ki; Kim, Hyeonjoo; Park, Young-Kwon; Peden, Charles HF; Kim, Do Heui

    2011-10-15

    In the process of producing liquid crystal displays (LCD), the emitted NOx is removed over an activated carbon catalyst by using selective catalytic reduction (SCR) with NH3 at low temperature. However, the catalyst rapidly deactivates primarily due to the deposition of boron discharged from the process onto the catalyst. Therefore, this study is aimed at developing an optimal regeneration process to remove boron from field-spent carbon catalysts. The spent carbon catalysts were regenerated by washing with a surfactant followed by drying and calcination. The physicochemical properties before and after the regeneration were investigated by using elemental analysis, TG/DTG (thermogravimetric/differential thermogravimetric) analysis, N2 adsorption-desorption and NH3 TPD (temperature programmed desorption). Spent carbon catalysts demonstrated a drastic decrease in DeNOx activity mainly due to heavy deposition of boron. Boron was accumulated to depths of about 50 {mu}m inside the granule surface of the activated carbons, as evidenced by cross-sectional SEM-EDX analysis. However, catalyst activity and surface area were significantly recovered by removing boron in the regeneration process, and the highest NOx conversions were obtained after washing with a non-ionic surfactant in H2O at 70 C, followed by treatment with N2 at 550 C.

  20. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and the solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will be performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing.

  1. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing. 5 refs., 1 tab.

  2. Size Dependence of Atomically Precise Gold Nanoclusters in Chemoselective Hydrogenation and Active Site Structure

    SciTech Connect

    Li, Gao; Jiang, Deen; Kumar, Santosh; Chen, Yuxiang; Jin, Rongchao

    2014-01-01

    We here investigate the catalytic properties of water-soluble Aun(SG)m nanocluster catalysts (H-SG = glutathione) of different sizes, including Au15(SG)13, Au18(SG)14, Au25(SG)18, Au38(SG)24, and captopril-capped Au25(Capt)18 nanoclusters. These Aun(SR)m nanoclusters (-SR represents thiolate generally) are used as homogeneous catalysts (i.e., without supports) in the chemoselective hydrogenation of 4-nitrobenzaldehyde (4-NO2PhCHO) to 4-nitrobenzyl alcohol (4-NO2PhCH2OH) in water with H2 gas (20 bar) as the hydrogen source. These nanocluster catalysts, except Au18(SG)14, remain intact after the catalytic reaction, evidenced by UV-vis spectra which are characteristic of each sized nanoclusters and thus serve as spectroscopic fingerprints . We observe a drastic size-dependence and steric effect of protecting ligands on the gold nanocluster catalysts in the hydrogenation reaction. Density functional theory (DFT) modeling of the 4-nitrobenzaldehyde adsorption shows that both the CHO and NO2 groups are in close interact with the S-Au-S staples on the gold nanocluster surface; the adsorption of the 4-nitrobenzaldehyde molecule on the four different sized Aun(SR)m nanoclusters are moderately strong and similar in strength. The DFT results suggest that the catalytic activity of the Aun(SR)m nanoclusters is primarily determined by the surface area of the Au nanocluster, consistent with the observed trend of the conversion of 4-nitrobenzaldehyde versus the cluster size. Overall, this work offers the molecular insight into the hydrogenation of 4-nitrobenzaldehyde and the catalytically active site structure on gold nanocluster catalysts.

  3. Promotion of the electrocatalytic activity of a bimetallic platinum-ruthenium catalyst by repetitive redox treatments for direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Huang, Sheng-Yang; Yeh, Chuin-Tih

    Pt-Ru/C catalyst (12 wt%) was prepared by the incipient wetness impregnation method followed by a redox heat-treatment. Transmission electron microscopy (TEM) results revealed uniformly distributed metallic crystallites of Pt-Ru alloy nanoparticles (d PtRu = 2.1 ± 1.0 nm). The effect of redox treatments of the impregnated catalysts on methanol oxidation reaction (MOR) was examined by cyclic voltammetry (CV). The MOR activity of the PtRu/C was significantly improved after each oxidation step of the redox treatment cycles. The enhanced catalytic activity was found to be quite stable in chronoamperometry (CA) measurements. CV, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) results strongly suggested that the improved catalytic activity was due to the formation of a stable c-RuO x (x = 2-3) domain during the oxidation treatments. A bifunctional based mechanism was proposed for the MOR on the oxidized PtRu/C catalysts. Formation of Ru-OH species on the surface of c-RuO x domains was suggested as stale sites for the oxidation of carbon monoxide adsorbed on the Pt catalytic sites.

  4. ROLE OF C AND P SITES ON THE CHEMICAL ACTIVITY OF METAL CARBIDE AND PHOSPHIDES: FROM CLUSTERS TO SINGLE-CRYSTAL SURFACES

    SciTech Connect

    RODRIGUEZ,J.A.; VINES, F.; LIU, P.; ILLAS, F.

    2007-07-01

    Transition metal carbides and phosphides have shown tremendous potential as highly active catalysts. At a microscopic level, it is not well understood how these new catalysts work. Their high activity is usually attributed to ligand or/and ensemble effects. Here, we review recent studies that examine the chemical activity of metal carbide and phosphides as a function of size, from clusters to extended surfaces, and metal/carbon or metal/phosphorous ratio. These studies reveal that the C and P sites in these compounds cannot be considered as simple spectators. They moderate the reactivity of the metal centers and provide bonding sites for adsorbates.

  5. Design of a high activity and selectivity alcohol catalyst

    SciTech Connect

    Foley, H.C.; Mills, G.A.

    1992-02-07

    Results of the pyridine adsorption, studies on native and K-doped alumina provide fundamental grounding for the observed methanol dehydration activity of these samples. Both the reactor studies and the pyridine adsorption studies support the conclusion that the K-doped sample had reduced Lewis acidity. Moreover, we were able to measurably alter the acidity of the support surface by our ion exchange treatment. More significantly, when reactor results for transition-metal loaded samples are reconsidered in combination with their surface characteristics suggested by our pyridine adsorption studies, our hypothesis that Rh and Mo have ultimately titrated the support surface seems all the more convincing. Hence, in light of the pyridine adsorption results, the attenuation of a transition-metal based decomposition pathway for methanol on the metal-loaded samples-as seen in the reactor testing-is all the more reasonable.

  6. Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions

    NASA Astrophysics Data System (ADS)

    Parapat, Riny Y.; Wijaya, Muliany; Schwarze, Michael; Selve, Sören; Willinger, Marc; Schomäcker, Reinhard

    2012-12-01

    We recently introduced a new method to synthesize an active and stable Pt catalyst, namely thermo-destabilization of microemulsions (see R. Y. Parapat, V. Parwoto, M. Schwarze, B. Zhang, D. S. Su and R. Schomäcker, J. Mater. Chem., 2012, 22 (23), 11605-11614). We are able to produce Pt nanocrystals with a small size (2.5 nm) of an isotropic structure i.e. truncated octahedral and deposit them well on support materials. Although we have obtained good results, the performance of the catalyst still needed to be improved and optimized. We followed the strategy to retain the small size but change the shape to an anisotropic structure of Pt nanocrystals which produces more active sites by means of a weaker reducing agent. We found that our catalysts are more active than those we reported before and even show the potential to be applied in a challenging reaction such as hydrogenation of levulinic acid.We recently introduced a new method to synthesize an active and stable Pt catalyst, namely thermo-destabilization of microemulsions (see R. Y. Parapat, V. Parwoto, M. Schwarze, B. Zhang, D. S. Su and R. Schomäcker, J. Mater. Chem., 2012, 22 (23), 11605-11614). We are able to produce Pt nanocrystals with a small size (2.5 nm) of an isotropic structure i.e. truncated octahedral and deposit them well on support materials. Although we have obtained good results, the performance of the catalyst still needed to be improved and optimized. We followed the strategy to retain the small size but change the shape to an anisotropic structure of Pt nanocrystals which produces more active sites by means of a weaker reducing agent. We found that our catalysts are more active than those we reported before and even show the potential to be applied in a challenging reaction such as hydrogenation of levulinic acid. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr32122j

  7. Exploring strontium titanate as a reforming catalyst for dodecane

    NASA Astrophysics Data System (ADS)

    Hbaieb, K.

    2016-08-01

    Yttrium-doped strontium titanate (YST)-based perovskite has been explored as catalyst for reforming dodecane. Active metal elements such as ruthenium, nickel and cobalt were doped on the B-site of the perovskite to boost the catalyst activity. Commercial Ni-alumina catalyst has been used for benchmarking. Both steam and autothermal reforming schemes have been used at 800 and 850 °C. Irrespective of the doping elements, all catalysts performed well and had comparable activity and conversion as the commercial catalyst with slight advantage for ruthenium followed by nickel-based catalysts. Hydrogen and syngas yields fall into the range of 65-75 and 83-91 %, respectively. Conversion was consistently between 84 and 90 %. As such, the YST-based perovskite is a promising catalyst for reforming of heavy liquid hydrocarbon fuel.

  8. Synthesis and characterization of mesoporous hydrocracking catalysts

    NASA Astrophysics Data System (ADS)

    Munir, D.; Usman, M. R.

    2016-08-01

    Mesoporous catalysts have shown great prospective for catalytic reactions due to their high surface area that aids better distribution of impregnated metal. They have been found to contain more adsorption sites and controlled pore diameter. Hydrocracking, in the presence of mesoporous catalyst is considered more efficient and higher conversion of larger molecules is observed as compared to the cracking reactions in smaller microporous cavities of traditional zeolites. In the present study, a number of silica-alumina based mesoporous catalysts are synthesized in the laboratory. The concentration and type of surfactants and quantities of silica and alumina sources are the variables studied in the preparation of catalyst supports. The supports prepared are well characterized using SEM, EDX, and N2-BET techniques. Finally, the catalysts are tested in a high pressure autoclave reactor to study the activity and selectivity of the catalysts for the hydrocracking of a model mixture of plastics comprising of LDPE, HDPE, PP, and PS.

  9. Identifying the role of N-heteroatom location in the activity of metal catalysts for alcohol oxidation

    SciTech Connect

    Chan-Thaw, Carine E.; Veith, Gabriel M.; Villa, Alberto; Prati, Laura

    2015-04-02

    Here, this work focuses on understanding how the bonding of nitrogen heteroatoms contained on/in a activated carbon support influence the stability and reactivity of a supported Pd catalyst for the oxidation of alcohols in solution. The results show that simply adding N groups via solution chemistry is insufficient to improve catalytic properties. Instead a strongly bound N moiety is required to activate the catalyst and stabilize the metal particles.

  10. A fully integrated high-throughput screening methodology for the discovery of new polyolefin catalysts: discovery of a new class of high temperature single-site group (IV) copolymerization catalysts.

    PubMed

    Boussie, Thomas R; Diamond, Gary M; Goh, Christopher; Hall, Keith A; LaPointe, Anne M; Leclerc, Margarete; Lund, Cheryl; Murphy, Vince; Shoemaker, James A W; Tracht, Ursula; Turner, Howard; Zhang, Jessica; Uno, Tetsuo; Rosen, Robert K; Stevens, James C

    2003-04-01

    For the first time, new catalysts for olefin polymerization have been discovered through the application of fully integrated high-throughput primary and secondary screening techniques supported by rapid polymer characterization methods. Microscale 1-octene primary screening polymerization experiments combining arrays of ligands with reactive metal complexes M(CH(2)Ph)(4) (M = Zr, Hf) and multiple activation conditions represent a new high-throughput technique for discovering novel group (IV) polymerization catalysts. The primary screening methods described here have been validated using a commercially relevant polyolefin catalyst, and implemented rapidly to discover the new amide-ether based hafnium catalyst [eta(2)-(N,O)[bond](2-MeO[bond]C(6)H(4))(2,4,6-Me(3)C(6)H(2))N]Hf(CH(2)Ph)(3) (1), which is capable of polymerizing 1-octene to high conversion. The molecular structure of 1 has been determined by X-ray diffraction. Larger scale secondary screening experiments performed on a focused 96-member amine-ether library demonstrated the versatile high temperature ethylene-1-octene copolymerization capabilities of this catalyst class, and led to significant performance improvements over the initial primary screening discovery. Conventional one gallon batch reactor copolymerizations performed using selected amide-ether hafnium compounds confirmed the performance features of this new catalyst class, serving to fully validate the experimental results from the high-throughput approaches described herein.

  11. Catalyst deactivation in residue hydrocracking

    SciTech Connect

    Oballa, M.C.; Wong, C.; Krzywicki, A.

    1994-12-31

    The existence of a computer-controlled bench scale hydrocracking units at the authors site has made cheaper the non-stop running of experiments for long periods of time. It was, therefore possible to show, at minimal costs, when three hydrocracking catalysts in service reach their maximum lifetime. Different parameters which are helpful for catalyst life and activity predictions were calculated, e.g., relative catalyst age and the effectiveness factor. Experimental results compared well with model, giving them the minimum and maximum catalyst lifetime, as well as the deactivation profile with regard to sulfur and metals removal. Reaction rate constants for demetallization and desulfurization were also determined. Six commercial catalysts were evaluated at short term runs and the three most active were used for long term runs. Out of three catalysts tested for deactivation at long term runs, it was possible to choose one whose useful life was higher than the others. All runs were carried out in a Robinson-Mahoney continuous flow stirred tank reactor, using 50/50 volumetric mixture of Cold Lake/Lloydminster atmospheric residue and NiMo/Al{sub 2}O{sub 3} catalyst.

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

    PubMed

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

    2015-04-01

    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. PMID:25600582

  13. Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

    PubMed

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

    The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature. PMID:27106147

  14. Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

    PubMed

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

    The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature.

  15. Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts

    NASA Astrophysics Data System (ADS)

    Binninger, Tobias; Mohamed, Rhiyaad; Waltar, Kay; Fabbri, Emiliana; Levecque, Pieter; Kötz, Rüdiger; Schmidt, Thomas J.

    2015-07-01

    In recent years, the oxygen evolution reaction (OER) has attracted increased research interest due to its crucial role in electrochemical energy conversion devices for renewable energy applications. The vast majority of OER catalyst materials investigated are metal oxides of various compositions. The experimental results obtained on such materials strongly suggest the existence of a fundamental and universal correlation between the oxygen evolution activity and the corrosion of metal oxides. This corrosion manifests itself in structural changes and/or dissolution of the material. We prove from basic thermodynamic considerations that any metal oxide must become unstable under oxygen evolution conditions irrespective of the pH value. The reason is the thermodynamic instability of the oxygen anion in the metal oxide lattice. Our findings explain many of the experimentally observed corrosion phenomena on different metal oxide OER catalysts.

  16. Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts

    PubMed Central

    Binninger, Tobias; Mohamed, Rhiyaad; Waltar, Kay; Fabbri, Emiliana; Levecque, Pieter; Kötz, Rüdiger; Schmidt, Thomas J.

    2015-01-01

    In recent years, the oxygen evolution reaction (OER) has attracted increased research interest due to its crucial role in electrochemical energy conversion devices for renewable energy applications. The vast majority of OER catalyst materials investigated are metal oxides of various compositions. The experimental results obtained on such materials strongly suggest the existence of a fundamental and universal correlation between the oxygen evolution activity and the corrosion of metal oxides. This corrosion manifests itself in structural changes and/or dissolution of the material. We prove from basic thermodynamic considerations that any metal oxide must become unstable under oxygen evolution conditions irrespective of the pH value. The reason is the thermodynamic instability of the oxygen anion in the metal oxide lattice. Our findings explain many of the experimentally observed corrosion phenomena on different metal oxide OER catalysts. PMID:26178185

  17. A general method for multimetallic platinum alloy nanowires as highly active and stable oxygen reduction catalysts

    SciTech Connect

    Bu, Lingzheng; Ding, Jiabao; Yao, Jianlin; Huang, Xiaoqing; Guo, Shaojun; Zhang, Xu; Lu, Gang; Su, Dong; Zhu, Xing; Guo, Jun

    2015-10-13

    The production of inorganic nanoparticles (NPs) with precise control over structures has always been a central target in various fields of chemistry and physics because the properties of NPs can be desirably manipulated by their structure.[1-4] There has been an intense search for high-performance noble metal NP catalysts particular for Pt.[5-9] Precious platinum (Pt) NPs are active catalysts for various heterogeneous reactions and show particularly superior performance in both the anodic oxidation reaction and the cathodic ORR in the fuel cells, but their rare content and high cost largely impede the practical application.[10-12] A potential strategy to address this tremendous challenge is alloying Pt NPs with the transition metals (TM).[13-16]

  18. A general method for multimetallic platinum alloy nanowires as highly active and stable oxygen reduction catalysts

    DOE PAGES

    Bu, Lingzheng; Ding, Jiabao; Yao, Jianlin; Huang, Xiaoqing; Guo, Shaojun; Zhang, Xu; Lu, Gang; Su, Dong; Zhu, Xing; Guo, Jun

    2015-10-13

    The production of inorganic nanoparticles (NPs) with precise control over structures has always been a central target in various fields of chemistry and physics because the properties of NPs can be desirably manipulated by their structure.[1-4] There has been an intense search for high-performance noble metal NP catalysts particular for Pt.[5-9] Precious platinum (Pt) NPs are active catalysts for various heterogeneous reactions and show particularly superior performance in both the anodic oxidation reaction and the cathodic ORR in the fuel cells, but their rare content and high cost largely impede the practical application.[10-12] A potential strategy to address this tremendousmore » challenge is alloying Pt NPs with the transition metals (TM).[13-16]« less

  19. Physico-Chemical Property and Catalytic Activity of a CeO2-Doped MnO(x)-TiO2 Catalyst with SO2 Resistance for Low-Temperature NH3-SCR of NO(x).

    PubMed

    Shin, Byeongkil; Chun, Ho Hwan; Cha, Jin-Sun; Shin, Min-Chul; Lee, Heesoo

    2016-05-01

    The effects of CeO2 addition on the catalytic activity and the SO2 resistance of CeO2-doped MnO(x)-TiO2 catalysts were investigated for the low-temperature selective catalytic reduction (SCR) with NH3 of NO(x) emissions in marine applications. The most active catalyst was obtained from 30 wt% CeO2-MnO(x)-TiO2 catalyst in the whole temperature range of 100-300 degrees C at a low gas hourly space velocity (GHSV) of 10,000 h(-)1, and its de-NO(x) efficiency was higher than 90% over 250 degrees C. The enhanced catalytic activity may contribute to the dispersion state and catalytic acidity on the catalyst surface, and the highly dispersed Mn and Ce on the nano-scaled TiO2 catalyst affects the increase of Lewis and Brønsted acid sites. A CeO2-rich additive on MnO(x)-TiO2 could provide stronger catalytic acid sites, associated with NH3 adsorption and the SCR performance. As the results of sulfur resistance in flue gas that contains SO2, the de-NO(x) efficiency of MnO(x)-TiO2 decreased by 15% over 200 degrees C, whereas that of 30 wt% ceria-doped catalyst increased by 14-21% over 150 degrees C. The high SO2 resistance of CeO2-MnO(x)-TiO2 catalysts that resulted from the addition of ceria suppressed the formation of Mn sulfate species, which led to deactivation on the surface of nano-catalyst. PMID:27483759

  20. Physico-Chemical Property and Catalytic Activity of a CeO2-Doped MnO(x)-TiO2 Catalyst with SO2 Resistance for Low-Temperature NH3-SCR of NO(x).

    PubMed

    Shin, Byeongkil; Chun, Ho Hwan; Cha, Jin-Sun; Shin, Min-Chul; Lee, Heesoo

    2016-05-01

    The effects of CeO2 addition on the catalytic activity and the SO2 resistance of CeO2-doped MnO(x)-TiO2 catalysts were investigated for the low-temperature selective catalytic reduction (SCR) with NH3 of NO(x) emissions in marine applications. The most active catalyst was obtained from 30 wt% CeO2-MnO(x)-TiO2 catalyst in the whole temperature range of 100-300 degrees C at a low gas hourly space velocity (GHSV) of 10,000 h(-)1, and its de-NO(x) efficiency was higher than 90% over 250 degrees C. The enhanced catalytic activity may contribute to the dispersion state and catalytic acidity on the catalyst surface, and the highly dispersed Mn and Ce on the nano-scaled TiO2 catalyst affects the increase of Lewis and Brønsted acid sites. A CeO2-rich additive on MnO(x)-TiO2 could provide stronger catalytic acid sites, associated with NH3 adsorption and the SCR performance. As the results of sulfur resistance in flue gas that contains SO2, the de-NO(x) efficiency of MnO(x)-TiO2 decreased by 15% over 200 degrees C, whereas that of 30 wt% ceria-doped catalyst increased by 14-21% over 150 degrees C. The high SO2 resistance of CeO2-MnO(x)-TiO2 catalysts that resulted from the addition of ceria suppressed the formation of Mn sulfate species, which led to deactivation on the surface of nano-catalyst.

  1. Carrier effects of active carbon for methanol carbonylation with supported transition metal catalysts

    SciTech Connect

    Fujimoto, K.; Omata, K.; Yagita, H.

    1996-10-01

    Transition metals such as nickel or noble metals showed excellent catalytic activities for the vapor phase carbonylation of methanol to acetic acid. Reaction proceeded via the carbonylation of methanol to methyl acetate and its successive carbonylation to acetic acid anhydride followed by the hydrolysis. Under slightly pressurized conditions and at around 250{degrees}C methanol was completely carbonylated to acetic acid with the selectivity of 97% or higher. Also, other group 8 metals including noble metals showed excellent catalytic activity only when they were supported on active carbon, whose activity, ordered by strength of metal-halogen bonding showed a volcano-shape relationship with the peak at Rh. The role of active carbon as the active carrier was clarified by kinetics and catalyst characterization which showed that active carbon promoted the reductive elimination of intermediate for acetic acid formation by donating electron from carbon to nickel species.

  2. Selective Dissolution of A-Site Cations in ABO3 Perovskites: A New Path to High-Performance Catalysts.

    PubMed

    Si, Wenzhe; Wang, Yu; Peng, Yue; Li, Junhua

    2015-06-26

    Selective dissolution is a common corrosion process in dealloying in which an alloy is immersed in acid to remove the active element, leaving behind an inert constituent. We introduce this technique into the treatment of oxide catalysts. A three-dimensionally ordered macroporous LaMnO3 perovskite has been prepared and treated with diluted HNO3 to selectively remove La cations, acquiring a novel γ-MnO2-like material. LaMnO3 is not a satisfactory catalyst on CO oxidation. Upon the removal of La cations, the obtained sample showed a significantly higher CO oxidation catalytic activity (T50=89 °C) than the initial precursor LaMnO3 (T50=237 °C) and ordinary γ-MnO2 (T50=148 °C). A large surface area, a high degree of mesoporosity, excellent low-temperature reducibility, and especially improved surface oxygen species are deduced to be responsible for CO oxidation at lower temperatures.

  3. Selective Dissolution of A-Site Cations in ABO3 Perovskites: A New Path to High-Performance Catalysts.

    PubMed

    Si, Wenzhe; Wang, Yu; Peng, Yue; Li, Junhua

    2015-06-26

    Selective dissolution is a common corrosion process in dealloying in which an alloy is immersed in acid to remove the active element, leaving behind an inert constituent. We introduce this technique into the treatment of oxide catalysts. A three-dimensionally ordered macroporous LaMnO3 perovskite has been prepared and treated with diluted HNO3 to selectively remove La cations, acquiring a novel γ-MnO2-like material. LaMnO3 is not a satisfactory catalyst on CO oxidation. Upon the removal of La cations, the obtained sample showed a significantly higher CO oxidation catalytic activity (T50=89 °C) than the initial precursor LaMnO3 (T50=237 °C) and ordinary γ-MnO2 (T50=148 °C). A large surface area, a high degree of mesoporosity, excellent low-temperature reducibility, and especially improved surface oxygen species are deduced to be responsible for CO oxidation at lower temperatures. PMID:25967677

  4. The contrasting catalytic efficiency and cancer cell antiproliferative activity of stereoselective organoruthenium transfer hydrogenation catalysts.

    PubMed

    Fu, Ying; Sanchez-Cano, Carlos; Soni, Rina; Romero-Canelon, Isolda; Hearn, Jessica M; Liu, Zhe; Wills, Martin; Sadler, Peter J

    2016-05-28

    The rapidly growing area of catalytic ruthenium chemistry has provided new complexes with potential as organometallic anticancer agents with novel mechanisms of action. Here we report the anticancer activity of four neutral organometallic Ru(II) arene N-tosyl-1,2-diphenylethane-1,2-diamine (TsDPEN) tethered transfer hydrogenation catalysts. The enantiomers (R,R)-[Ru(η(6)-C6H5(CH2)3-TsDPEN-N-Me)Cl] (8) and (S,S)-[Ru(η(6)-C6H5(CH2)3-TsDPEN-N-Me)Cl] (8a) exhibited higher potency than cisplatin against A2780 human ovarian cancer cells. When the N-methyl was replaced by N-H, i.e. to give (R,R)-[Ru(η(6)-Ph(CH2)3-TsDPEN-NH)Cl] (7) and (S,S)-[Ru(η(6)-Ph(CH2)3-TsDPEN-NH)Cl] (7a), respectively, anticancer activity decreased >5-fold. Their antiproliferative activity appears to be linked to their ability to accumulate in cells, and their mechanism of action might involve inhibition of tubulin polymerisation. This appears to be the first report of the potent anticancer activity of tethered Ru(II) arene complexes, and the structure-activity relationship suggests that the N-methyl substituents are important for potency. In the National Cancer Institute 60-cancer-cell-line screen, complexes 8 and 8a exhibited higher activity than cisplatin towards a broad range of cancer cell lines. Intriguingly, in contrast to their potent anticancer properties, complexes 8/8a are poor catalysts for asymmetric transfer hydrogenation, whereas complexes 7/7a are effective asymmetric hydrogenation catalysts. PMID:27109147

  5. Preparation and characterization of nanosized gold catalysts supported on Co3O4 and their activities for CO oxidation.

    PubMed

    Kim, Ki-Joong; Song, Jae-Koon; Shin, Seong-Soo; Kang, Sang-Jun; Chung, Min-Chul; Jung, Sang-Chul; Jeong, Woon-Jo; Ahn, Ho-Geun

    2011-02-01

    Gold catalysts supported on Co3O4 were prepared by co-precipitation (CP), deposition-precipitation (DP), and impregnation (IMP) methods. The Au/Co3O4 catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and temperature programmed reduction (TPR) to understand the different activities for CO oxidation with different preparation methods. Gold particles below 5 nm supported on Co3O4 by DP method were found to be more exposed to the surface than those by CP and IMP methods, and this catalyst was highly active and stable in CO oxidation. Finally, catalytic activity of Au/Co3O4 catalyst for CO oxidation was strongly dependent on the gold particle size. PMID:21456247

  6. Degradation of refractory dibutyl phthalate by peroxymonosulfate activated with novel catalysts cobalt metal-organic frameworks: Mechanism, performance, and stability.

    PubMed

    Li, Huanxuan; Wan, Jinquan; Ma, Yongwen; Wang, Yan; Chen, Xi; Guan, Zeyu

    2016-11-15

    In this work, a new effective and relatively stable heterogeneous catalyst of Metal-Organic Framework Co3(BTC)2·12H2O (Co-BTC) has been synthesized and tested to activate peroxymonosulfate (PMS) for removal of refractory dibutyl phthalate (DBP). Co-BTC(A) and Co-BTC(B) were synthesized by different methods, which resulted in different activity towards PMS. The results indicated that Co-BTC(A) showed better performance on DBP degradation. The highest degradation rate of 100% was obtained within 30min. The initial pH showed respective level on DBP degradation with a rank of 5.0>2.75>9.0>7.0>11.0 in PMS/Co-BTC(A) system. No remarkable reduction of DBP was observed in the catalytic activity of Co-BTC(A) at 2nd run as demonstrated by recycling. However, the DBP degradation efficiency decreased by 8.26%, 10.9% and 25.6% in the 3rd, 4th, and 5th runs, respectively. The loss of active catalytic sites of Co(II) from Co-BTC(A) is responsible for the activity decay. Sulfate radicals (SO4(-)) and hydroxyl radicals (OH) were found at pH 2.75. Here, we propose the possible mechanism for activation of PMS by Co-BTC(A), which is involved in homogeneous and heterogeneous reactions in the solutions and the surface of Co-BTC(A), respectively. PMID:27420387

  7. Pillared montmorillonite catalysts for coal liquefaction

    SciTech Connect

    Sharma, R.K.; Olson, E.S.

    1994-12-31

    Pillared clays contain large micropores and have considerable potential for catalytic hydrogenation and cleavage of coal macromolecules. Pillared montmorillonite-supported catalysts were prepared by the intercalation of polynuclear hydroxychromium cations and subsequent impregnation of nickel and molybdenum. Infrared and thermogravimetric studies of pyridine-adsorbed catalysts indicated the presence of both Lewis and Bronsted acid sites. Thus, the catalysts have both acidic properties that can aid in hydrocracking and cleavage of carbon-heteroatom bonds as well as hydrogen-activating bimetallic sites. These catalysts were applied to the hydrodesulfurization and liquefaction of coal-derived intermediates. The reactions of model organosulfur compounds and coal liquids were carried out at 300{degrees}-400{degrees}C for 3 hours in the presence of 1000 psi of molecular hydrogen. Reaction products were analyzed by GC/FT-IR/MS/AED. The catalysts have been found to be very effective in removing sulfur from model compounds as well as liquefaction products.

  8. Shape Fixing via Salt Recrystallization: A Morphology-Controlled Approach To Convert Nanostructured Polymer to Carbon Nanomaterial as a Highly Active Catalyst for Oxygen Reduction Reaction.

    PubMed

    Ding, Wei; Li, Li; Xiong, Kun; Wang, Yao; Li, Wei; Nie, Yao; Chen, Siguo; Qi, Xueqiang; Wei, Zidong

    2015-04-29

    Herein, we report a "shape fixing via salt recrystallization" method to efficiently synthesize nitrogen-doped carbon material with a large number of active sites exposed to the three-phase zones, for use as an ORR catalyst. Self-assembled polyaniline with a 3D network structure was fixed and fully sealed inside NaCl via recrystallization of NaCl solution. During pyrolysis, the NaCl crystal functions as a fully sealed nanoreactor, which facilitates nitrogen incorporation and graphitization. The gasification in such a closed nanoreactor creates a large number of pores in the resultant samples. The 3D network structure, which is conducive to mass transport and high utilization of active sites, was found to have been accurately transferred to the final N-doped carbon materials, after dissolution of the NaCl. Use of the invented cathode catalyst in a proton exchange membrane fuel cell produces a peak power of 600 mW cm(-2), making this among the best nonprecious metal catalysts for the ORR reported so far. Furthermore, N-doped carbon materials with a nanotube or nanoshell morphology can be realized by the invented method.

  9. Manganese oxide-induced strategy to high-performance iron/nitrogen/carbon electrocatalysts with highly exposed active sites

    NASA Astrophysics Data System (ADS)

    Sun, Tao; Wu, Qiang; Zhuo, Ou; Jiang, Yufei; Bu, Yongfeng; Yang, Lijun; Wang, Xizhang; Hu, Zheng

    2016-04-01

    Iron/nitrogen/carbon (Fe/N/C) catalyst is so far the most promising non-precious metal electrocatalyst for oxygen reduction reaction (ORR) in acidic medium, whose performance depends closely on the synthesis chemistry. Herein, we report a MnOx-induced strategy to construct the Fe/N/C with highly exposed Fe-Nx active sites, which involves the uniform spreading of polyaniline on hierarchical N-doped carbon nanocages by a reactive-template polymerization, followed by the successive iron incorporation and polyaniline pyrolysis. The resulting Fe/N/C demonstrates an excellent ORR performance, including an onset potential of 0.92 V (vs. RHE), four electron selectivity, superb stability and immunity to methanol crossover. The excellent performance is well correlated with the greatly enhanced surface active sites of the catalyst stemming from the unique MnOx-induced strategy. This study provides an efficient approach for exploring the advanced ORR electrocatalysts by increasing the exposed active sites.Iron/nitrogen/carbon (Fe/N/C) catalyst is so far the most promising non-precious metal electrocatalyst for oxygen reduction reaction (ORR) in acidic medium, whose performance depends closely on the synthesis chemistry. Herein, we report a MnOx-induced strategy to construct the Fe/N/C with highly exposed Fe-Nx active sites, which involves the uniform spreading of polyaniline on hierarchical N-doped carbon nanocages by a reactive-template polymerization, followed by the successive iron incorporation and polyaniline pyrolysis. The resulting Fe/N/C demonstrates an excellent ORR performance, including an onset potential of 0.92 V (vs. RHE), four electron selectivity, superb stability and immunity to methanol crossover. The excellent performance is well correlated with the greatly enhanced surface active sites of the catalyst stemming from the unique MnOx-induced strategy. This study provides an efficient approach for exploring the advanced ORR electrocatalysts by increasing the

  10. Catalytic Y-tailed amphiphilic homopolymers - aqueous nanoreactors for high activity, low loading SCS pincer catalysts.

    PubMed

    Patterson, Joseph P; Cotanda, Pepa; Kelley, Elizabeth G; Moughton, Adam O; Lu, Annhelen; Epps, Thomas H; O'Reilly, Rachel K

    2013-01-01

    A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. This allows carbon-carbon bond forming reactions to be performed in water with reduced catalyst loadings and enhanced activity.

  11. Modification of Au/TiO(2) Nanosystems by SiO(2) Monolayers: Toward the Control of the Catalyst Activity and Stability

    SciTech Connect

    Dai, Sheng; Rashkeev, Sergey; Overbury, Steven {Steve} H

    2010-01-01

    The activity and stability of Au/TiO{sub 2} catalysts depend on several different factors such as the anchoring strength of the Au particles at the TiO{sub 2} surface, the particle sintering, and the surface mobility of individual gold atoms and/or gold particles. Au/TiO{sub 2} catalysts can be made resistant to sintering by atomic layer deposition (ALD) of a layer of SiO{sub 2} onto the catalysts. In this study, first-principles density-functional calculations are used to investigate how the stability of Au nanoparticles is modified when a partial monolayer of SiO{sub 2} is deposited on a Au/TiO{sub 2} catalyst. We find that SiO{sub 2} structures deposited on a pure TiO{sub 2} substrate exhibit lattice-mismatch instabilities that result in the formation of additional strong anchoring sites for Au atoms/nanoparticles. An atomic-scale roughness introduced by a partial monolayer of SiO{sub 2} can slow the atomic surface diffusion and inhibit Au nanoparticle growth/sintering, in agreement with previous experimental results.

  12. Modification of Au/TiO2 nanosystems by SiO2 monolayers: Toward the control of the catalyst activity and stability

    SciTech Connect

    Sergey N. Rashkeev

    2010-02-01

    The activity and stability of Au/TiO2 catalysts depend on several different factors such as the anchoring strength of Au particles at the TiO2 surface, the particle sintering, and the surface mobility of individual gold atoms and/or gold particles. Au/TiO2 catalysts can be made resistant to sintering by ALD deposition of a layer of SiO2 onto the catalysts. In this study, first-principles density-functional calculations are used to investigate how stability of Au nanoparticles is modified when a partial monolayer of SiO2 is deposited on a Au/TiO2 catalyst. We find that SiO2 structures deposited on a pure TiO2 substrate exhibits lattice-mismatch instabilities which result in a formation of additional strong anchoring sites for Au atoms/nanoparticles. An atomic-scale roughness introduced by a partial monolayer of SiO2 may slow down the atomic surface diffusion and inhibit Au nanoparti-cles growth/sintering, in agreement with previous experimental results.

  13. The effect of catalyst preparation on the performance of alumina-supported ruthenium catalysts. I. The impact of catalytic precursor on particle size and catalytic activity

    SciTech Connect

    Mieth, J.A.; Schwarz, J.A. )

    1989-07-01

    The effect of preparation method and the choice of metallic precursor on the performance of a series of Ru/Al{sub 2}O{sub 3} catalysts were studied. Wet impregnation and incipient wetness were the methods employed; ruthenium nitrosylnitrate and ruthenium trichloride were the reagents. In the latter case, either Ru(III)/Ru(IV) chlorospecies or mixtures of Ru(II) hydrazine complexes were the catalytic precursors. The series of Ru/Al{sub 2}O{sub 3} catalysts, with metal loadings from 0.7-5% by weight, were subjected to a battery of performance tests: CO temperature-programmed reaction, steady-state CO hydrogenation, and temperature-programmed surface reaction. The methanation activity and carbon deposited during steady-state reaction varied systematically with the dispersion of Ru on the alumina. High rates of methane production were found on catalysts containing a large reservoir of carbon-containing reaction intermediates. The performance of these catalysts depended on the precursor used in their preparation. The effects of weight loading, method of preparation, and variations in the impregnant pH were small within a group prepared from a common precursor.

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

    NASA Astrophysics Data System (ADS)

    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

  15. Active Hydrogenation Catalyst with a Structured, Peptide-Based Outer-Coordination Sphere

    SciTech Connect

    Jain, Avijita; Buchko, Garry W.; Reback, Matthew L.; O'Hagan, Molly J.; Ginovska-Pangovska, Bojana; Linehan, John C.; Shaw, Wendy J.

    2012-10-05

    The synthesis, catalytic activity, and structural features of a rhodium-based hydrogenation catalyst containing a phosphine ligand coupled to a 14-residue peptide are reported. Both CD and NMR spectroscopy show that the peptide adopts a helical structure in 1:1:1 TFE/MeCN/H2O that is maintained when the peptide is attached to the ligand and when the ligand is attached to the metal complex. The metal complex hydrogenates aqueous solutions of 3-butenol to 1-butanol at 360 ± 50 turnovers/Rh/h at 294 K. This peptide- based catalyst represents a starting point for developing and characterizing a peptide-based outer-coordination sphere that can be used to introduce enzyme-like features into molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (AJ, JCL and WJS), the Office of Science Early Career Research Program through the Office of Basic Energy Sciences (GWB, MLR and WJS). Part of the research was conducted at the W.R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. Department of Energy’s Office of Biolog-ical and Environmental Research (BER) program located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.

  16. CO2 copolymers from epoxides: catalyst activity, product selectivity, and stereochemistry control.

    PubMed

    Lu, Xiao-Bing; Ren, Wei-Min; Wu, Guang-Peng

    2012-10-16

    The use of carbon dioxide as a carbon source for the synthesis of organic chemicals can contribute to a more sustainable chemical industry. Because CO(2) is such a thermodynamically stable molecule, few effective catalysts are available to facilitate this transformation. Currently, the major industrial processes that convert CO(2) into viable products generate urea and hydroxybenzoic acid. One of the most promising new technologies for the use of this abundant, inexpensive, and nontoxic renewable resource is the alternating copolymerization of CO(2) and epoxides to provide biodegradable polycarbonates, which are highly valuable polymeric materials. Because this process often generates byproducts, such as polyether or ether linkages randomly dispersed within the polycarbonate chains and/or the more thermodynamically stable cyclic carbonates, the choice of catalyst is critical for selectively obtaining the expected product. In this Account, we outline our efforts to develop highly active Co(III)-based catalysts for the selective production of polycarbonates from the alternating copolymerization of CO(2) with epoxides. Binary systems consisting of simple (salen)Co(III)X and a nucleophilic cocatalyst exhibited high activity under mild conditions even at 0.1 MPa CO(2) pressure and afforded copolymers with >99% carbonate linkages and a high regiochemical control (∼95% head-to-tail content). Discrete, one-component (salen)Co(III)X complexes bearing an appended quaternary ammonium salt or sterically hindered Lewis base showed excellent activity in the selectively alternating copolymerization of CO(2) with both aliphatic epoxides and cyclohexene oxide at high temperatures with low catalyst loading and/or low pressures of CO(2). Binary or one-component catalysts based on unsymmetric multichiral Co(III) complexes facilitated the efficient enantioselective copolymerization of CO(2) with epoxides, providing aliphatic polycarbonates with >99% head-to-tail content. These

  17. Activity of calcined Ag,Cu,Au/TiO2 catalysts in the dehydrogenation/dehydration of ethanol

    NASA Astrophysics Data System (ADS)

    Mai, Do Tkhyui; Pylinina, A. I.; Mikhailenko, I. I.

    2015-07-01

    The catalytic activity of the anatase TiO2 and M z+/TiO2 with supported ions M z+ = Ag+, Cu2+, Au3+ in vapor phase conversions of ethanol is investigated at temperatures of 100-400°C. It is shown that the yields of acetaldehyde and ethylene decline for the most active catalyst Cu2+/TiO2 but increase for TiO2 and Ag/TiO2. The drop in the activation energy of the dehydrogenation reaction over calcined samples is linearly correlated with the one in the reduction potential of M z+ to Cu+, Au+, Ag0 and the ionic radius of M z+ in the crystal. The energies of activation for ethylene formation change in the series TiO2 > Au3+ > Cu2+ >Ag+ and TiO2 ≈ Cu2+ ≈ Ag+ > Au3+ for the calcined samples. The rate of pyridine adsorption, considered as an indicator of the activity of acid sites, is a linear function of ion charge + z = 1, 2, 3, and slows by two-thirds after calcination.

  18. The influence of carbon support porosity on the activity of PtRu/Sibunit anode catalysts for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Rao, V.; Simonov, P. A.; Savinova, E. R.; Plaksin, G. V.; Cherepanova, S. V.; Kryukova, G. N.; Stimming, U.

    In this paper we analyse the promises of homemade carbon materials of Sibunit family prepared through pyrolysis of natural gases on carbon black surfaces as supports for the anode catalysts of direct methanol fuel cells. Specific surface area ( SBET) of the support is varied in the wide range from 6 to 415 m 2 g -1 and the implications on the electrocatalytic activity are scrutinized. Sibunit supported PtRu (1:1) catalysts are prepared via chemical route and the preparation conditions are adjusted in such a way that the particle size is constant within ±1 nm in order to separate the influence of support on the (i) catalyst preparation and (ii) fuel cell performance. Comparison of the metal surface area measured by gas phase CO chemisorption and electrochemical CO stripping indicates close to 100% utilisation of nanoparticle surfaces for catalysts supported on low (22-72 m 2 g -1) surface area Sibunit carbons. Mass activity and specific activity of PtRu anode catalysts change dramatically with SBET of the support, increasing with the decrease of the latter. 10%PtRu catalyst supported on Sibunit with specific surface area of 72 m 2 g -1 shows mass specific activity exceeding that of commercial 20%PtRu/Vulcan XC-72 by nearly a factor of 3.

  19. Catalyst dispersion and activity under conditions of temperature- staged liquefaction. Technical progress report, July--September 1991

    SciTech Connect

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

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

  20. Catalyst dispersion and activity under conditions of temperature-staged liquefaction. Technical progress report, October--December 1991

    SciTech Connect

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

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of the catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

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

    DOEpatents

    Muzio, Lawrence J.; Smith, Randall A.

    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.

  2. A Mechanochemically Triggered "Click" Catalyst.

    PubMed

    Michael, Philipp; Binder, Wolfgang H

    2015-11-16

    "Click" chemistry represents one of the most powerful approaches for linking molecules in chemistry and materials science. Triggering this reaction by mechanical force would enable site- and stress-specific "click" reactions--a hitherto unreported observation. We introduce the design and realization of a homogeneous Cu catalyst able to activate through mechanical force when attached to suitable polymer chains, acting as a lever to transmit the force to the central catalytic system. Activation of the subsequent copper-catalyzed "click" reaction (CuAAC) is achieved either by ultrasonication or mechanical pressing of a polymeric material, using a fluorogenic dye to detect the activation of the catalyst. Based on an N-heterocyclic copper(I) carbene with attached polymeric chains of different flexibility, the force is transmitted to the central catalyst, thereby activating a CuAAC in solution and in the solid state. PMID:26420664

  3. Comparison of the Activity and the Stability in CO Oxidation of Au-Cu Catalysts Supported on TiO2 in Anatase or Rutile Phase.

    PubMed

    Zanella, Rodolfo; Bokhimi, Xim; Maturano, Viridiana; Morales, Antonio

    2015-09-01

    Au-Cu catalysts supported on anatase or rutile phases were prepared by deposition-precipitation method. The titania polymorph used as the support determined the catalytic behavior. For the Au-Cu/rutile catalysts, the metallic phase had smaller dimensions than for the Au-Cu/anatase catalysts. The catalysts supported on anatase, however, were more active and stable than those supported on rutile. A systematic study of the catalytic activity for CO oxidation as a function of the temperature of activation and the aging time was performed. The catalytic properties were correlated with the properties of the catalysts analyzed with X-ray powder diffraction, refinement of the crystalline structures with the Rietveld method, and transmission electron microscopy. When the support was anatase, a pretreatment at 400 degrees C in air led to the most active catalysts, whereas when the support was rutile, a pretreatment between 200 and 300 degrees C in air led to the most active catalysts; activation under hydrogen generated less active catalysts. The Au-Cu catalysts activated in air were more active for the oxidation of CO than the respective monometallic gold catalysts, indicating a promoting effect between gold and copper to catalyze this reaction.

  4. Control of active sites in flocculation: Concept of equivalent active sites''

    SciTech Connect

    Behl, S.; Moudgil, B.M. . Dept. of Materials Science and Engineering)

    1993-12-01

    Flocculation and dispersion of solids are strong functions of the amount and conformation of the adsorbed polymer. Regions of dispersion and flocculation of solids with particular polymer molecules may be deduced from saturation adsorption data. The concept of equivalent active sites'' is proposed to explain flocculation and dispersion behavior irrespective of the amount or conformation of the adsorbed polymer. The concept has been further extended to study the selective flocculation process.

  5. Development of Novel Supported Gold Catalysts: A Materials Perspective

    SciTech Connect

    Dai, Sheng; Ma, Zhen

    2011-01-01

    Since Haruta et al. discovered that small gold nanoparticles finely dispersed on certain metal oxide supports can exhibit surprisingly high activity in CO oxidation below room temperature, heterogeneous catalysis by supported gold nanoparticles has attracted tremendous attention. The majority of publications deal with the preparation and characterization of conventional gold catalysts (e.g., Au/TiO{sub 2}), the use of gold catalysts in various catalytic reactions, as well as elucidation of the nature of the active sites and reaction mechanisms. In this overview, we highlight the development of novel supported gold catalysts from a materials perspective. Examples, mostly from those reported by our group, are given concerning the development of simple gold catalysts with single metal-support interfaces and heterostructured gold catalysts with complicated interfacial structures. Catalysts in the first category include active Au/SiO{sub 2} and Au/metal phosphate catalysts, and those in the second category include catalysts prepared by pre-modification of supports before loading gold, by post-modification of supported gold catalysts, or by simultaneous dispersion of gold and an inorganic component onto a support. CO oxidation has generally been employed as a probe reaction to screen the activities of these catalysts. These novel gold catalysts not only provide possibilities for applied catalysis, but also furnish grounds for fundamental research.

  6. Sol-gel derived mesoporous cobalt silica catalyst: Synthesis, characterization and its activity in the oxidation of phenol

    NASA Astrophysics Data System (ADS)

    Andas, Jeyashelly; Adam, Farook; Rahman, Ismail Ab.

    2014-10-01

    Highly mesoporous cobalt silica rice husk catalysts with (5-15 wt.%) Co2+ loading were prepared via a simple sol-gel technique at room temperature. The successful insertion of cobalt ions into silica matrix was evidenced from FT-IR, NMR, XPS and AAS analyses. Preservation of the mesoporosity nature of silica upon incorporating Co2+ was confirmed from the N2-sorption studies. The topography and morphology viewed by TEM analysis differs as the cobalt concentration varies from 5 to 15 wt.%. Parallel pore channels and spherical nanoparticles of 9.44 nm were achieved for cobalt silica catalysts with 10 and 15 wt.% respectively. Cobalt catalysts were active in the liquid-phase oxidation of phenol with H2O2 as an oxygen source. The performances of the catalysts were greatly influenced by various parameters such as reaction temperature, catalyst amount, molar ratio of substrate to oxidant, nature of solvent, metal loading and homogeneous precursor salt. Water served as the best reaction medium for this oxidation system. The regeneration studies confirmed cobalt catalyst could be reused for five cycles without experiencing large loss in the conversion. Both leaching and reusability studies testified that the catalysts were truly heterogeneous.

  7. Dehydrogenation of isopropanol on a cerium-nickel catalyst

    NASA Astrophysics Data System (ADS)

    Platonov, E. A.; Naumkin, A. V.; Maslakov, K. I.; Yagodovskii, V. D.

    2012-12-01

    The effect of a cerium additive on the catalytic activity of a 2 wt % Ni/SiO2 catalyst is studied. It found that under both flow and static conditions the activity of (2 wt % Ni + 0.2 wt % Ce)/SiO2 catalyst is higher than that of the original sample; the increase in activity results from a sharp increase in the number of active sites. A change in the composition of the surface layer of the catalysts is analyzed by X-ray photoelectron spectroscopy. It was found that the fraction of nickel decreases and the fraction of carbon increases in cerium-containing catalyst. An explanation of the change in the elemental composition of the catalytic active sites of a nickel catalyst in the presence of cerium is proposed on the basis of XPS data and previous quantum chemical calculations.

  8. The Influence of the Anionic Counter-Ion on the Activity of Ammonium Substituted Hoveyda-Type Olefin Metathesis Catalysts in Aqueous Media

    NASA Astrophysics Data System (ADS)

    Gułajski, Łukasz; Grela, Karol

    Polar olefin metathesis catalysts, bearing an ammonium group are presented. The electron withdrawing ammonium group not only activates the catalysts electronically, but at the same time makes the catalysts more hydrophilic. Catalysts can be therefore efficiently used not only in traditional media, such as methylene chloride and toluene, but also in technical-grade alcohols, alcohol— water mixtures and in neat water. Finally, in this overview the influence of the anionic counter-ion on the activity of ammonium substituted Hoveyda-type olefin metathesis catalysts in aqueous media is presented.

  9. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    SciTech Connect

    Ju, Hua; Li, Zhihu; Xu, Yanhui

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  10. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water

    SciTech Connect

    Moliner, Manuel; Roman-Leshkov, Yuriy; Davis, Mark E.

    2010-04-06

    The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (1:50 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here].

  11. Enzyme-mediated methodology for the site-specific radiolabeling of antibodies based on catalyst-free click chemistry.

    PubMed

    Zeglis, Brian M; Davis, Charles B; Aggeler, Robert; Kang, Hee Chol; Chen, Aimei; Agnew, Brian J; Lewis, Jason S

    2013-06-19

    An enzyme- and click chemistry-mediated methodology for the site-selective radiolabeling of antibodies on the heavy chain glycans has been developed and validated. To this end, a model system based on the prostate specific membrane antigen-targeting antibody J591, the positron-emitting radiometal (89)Zr, and the chelator desferrioxamine has been employed. The methodology consists of four steps: (1) the removal of sugars on the heavy chain region of the antibody to expose terminal N-acetylglucosamine residues; (2) the incorporation of azide-modified N-acetylgalactosamine monosaccharides into the glycans of the antibody; (3) the catalyst-free click conjugation of desferrioxamine-modified dibenzocyclooctynes to the azide-bearing sugars; and (4) the radiolabeling of the chelator-modified antibody with (89)Zr. The site-selective labeling methodology has proven facile, reproducible, and robust, producing (89)Zr-labeled radioimmunoconjguates that display high stability and immunoreactivity in vitro (>95%) in addition to highly selective tumor uptake (67.5 ± 5.0%ID/g) and tumor-to-background contrast in athymic nude mice bearing PSMA-expressing subcutaneous LNCaP xenografts. Ultimately, this strategy could play a critical role in the development of novel well-defined and highly immunoreactive radioimmunoconjugates for both the laboratory and clinic.

  12. Design of active and stable Co-Mo-Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction.

    PubMed

    Staszak-Jirkovský, Jakub; Malliakas, Christos D; Lopes, Pietro P; Danilovic, Nemanja; Kota, Subrahmanyam S; Chang, Kee-Chul; Genorio, Bostjan; Strmcnik, Dusan; Stamenkovic, Vojislav R; Kanatzidis, Mercouri G; Markovic, Nenad M

    2016-02-01

    Three of the fundamental catalytic limitations that have plagued the electrochemical production of hydrogen for decades still remain: low efficiency, short lifetime of catalysts and a lack of low-cost materials. Here, we address these three challenges by establishing and exploring an intimate functional link between the reactivity and stability of crystalline (CoS2 and MoS2) and amorphous (CoSx and MoSx) hydrogen evolution catalysts. We propose that Co(2+) and Mo(4+) centres promote the initial discharge of water (alkaline solutions) or hydronium ions (acid solutions). We establish that although CoSx materials are more active than MoSx they are also less stable, suggesting that the active sites are defects formed after dissolution of Co and Mo cations. By combining the higher activity of CoSx building blocks with the higher stability of MoSx units into a compact and robust CoMoSx chalcogel structure, we are able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.

  13. Self-assembly of cobalt-centered metal organic framework and multiwalled carbon nanotubes hybrids as a highly active and corrosion-resistant bifunctional oxygen catalyst

    NASA Astrophysics Data System (ADS)

    Fang, Yiyun; Li, Xinzhe; Li, Feng; Lin, Xiaoqing; Tian, Min; Long, Xuefeng; An, Xingcai; Fu, Yan; Jin, Jun; Ma, Jiantai

    2016-09-01

    Metal organic frameworks (MOF) derived carbonaceous materials have emerged as promising bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts for electrochemical energy conversion and storage. But previous attempts to overcome the poor electrical conductivity of MOFs hybrids involve a harsh high-template pyrolytic process to in situ form carbon, which suffer from extremely complex operation and inevitable carbon corrosion at high positive potentials when OER is operated. Herein, a self-assembly approach is presented to synthesize a non-precious metal-based, high active and strong durable Co-MOF@CNTs bifunctional catalyst for OER and ORR. CNTs not only improve the transportation of the electrons but also can sustain the harsh oxidative environment of OER without carbon corrosion. Meanwhile, the unique 3D hierarchical structure offers a large surface area and stable anchoring sites for active centers and CNTs, which enables the superior durability of hybrid. Moreover, a synergistic catalysis of Co(II), organic ligands and CNTs will enhance the bifunctional electrocatalytic performance. Impressively, the hybrid exhibits comparable OER and ORR catalytic activity to RuO2 and 20 wt% Pt/C catalysts and superior stability. This facile and versatile strategy to fabricating MOF-based hybrids may be extended to other electrode materials for fuel cell and water splitting applications.

  14. Design of active and stable Co-Mo-Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Staszak-Jirkovský, Jakub; Malliakas, Christos D.; Lopes, Pietro P.; Danilovic, Nemanja; Kota, Subrahmanyam S.; Chang, Kee-Chul; Genorio, Bostjan; Strmcnik, Dusan; Stamenkovic, Vojislav R.; Kanatzidis, Mercouri G.; Markovic, Nenad M.

    2016-02-01

    Three of the fundamental catalytic limitations that have plagued the electrochemical production of hydrogen for decades still remain: low efficiency, short lifetime of catalysts and a lack of low-cost materials. Here, we address these three challenges by establishing and exploring an intimate functional link between the reactivity and stability of crystalline (CoS2 and MoS2) and amorphous (CoSx and MoSx) hydrogen evolution catalysts. We propose that Co2+ and Mo4+ centres promote the initial discharge of water (alkaline solutions) or hydronium ions (acid solutions). We establish that although CoSx materials are more active than MoSx they are also less stable, suggesting that the active sites are defects formed after dissolution of Co and Mo cations. By combining the higher activity of CoSx building blocks with the higher stability of MoSx units into a compact and robust CoMoSx chalcogel structure, we are able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.

  15. Design of active and stable Co-Mo-Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction.

    PubMed

    Staszak-Jirkovský, Jakub; Malliakas, Christos D; Lopes, Pietro P; Danilovic, Nemanja; Kota, Subrahmanyam S; Chang, Kee-Chul; Genorio, Bostjan; Strmcnik, Dusan; Stamenkovic, Vojislav R; Kanatzidis, Mercouri G; Markovic, Nenad M

    2016-02-01

    Three of the fundamental catalytic limitations that have plagued the electrochemical production of hydrogen for decades still remain: low efficiency, short lifetime of catalysts and a lack of low-cost materials. Here, we address these three challenges by establishing and exploring an intimate functional link between the reactivity and stability of crystalline (CoS2 and MoS2) and amorphous (CoSx and MoSx) hydrogen evolution catalysts. We propose that Co(2+) and Mo(4+) centres promote the initial discharge of water (alkaline solutions) or hydronium ions (acid solutions). We establish that although CoSx materials are more active than MoSx they are also less stable, suggesting that the active sites are defects formed after dissolution of Co and Mo cations. By combining the higher activity of CoSx building blocks with the higher stability of MoSx units into a compact and robust CoMoSx chalcogel structure, we are able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments. PMID:26618882

  16. Pore structure effects on Ca-based sorbent sulfation capacity at medium temperatures: activated carbon as sorbent/catalyst support.

    PubMed

    Tseng, Hui-Hsin; Wey, Ming-Yen; Lin, Chiou-Liang; Chang, Yu-Chen

    2002-11-01

    The reaction between three different Ca-based sorbents and SO2 were studied in a medium temperature range (473-773 K). The largest SO2 capture was found with Ca(OH)2 at 773 K, 126.31 mg SO2 x g Ca(OH)2(-1), and the influence of SO2 concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sulfated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO2, one kind of CaO/ activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO2 than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO2 and Ca-based sorbents and the prepared CaO/AC sorbents/catalysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the desulfurization reaction. AC acting as the support can play a role to supply O2 to increase the affinity to SO2. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO2 adsorption.

  17. Gold nanoparticles-graphene hybrids as active catalysts for Suzuki reaction

    SciTech Connect

    Li, Yang; Fan, Xiaobin; Qi, Junjie; Ji, Junyi; Wang, Shulan; Zhang, Guoliang; Zhang, Fengbao

    2010-10-15

    Graphene was successfully modified with gold nanoparticles in a facile route by reducing chloroauric acid in the presence of sodium dodecyl sulfate, which is used as both a surfactant and reducing agent. The gold nanoparticles-graphene hybrids were characterized by high-resolution transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray diffraction and energy X-ray spectroscopy. We demonstrate for the first time that the gold nanoparticles-graphene hybrids can act as efficient catalysts for the Suzuki reaction in water under aerobic conditions. The catalytic activity of gold nanoparticles-graphene hybrids was influenced by the size of the gold nanoparticles.

  18. Diarylrhodates as promising active catalysts for the arylation of vinyl ethers with Grignard reagents.

    PubMed

    Iwasaki, Takanori; Miyata, Yoshinori; Akimoto, Ryo; Fujii, Yuuki; Kuniyasu, Hitoshi; Kambe, Nobuaki

    2014-07-01

    Anionic diarylrhodium complexes, generated by reacting [RhCl(cod)]2 with 2 equiv of aryl Grignard reagents, were found to be effective active catalysts in cross-coupling reactions of vinyl ethers with aryl Grignard reagents, giving rise to the production of vinyl arenes. In this catalytic system, vinyl-O bonds were preferably cleaved over Ar-O or Ar-Br bonds. A lithium rhodate complex was isolated, and its crystal structure was determined by X-ray crystallography. PMID:24957673

  19. Active and Durable Hydrogen Evolution Reaction Catalyst Derived from Pd-Doped Metal-Organic Frameworks.

    PubMed

    Chen, Jitang; Xia, Guoliang; Jiang, Peng; Yang, Yang; Li, Ren; Shi, Ruohong; Su, Jianwei; Chen, Qianwang

    2016-06-01

    The water electrolysis is of critical importance for sustainable hydrogen production. In this work, a highly efficient and stable PdCo alloy catalyst (PdCo@CN) was synthesized by direct annealing of Pd-doped metal-organic frameworks (MOFs) under N2 atmosphere. In 0.5 M H2SO4 solution, PdCo@CN displays remarkable electrocatalytic performance with overpotential of 80 mV, a Tafel slope of 31 mV dec(-1), and excellent stability of 10 000 cycles. Our studies reveal that noble metal doped MOFs are ideal precursors for preparing highly active alloy electrocatalysts with low content of noble metal.

  20. Lattice-Strain Control of the Activity in Dealloyed Core-Shell Fuel Cell Catalysts

    SciTech Connect

    Strasser, P.; Koh, Shirlaine; Anniyev, Toyli; Greeley, Jeff; More, Karren Leslie; Yu, Chengfei; Liu, Zengcai; Kaya, Sarpa; Nordlund, Dennis; Ogasawara, Hirohito; Toney, Michael F.; Anders, Nilsson

    2010-01-01

    Electrocatalysis will play a key role in future energy conversion and storage technologies, such as water electrolysers, fuel cells and metal-air batteries. Molecular interactions between chemical reactants and the catalytic surface control the activity and efficiency, and hence need to be optimized; however, generalized experimental strategies to do so are scarce. Here we show how lattice strain can be used experimentally to tune the catalytic activity of dealloyed bimetallic nanoparticles for the oxygen-reduction reaction, a key barrier to the application of fuel cells and metal-air batteries. We demonstrate the core-shell structure of the catalyst and clarify the mechanistic origin of its activity. The platinum-rich shell exhibits compressive strain, which results in a shift of the electronic band structure of platinum and weakening chemisorption of oxygenated species. We combine synthesis, measurements and an understanding of strain from theory to generate a reactivity-strain relationship that provides guidelines for tuning electrocatalytic activity.

  1. Sunlight-driven copper-catalyst activation applied to photolatent click chemistry.

    PubMed

    Beniazza, Rédouane; Lambert, Romain; Harmand, Lydie; Molton, Florian; Duboc, Carole; Denisov, Sergey; Jonusauskas, Gedeminas; McClenaghan, Nathan D; Lastécouères, Dominique; Vincent, Jean-Marc

    2014-10-01

    The synthesis, full characterization, photoreduction properties, and catalytic activity for the copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction of a copper(II)-DMEDA (N,N'-dimethylethylendiamine) complex is reported. Spectroscopic studies (UV/Vis, EPR) demonstrated that under daylight illumination highly effective copper(II) to copper(I) reduction occurs in this complex. These findings are in agreement with a high photoreduction quantum yield value of 0.22 in MeOH, and a value approaching unity as determined in THF. The reduction process, which can also be conducted by irradiation at 365 nm by using a standard TLC (thin layer chromatography) lamp, is ascribed to a highly efficient photoinduced electron transfer (PET) process mediated by the benzophenone photosensitizer present in the carboxylate counterion. Having deaerated the reaction mixture, the photogenerated copper(I) species proved to be highly active for the CuAAC reaction, demonstrated by reactions conducted with low catalyst loading (0.5 mol %) on a range of clickable protected and non-protected mono- and disaccharides. Once initiated, the reaction can be stopped at any time on introducing air into the reaction medium. Deoxygenation followed by irradiation restores the activity, making the copper(II)-DMEDA complex a switchable catalyst of practical value. PMID:25171758

  2. Comparison of preparation methods for ceria catalyst and the effect of surface and bulk sulfates on its activity toward NH3-SCR.

    PubMed

    Chang, Huazhen; Ma, Lei; Yang, Shijian; Li, Junhua; Chen, Liang; Wang, Wei; Hao, Jiming

    2013-11-15

    A series of CeO2 catalysts prepared with sulfate (S) and nitrate (N) precursors by hydrothermal (H) and precipitation (P) methods were investigated in selective catalytic reduction of NOx by NH3 (NH3-SCR). The catalytic activity of CeO2 was significantly affected by the preparation methods and the precursor type. CeO2-SH, which was prepared by hydrothermal method with cerium (IV) sulfate as a precursor, showed excellent SCR activity and high N2 selectivity in the temperature range of 230-450 °C. Based on the results obtained by temperature-programmed reduction (H2-TPR), transmission infrared spectra (IR) and thermal gravimetric analysis (TGA), the excellent performance of CeO2-SH was correlated with the surface sulfate species formed in the hydrothermal reaction. These results indicated that sulfate species bind with Ce(4+) on the CeO2-SH catalyst, and the specific sulfate species, such as Ce(SO4)2 or CeOSO4, were formed. The adsorption of NH3 was promoted by these sulfate species, and the probability of immediate oxidation of NH3 to N2O on Ce(4+) was reduced. Accordingly, the selective oxidation of NH3 was enhanced, which contributed to the high N2 selectivity in the SCR reaction. However, the location of sulfate on the CeO2-SP catalyst was different. Plenty of sulfate species were likely deposited on CeO2-SP surface, covering the active sites for NO oxidation, which resulted in poor SCR activity in the test temperature range. Moreover, the resistance to alkali metals, such as Na and K, was improved over the CeO2-SH catalyst.

  3. Surface state and catalytic activity and selectivity of nickel catalysts in hydrogenation reactions--3. Electronic and catalytic properties of nickel catalysts. [Butylene oxides

    SciTech Connect

    Okamoto, Y.; Nitta, Y.; Imanaka, T.; Teranishi, S.

    1980-08-01

    A relationship between a parameter ..delta.. q and the ESCA chemical shift was derived from available extended Hueckel calculation results and ESCA data for nickel boride and nickel phosphide. The ..delta.. q parameter described the change in electron density at the nickel metal that occurred due to the electron transfer between nickel and the other element. The ..delta.. q parameters were estimated for Rayney nickel and Urushibara nickel, which contained aluminum and zinc alloy components, respectively, from product ratios and rate ratios measured for cyclohexene and cyclooctene hydrogenation on these catalysts. The ..delta.. q parameter correlated the increase in specific activities with increasing electron density in the hydrogenation of styrene, the increase in poisoning coefficient for carbon disulfide and triphenylphosphine with increasing electron density in the hydrogenation of styrene, and the selectivity for n-butyl alcohol in the hydrogenation of 1,2-butylene oxide on various nickel catalysts.

  4. Modelling metal centres, acid sites and reaction mechanisms in microporous catalysts.

    PubMed

    O'Malley, Alexander J; Logsdail, A J; Sokol, A A; Catlow, C R A

    2016-07-01

    We discuss the role of QM/MM (embedded cluster) computational techniques in catalytic science, in particular their application to microporous catalysis. We describe the methodologies employed and illustrate their utility by briefly summarising work on metal centres in zeolites. We then report a detailed investigation into the behaviour of methanol at acidic sites in zeolites H-ZSM-5 and H-Y in the context of the methanol-to-hydrocarbons/olefins process. Studying key initial steps of the reaction (the adsorption and subsequent methoxylation), we probe the effect of framework topology and Brønsted acid site location on the energetics of these initial processes. We find that although methoxylation is endothermic with respect to the adsorbed system (by 17-56 kJ mol(-1) depending on the location), there are intriguing correlations between the adsorption/reaction energies and the geometries of the adsorbed species, of particular significance being the coordination of methyl hydrogens. These observations emphasise the importance of adsorbate coordination with the framework in zeolite catalysed conversions, and how this may vary with framework topology and site location, particularly suited to investigation by QM/MM techniques. PMID:27136967

  5. Platinum-Promoted Ga/Al2O3 as Highly Active, Selective, and Stable Catalyst for the Dehydrogenation of Propane**

    PubMed Central

    Sattler, Jesper J H B; Gonzalez-Jimenez, Ines D; Luo, Lin; Stears, Brien A; Malek, Andrzej; Barton, David G; Kilos, Beata A; Kaminsky, Mark P; Verhoeven, Tiny W G M; Koers, Eline J; Baldus, Marc; Weckhuysen, Bert M

    2014-01-01

    A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga3+ species are the active species and where Pt functions as a promoter. PMID:24989975

  6. Composite catalyst surfaces: Effect of inert and active heterogeneities on pattern formation

    SciTech Connect

    Baer, M.; Bangia, A.K.; Kevrekidis, I.G.; Haas, G.; Rotermund, H.H.; Ertl, G.

    1996-12-05

    Spatiotemporal dynamics in reaction-diffusion systems can be altered through the properties (reactivity, diffusivity) of the medium in which they occur. We construct active heterogeneous media (composite catalytic surfaces with inert as well as active illusions) using microelectronics fabrication techniques and study the spatiotemporal dynamics of heterogeneous catalytic reactions on these catalysts. In parallel, we perform simulations as well as numerical stability and bifurcation analysis of these patterns using mechanistic models. At the limit of large heterogeneity `grain size` (compared to the wavelength of spontaneously arising structures) the interaction patterns with inert or active boundaries dominates (e.g., pinning, transmission, and boundary breakup of spirals, interaction of pulses with corners, `pacemaker` effects). At the opposite limit of very small or very finely distributed heterogeneity, effective behavior is observed (slight modulation of pulses, nearly uniform oscillations, effective spirals). Some representative studies of transitions between the two limits are presented. 48 refs., 11 figs.

  7. Systematic preparation of selective heterogeneous catalysts

    SciTech Connect

    Augustine, R.L.

    1991-11-07

    The Single Turnover (STO) procedure, involving pulses of hydrogen and 1-butene, was developed for studying the types of active sites present on supported metal catalysts. The STO procedure was used to study direct saturated sites and other topics. Frontier molecular orbital studies were also made.

  8. Dissecting the active site of a photoreceptor protein

    NASA Astrophysics Data System (ADS)

    Hoff, Wouter; Hara, Miwa; Ren, Jie; Moghadam, Farzaneh; Xie, Aihua; Kumauchi, Masato

    While enzymes are quite large molecules, functionally important chemical events are often limited to a small region of the protein: the active site. The physical and chemical properties of residues at such active sites are often strongly altered compared to the same groups dissolved in water. Understanding such effects is important for unraveling the mechanisms underlying protein function and for protein engineering, but has proven challenging. Here we report on our ongoing efforts on using photoactive yellow protein (PYP), a bacterial photoreceptor, as a model system for such effects. We will report on the following questions: How many residues affect active site properties? Are these residues in direct physical contact with the active site? Can functionally important residues be recognized in the crystal structure of a protein? What structural resolution is needed to understand active sites? What spectroscopic techniques are most informative? Which weak interactions dominate active site properties?

  9. Highly dispersed SiOx/Al2O3 catalysts illuminate the reactivity of isolated silanol sites

    DOE PAGES

    Mouat, Aidan R.; George, Cassandra; Kobayashi, Takeshi; Pruski, Marek; van Duyne, Richard P.; Marks, Tobin J.; Stair, Peter C.

    2015-09-23

    The reaction of γ-alumina with tetraethylorthosilicate (TEOS) vapor at low temperatures selectively yields monomeric SiOx species on the alumina surface. These isolated (-AlO)3Si(OH) sites are characterized by PXRD, XPS, DRIFTS of adsorbed NH3, CO, and pyridine, and 29Si and 27Al DNP-enhanced solid-state NMR spectroscopy. The formation of isolated sites suggests that TEOS reacts preferentially at strong Lewis acid sites on the γ-Al2O3 surface, functionalizing the surface with “mild” Brønsted acid sites. As a result, for liquid-phase catalytic cyclohexanol dehydration, these SiOx sites exhibit up to 3.5-fold higher specific activity than the parent alumina with identical selectivity.

  10. Selenium-ligated palladium(II) complexes as highly active catalysts for carbon-carbon coupling reactions: the Heck reaction.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Zheng, Chong

    2004-08-19

    Three selenium-ligated Pd(II) complexes were readily synthesized and shown to be extremely active catalysts for the Heck reaction of various aryl bromides, including deactivated and heterocyclic ones. The catalytic activity of the selenide-based Pd(II) complexes not only rivals but vastly outperforms that of the corresponding phosphorus and sulfur analogues. Practical advantages of the selenium-based catalysts include their straightforward synthesis and high activity in the absence of any additives as well as the enhanced stability of the selenide ligands toward air oxidation. PMID:15330667

  11. Selenium-ligated palladium(II) complexes as highly active catalysts for carbon-carbon coupling reactions: the Heck reaction.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Zheng, Chong

    2004-08-19

    Three selenium-ligated Pd(II) complexes were readily synthesized and shown to be extremely active catalysts for the Heck reaction of various aryl bromides, including deactivated and heterocyclic ones. The catalytic activity of the selenide-based Pd(II) complexes not only rivals but vastly outperforms that of the corresponding phosphorus and sulfur analogues. Practical advantages of the selenium-based catalysts include their straightforward synthesis and high activity in the absence of any additives as well as the enhanced stability of the selenide ligands toward air oxidation.

  12. Antimicrobial activities of silver used as a polymerization catalyst for a wound-healing matrix

    PubMed Central

    Babu, Ranjith; Zhang, Jianying; Beckman, Eric J.; Virji, Mohammed; Pasculle, William A.; Wells, Alan

    2007-01-01

    Wound healing is a complex and orchestrated process that re-establishes the barrier and other functions of the skin. While wound healing proceeds apace in healthy individual, bacterial overgrowth and infection disrupts this process with significant morbidity and mortality. As such, any artificial matrix to promote wound healing must also control infecting microbes. We had earlier developed a two-part space-conforming gel backbone based on polyethyleneglycol (PEG) or lactose, which used ionic silver as the catalyst for gelation. As silver is widely used as an in vitro antimicrobial, use of silver as a catalyst for gelation provided the opportunity to assess its function as an anti-microbial agent in the gels. We found that these gels show bacteriostatic and bactericidal activity for a range of Gram-negative and Gram-positive organisms, including aerobic as well as anaerobic bacteria. This activity lasted for days, as silver leached out of the formed gels over a day in the manner of second-order decay. Importantly the gels did not limit either cell growth or viability, though cell migration was affected. Adding collagen I fragments to the gels corrected this effect on cell migration. We also found that the PEG gel did not interfere with hemostasis. These observations provide the basis for use of the gel backbones for incorporation of anesthetic agents and factors that promote wound repair. In conclusion, silver ions can serve dual functions of catalyzing gelation and providing anti-microbial properties to a biocompatible polymer. PMID:16635526

  13. Isoselenazolones as catalysts for the activation of bromine: bromolactonization of alkenoic acids and oxidation of alcohols.

    PubMed

    Balkrishna, Shah Jaimin; Prasad, Ch Durga; Panini, Piyush; Detty, Michael R; Chopra, Deepak; Kumar, Sangit

    2012-11-01

    Isoselenazolones were synthesized by a copper-catalyzed Se-N bond forming reaction between 2-halobenzamides and selenium powder. The catalytic activity of the various isoselenazolones was studied in the bromolactonization of pent-4-enoic acid. Isoselenazolone 9 was studied as a catalyst in several reactions: the bromolactonization of a series of alkenoic acids with bromine or N-bromosuccinimide (NBS) in the presence of potassium carbonate as base, the bromoesterification of a series of alkenes using NBS and a variety of carboxylic acids, and the oxidation of secondary alcohols to ketones using bromine as an oxidizing reagent. Mechanistic details of the isoselenazolone-catalyzed bromination reaction were revealed by (77)Se NMR spectroscopic and ES-MS studies. The oxidative addition of bromine to the isoselenazolone gives the isoselenazolone(IV) dibromide, which could be responsible for the activation of bromine under the reaction conditions. Steric effects from an N-phenylethyl group on the amide of the isoselenazolone and electron-withdrawing fluoro substituents on the benzo fused-ring of the isoselenazolone appear to enhance the stability of the isoselenazolone as a catalyst for the bromination reaction. PMID:23046286

  14. CO Oxidation on Au/TiO2: Condition-Dependent Active Sites and Mechanistic Pathways.

    PubMed

    Wang, Yang-Gang; Cantu, David C; Lee, Mal-Soon; Li, Jun; Glezakou, Vassiliki-Alexandra; Rousseau, Roger

    2016-08-24

    We present results of ab initio electronic structure and molecular dynamics simulations (AIMD), as well as a microkinetic model of CO oxidation catalyzed by TiO2 supported Au nanocatalysts. A coverage-dependent microkinetic analysis, based on energetics obtained with density functional methods, shows that the dominant kinetic pathway, activated oxygen species, and catalytic active sites are all strongly depended on both temperature and oxygen partial pressure. Under oxidizing conditions and T < 400 K, the prevalent pathway involves a dynamic single atom catalytic mechanism. This reaction is catalyzed by a transient Au-CO species that migrates from the Au-cluster onto a surface oxygen adatom. It subsequently reacts with the TiO2 support via a Mars van Krevelen mechanism to form CO2 and finally the Au atom reintegrates back into the gold cluster to complete the catalytic cycle. At 300 ≤ T ≤ 600 K, oxygen-bound single Oad-Au(+)-CO sites and the perimeter Au-sites of the nanoparticle work in tandem to optimally catalyze the reaction. Above 600 K, a variety of alternate pathways associated with both single-atom and the perimeter sites of the Au nanoparticle are found to be active. Under low oxygen pressures, Oad-Au(+)-CO species can be a source of catalyst deactivation and the dominant pathway involves only Au-perimeter sites. A detailed comparison of the current model and the existing literature resolves many apparent inconsistencies in the mechanistic interpretations. PMID:27480512

  15. Surface characterization and dehydrocyclization activity of Pt/KL catalysts prepared by different methods

    NASA Astrophysics Data System (ADS)

    Arcoya, Adolfo; Seoane, Xosé Lois; Grau, Javier Mario

    2003-01-01

    Three Pt/KL-zeolite catalysts containing 1 wt.% of metal were prepared by different procedures: CI-1 and CI-2 by wetness impregnation of the zeolite with aqueous solutions of Pt(NH 3) 4(OH) 2 and Pt(NH 3) 4(NO 3) 2, respectively, and CE-3 by ion exchange with a Pt(NH 3) 4(OH) 2 solution. These samples were successively calcined at 573 K and reduced at 773 K. An additional sample, CE-3-n, was obtained from CE-3 by ion-exchange with KNO 3. The catalysts were characterized by H 2-O 2 titration, TPD of NH 3, XRD, CO-FTIR and XPS and tested in the dehydrocyclization of n-heptane to toluene at 723 K, 100 kPa, WHSV=3.4 h -1 and H 2/ nC 7=7.3 mol mol -1 in a fixed bed tubular reactor. Characterization results show that Pt dispersion for the ion exchanged samples is higher than for the impregnated ones and CE-3 is the more acidic catalyst. FTIR measurements indicate that the highest population of electron reach platinum species (Pt δ- ) is found in CE-3-n, while CE-3 exhibits the highest concentration of electron deficient platinum species (Pt δ+ ). The order of dehydrocyclization activity, CE-3-n>CI-2>CI-1>CE-3, roughly correlates with that of the intensity of the FTIR bands attributed to Pt δ- . The low selectivity toward toluene of CE-3 is attributed to the protons generated during the reduction of Pt 2+ exchanged.

  16. Renewable Feedstocks: The Problem of Catalyst Deactivation and its Mitigation.

    PubMed

    Lange, Jean-Paul

    2015-11-01

    Much research has been carried out in the last decade to convert bio-based feedstock into fuels and chemicals. Most of the research focuses on developing active and selective catalysts, with much less attention devoted to their long-term stability. This Review considers the main challenges in long-term catalyst stability, discusses some fundamentals, and presents options for their mitigation. Three main challenges are discussed: catalyst fouling, catalyst poisoning, and catalyst destruction. Fouling is generally related to the deposition of insoluble components present in the feed or formed by degradation of the feed or intermediates. Poisoning is related to the deposition of electropositive contaminants (e.g. alkali and alkaline earth metals) on acid sites or of electronegative contaminants (e.g. N and S) at hydrogenation sites. Catalyst destruction results from the thermodynamic instability of most oxidic supports, solid acids/bases, and hydrogenation functions under hydrothermal conditions. PMID:26457585

  17. Mars Surveyor Project Landing Site Activities

    NASA Technical Reports Server (NTRS)

    Gulick, Virginia C.; Briggs, Geoffrey; Saunders, R. Stephen; Gilmore, Martha; Soderblom, Larry

    1999-01-01

    The Mars Surveyor Program --now a cooperative program led by NASA and CNES along with other international partners -- is underway. It has the primary science objective of furthering our understanding of the biological potential and possible biological history of Mars and has the complementary objective of improving our understanding of martian climate evolution and planetary history The missions will develop technology and acquire data necessary for eventual human Exploration. Launches of orbiters, landers and rovers will take place in 2001 and in 2003; in 2005 a complete system will be launched capable of returning samples to Earth by 2008. A key aspect of the program is the selection of landing sites. This abstract 1) reports on the status of the landing site selection process that begins with the 2001 lander mission and 2) outlines be opportunities for the Mars community to provide input into the landing site selection process.

  18. Mars Surveyor Project Landing Site Activities

    NASA Technical Reports Server (NTRS)

    Gulick, V. C.; Briggs, Geoffrey; Saunders, R. Stephen; Gilmore, Martha; Soderblom, Larry

    1999-01-01

    The Mars Surveyor Program -- now a cooperative program led by NASA and CNES along with other international partners -- is underway. It has the primary science objective of furthering our understanding of the biological potential and possible biological history of Mars and has the complementary objective of improving our understanding of martian climate evolution and planetary history. The missions will develop technology and acquire data necessary for eventual human exploration. Launches of orbiters, landers and rovers will take place in 2001 and in 2003; in 2005 a complete system will be launched capable of returning samples to Earth by 2008. A key aspect of the program is the selection of landing sites. This abstract 1) reports on the status of the landing site selection process that begins with the 2001 lander mission and 2) outlines the opportunities for the Mars community to provide input into the landing site selection process.

  19. Ruthenium carbenes supported on mesoporous silicas as highly active and selective hybrid catalysts for olefin metathesis reactions under continuous flow.

    PubMed

    Bru, Miriam; Dehn, Richard; Teles, J Henrique; Deuerlein, Stephan; Danz, Manuel; Müller, Imke B; Limbach, Michael

    2013-08-26

    In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex. PMID:23852995

  20. Ruthenium carbenes supported on mesoporous silicas as highly active and selective hybrid catalysts for olefin metathesis reactions under continuous flow.

    PubMed

    Bru, Miriam; Dehn, Richard; Teles, J Henrique; Deuerlein, Stephan; Danz, Manuel; Müller, Imke B; Limbach, Michael

    2013-08-26

    In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex.

  1. Hydrogen evolution across nano-Schottky junctions at carbon supported MoS2 catalysts in biphasic liquid systems.

    PubMed

    Ge, Peiyu; Scanlon, Micheál D; Peljo, Pekka; Bian, Xiaojun; Vubrel, Heron; O'Neill, Arlene; Coleman, Jonathan N; Cantoni, Marco; Hu, Xile; Kontturi, Kyösti; Liu, Baohong; Girault, Hubert H

    2012-07-01

    The activities of a series of MoS(2)-based hydrogen evolution catalysts were studied by biphasic reactions monitored by UV/Vis spectroscopy. Carbon supported MoS(2) catalysts performed best due to an abundance of catalytic edge sites and strong electronic coupling of catalyst to support.

  2. Activation of Inhibitors by Sortase Triggers Irreversible Modification of the Active Site*S

    PubMed Central

    Maresso, Anthony W.; Wu, Ruiying; Kern, Justin W.; Zhang, Rongguang; Janik, Dorota; Missiakas, Dominique M.; Duban, Mark-Eugene; Joachimiak, Andrzej; Schneewind, Olaf

    2011-01-01

    Sortases anchor surface proteins to the cell wall of Gram-positive pathogens through recognition of specific motif sequences. Loss of sortase leads to large reductions in virulence, which identifies sortase as a target for the development of antibacterials. By screening 135,625 small molecules for inhibition, we report here that aryl (β-amino)ethyl ketones inhibit sortase enzymes from staphylococci and bacilli. Inhibition of sortases occurs through an irreversible, covalent modification of their active site cysteine. Sortases specifically activate this class of molecules via β-elimination, generating a reactive olefin intermediate that covalently modifies the cysteine thiol. Analysis of the three-dimensional structure of Bacillus anthracis sortase B with and without inhibitor provides insights into the mechanism of inhibition and reveals binding pockets that can be exploited for drug discovery. PMID:17545669

  3. Oxide Nanocrystal Model Catalysts.

    PubMed

    Huang, Weixin

    2016-03-15

    as the active sites, respectively, to produce acrolein, propylene oxide, and CO2. Ceria rods enclosed with the {110} and {100} crystal planes, ceria cubes enclosed with the {100} crystal planes, and ceria octahedra enclosed with the {111} crystal planes exhibit distinct morphology-dependent oxygen vacancy concentrations and structures that can be well correlated with the surface compositions and structures of exposed crystal planes. Consequently, the metal-ceria interactions, structures, and catalytic performances of ceria-supported catalysts depend on the CeO2 morphology. Our results comprehensively reveal the morphology-dependent surface chemistry and catalysis of oxide nanocrystals that not only greatly deepen the fundamental understanding of oxide catalysis but also demonstrate a morphology-engineering strategy to optimize the catalytic performance of oxide catalysts. These results adequately exemplify the concept of oxide nanocrystal model catalysts for the fundamental investigations of oxide catalysis without the "materials gap" and "pressure gap". With the structure-catalytic property relationships learned from oxide nanocrystal model catalyst studies and the advancement of controlled-synthesis methods, it is promising to realize the structural design and controlled synthesis of novel efficient oxide catalysts in the future.

  4. The bifunctional active site of s-adenosylmethionine synthetase. Roles of the active site aspartates.

    PubMed

    Taylor, J C; Markham, G D

    1999-11-12

    S-Adenosylmethionine (AdoMet) synthetase catalyzes the biosynthesis of AdoMet in a unique enzymatic reaction. Initially the sulfur of methionine displaces the intact tripolyphosphate chain (PPP(i)) from ATP, and subsequently PPP(i) is hydrolyzed to PP(i) and P(i) before product release. The crystal structure of Escherichia coli AdoMet synthetase shows that the active site contains four aspartate residues. Aspartate residues Asp-16* and Asp-271 individually provide the sole protein ligand to one of the two required Mg(2+) ions (* denotes a residue from a second subunit); aspartates Asp-118 and Asp-238* are proposed to interact with methionine. Each aspartate has been changed to an uncharged asparagine, and the metal binding residues were also changed to alanine, to assess the roles of charge and ligation ability on catalytic efficiency. The resultant enzyme variants all structurally resemble the wild type enzyme as indicated by circular dichroism spectra and are tetramers. However, all have k(cat) reductions of approximately 10(3)-fold in AdoMet synthesis, whereas the MgATP and methionine K(m) values change by less than 3- and 8-fold, respectively. In the partial reaction of PPP(i) hydrolysis, mutants of the Mg(2+) binding residues have >700-fold reduced catalytic efficiency (k(cat)/K(m)), whereas the D118N and D238*N mutants are impaired less than 35-fold. The catalytic efficiency for PPP(i) hydrolysis by Mg(2+) site mutants is improved by AdoMet, like the wild type enzyme. In contrast AdoMet reduces the catalytic efficiency for PPP(i) hydrolysis by the D118N and D238*N mutants, indicating that the events involved in AdoMet activation are hindered in these methionyl binding site mutants. Ca(2+) uniquely activates the D271A mutant enzyme to 15% of the level of Mg(2+), in contrast to the approximately 1% Ca(2+) activation of the wild type enzyme. This indicates that the Asp-271 side chain size is a discriminator between the activating ability of Ca(2+) and the

  5. Facile synthesis of a platinum-lead oxide nanocomposite catalyst with high activity and durability for ethanol electrooxidation.

    PubMed

    Yang, Wei-Hua; Wang, Hong-Hui; Chen, De-Hao; Zhou, Zhi-You; Sun, Shi-Gang

    2012-12-21

    Aimed at searching for highly active and stable nano-scale Pt-based catalysts that can improve significantly the energy conversion efficiency of direct ethanol fuel cells (DEFCs), a novel Pt-PbO(x) nanocomposite (Pt-PbO(x) NC) catalyst with a mean size of 3.23 nm was synthesized through a simple wet chemistry method without using a surfactant, organometallic precursors and high temperature. Electrocatalytic tests demonstrated that the as-prepared Pt-PbO(x) NC catalyst possesses a much higher catalytic activity and a longer durability than Pt nanoparticles (nm-Pt) and commercial Pt black catalysts for ethanol electrooxidation. For instance, Pt-PbO(x) NC showed an onset potential that was 30 mV and 44 mV less positive, together with a peak current density 1.7 and 2.6 times higher than those observed for nm-Pt and Pt black catalysts in the cyclic voltammogram tests. The ratio of current densities per unit Pt mass on Pt-PbO(x) NC, nm-Pt and Pt black catalysts is 27.3 : 3.4 : 1 for the long-term (2 hours) chronoamperometric experiments measured at -0.4 V (vs. SCE). In situ FTIR spectroscopic studies revealed that the activity of breaking C-C bonds of ethanol of the Pt-PbO(x) NC is as high as 5.17 times that of the nm-Pt, which illustrates a high efficiency of ethanol oxidation to CO(2) on the as-prepared Pt-PbO(x) NC catalyst.

  6. Significant role of Mn(III) sites in e(g)(1) configuration in manganese oxide catalysts for efficient artificial water oxidation.

    PubMed

    Indra, Arindam; Menezes, Prashanth W; Schuster, Felix; Driess, Matthias

    2015-11-01

    Development of efficient bio-inspired water oxidation system with transition metal oxide catalyst has been considered as the one of the most challenging task in the recent years. As the oxygen evolving center of photosystem II consists of Mn4CaO5 cluster, most of the water oxidation study was converged to build up manganese oxide based catalysts. Here we report the synthesis of efficient artificial water oxidation catalysts by transferring the inactive manganese monooxide (MnO) under highly oxidizing conditions with ceric ammonium nitrate (CAN) and ozone (O3). MnO was partially oxidized to form mixed-valent manganese oxide (MnOx) with CAN whereas completely oxidized to mineral phase of ε-MnO2 (Akhtenskite) upon treatment of O3 in acidic solution, which we explore first time as a water oxidation catalyst. Chemical water oxidation, as well as the photochemical water oxidation in the presence of sacrificial electron acceptor and photosensitizer with the presented catalysts were carried out that followed the trends: MnOx>MnO2>MnO. Structural and activity correlation reveals that the presence of larger extent of Mn(III) in MnOx is the responsible factor for higher activity compared to MnO2. Mn(III) species in octahedral system with eg(1) configuration furnishes and facilitates the Mn-O and Mn-Mn bond enlargement with required structural flexibility and disorder in the manganese oxide structure which indeed facilitates water oxidation.

  7. Dinuclear thiazolylidene copper complex as highly active catalyst for azid-alkyne cycloadditions.

    PubMed

    Schöffler, Anne L; Makarem, Ata; Rominger, Frank; Straub, Bernd F

    2016-01-01

    A dinuclear N-heterocyclic carbene (NHC) copper complex efficiently catalyzes azide-alkyne cycloaddition (CuAAC) "click" reactions. The ancillary ligand comprises two 4,5-dimethyl-1,3-thiazol-2-ylidene units and an ethylene linker. The three-step preparation of the complex from commercially available starting compounds is more straightforward and cost-efficient than that of the previously described 1,2,4-triazol-5-ylidene derivatives. Kinetic experiments revealed its high catalytic CuAAC activity in organic solvents at room temperature. The activity increases upon addition of acetic acid, particularly for more acidic alkyne substrates. The modular catalyst design renders possible the exchange of N-heterocyclic carbene, linker, sacrificial ligand, and counter ion. PMID:27559407

  8. Nonactivated and Activated Biochar Derived from Bananas as Alternative Cathode Catalyst in Microbial Fuel Cells

    PubMed Central

    Yuan, Haoran; Deng, Lifang; Qi, Yujie; Kobayashi, Noriyuki; Tang, Jiahuan

    2014-01-01

    Nonactivated and activated biochars have been successfully prepared by bananas at different thermotreatment temperatures. The activated biochar generated at 900°C (Biochar-act900) exhibited improved oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performances in alkaline media, in terms of the onset potential and generated current density. Rotating disk electron result shows that the average of 2.65 electrons per oxygen molecule was transferred during ORR of Biochar-act900. The highest power density of 528.2 mW/m2 and the maximum stable voltage of 0.47 V were obtained by employing Biochar-act900 as cathode catalyst, which is comparable to the Pt/C cathode. Owning to these advantages, it is expected that the banana-derived biochar cathode can find application in microbial fuel cell systems. PMID:25243229

  9. Nonactivated and activated biochar derived from bananas as alternative cathode catalyst in microbial fuel cells.

    PubMed

    Yuan, Haoran; Deng, Lifang; Qi, Yujie; Kobayashi, Noriyuki; Tang, Jiahuan

    2014-01-01

    Nonactivated and activated biochars have been successfully prepared by bananas at different thermotreatment temperatures. The activated biochar generated at 900°C (Biochar-act900) exhibited improved oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performances in alkaline media, in terms of the onset potential and generated current density. Rotating disk electron result shows that the average of 2.65 electrons per oxygen molecule was transferred during ORR of Biochar-act900. The highest power density of 528.2 mW/m(2) and the maximum stable voltage of 0.47 V were obtained by employing Biochar-act900 as cathode catalyst, which is comparable to the Pt/C cathode. Owning to these advantages, it is expected that the banana-derived biochar cathode can find application in microbial fuel cell systems.

  10. Methane-induced Activation Mechanism of Fused Ferric Oxide-Alumina Catalysts during Methane Decomposition.

    PubMed

    Reddy Enakonda, Linga; Zhou, Lu; Saih, Youssef; Ould-Chikh, Samy; Lopatin, Sergei; Gary, Daniel; Del-Gallo, Pascal; Basset, Jean-Marie

    2016-08-01

    Activation of Fe2 O3 -Al2 O3 with CH4 (instead of H2 ) is a meaningful method to achieve catalytic methane decomposition (CMD). This reaction of CMD is more economic and simple against commercial methane steam reforming (MSR) as it produces COx -free H2 . In this study, for the first time, structure changes of the catalyst were screened during CH4 reduction with time on stream. The aim was to optimize the pretreatment conditions through understanding the activation mechanism. Based on results from various characterization techniques, reduction of Fe2 O3 by CH4 proceeds in three steps: Fe2 O3 →Fe3 O4 →FeO→Fe0. Once Fe0 is formed, it decomposes CH4 with formation of Fe3 C, which is the crucial initiation step in the CMD process to initiate formation of multiwall carbon nanotubes. PMID:27345621

  11. Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

    PubMed Central

    Schöffler, Anne L; Makarem, Ata; Rominger, Frank

    2016-01-01

    Summary A dinuclear N-heterocyclic carbene (NHC) copper complex efficiently catalyzes azide–alkyne cycloaddition (CuAAC) “click” reactions. The ancillary ligand comprises two 4,5-dimethyl-1,3-thiazol-2-ylidene units and an ethylene linker. The three-step preparation of the complex from commercially available starting compounds is more straightforward and cost-efficient than that of the previously described 1,2,4-triazol-5-ylidene derivatives. Kinetic experiments revealed its high catalytic CuAAC activity in organic solvents at room temperature. The activity increases upon addition of acetic acid, particularly for more acidic alkyne substrates. The modular catalyst design renders possible the exchange of N-heterocyclic carbene, linker, sacrificial ligand, and counter ion. PMID:27559407

  12. Pt-Co Bimetallic Catalyst Supported on Single Walled Carbon Nanotube: XAS and Aqueous Phase Reforming Activity Studies

    SciTech Connect

    Wang, X.; Li, N; Pfefferle, L; Haller, G

    2009-01-01

    We have developed a simple method to create a catalyst with atomically dispersed Pt on top of Co nanoparticles on single walled carbon nanotubes (SWNT) supports by sequential impregnation of Pt(II) and Co(II) solutions following by hydrogen reduction. The aqueous phase reforming activity is much higher than for Pt monometallic catalysts on SWNT supports prepared by several methods, either pre-reduced in hydrogen or in the liquid phase. The high selectivity of the monometallic catalysts is maintained for the bimetallic systems. The Extended X-ray Absorption Fine Structure (EXAFS) results at the Pt LIII edge show no observable Pt-Pt bond. Only Pt-Co bonds were observed, indicating high dispersion of Pt. The enhanced activity comes from two sources: the high dispersion of Pt and the effect of the Co as co-catalyst or modifier. This contribution demonstrates the possibility to further engineer bimetallic catalysts to improve the aqueous phase reforming activity, especially to retain good selectivity at high conversion.

  13. Enhancing low-temperature activity and durability of Pd-based diesel oxidation catalysts using ZrO2 supports

    DOE PAGES

    Kim, Mi -Young; Kyriakidou, Eleni A.; Choi, Jae -Soon; Toops, Todd J.; Binder, Andrew J.; Thomas, Cyril; Schwartz, Viviane; Chen, Jihua; Hensley, Dale K.; Parks, II, James E.

    2016-01-18

    In this study, we investigated the impact of ZrO2 on the performance of palladium-based oxidation catalysts with respect to low-temperature activity, hydrothermal stability, and sulfur tolerance. Pd supported on ZrO2 and SiO2 were synthesized for a comparative study. Additionally, in an attempt to maximize the ZrO2 surface area and improve sulfur tolerance, a Pd support with ZrO2-dispersed onto SiO2 was studied. The physicochemical properties of the catalysts were examined using ICP, N2 sorption, XRD, SEM, TEM, and NH3-, CO2-, and NOx-TPD. The activity of the Pd catalysts were measured from 60 to 600 °C in a flow of 4000 ppmmore » CO, 500 ppm NO, 1000 ppm C3H6, 4% O2, 5% H2O, and Ar balance. The Pd catalysts were evaluated in fresh, sulfated, and hydrothermally aged states. Overall, the ZrO2-containing catalysts showed considerably higher CO and C3H6 oxidation activity than Pd/SiO2 under the reaction conditions studied.« less

  14. Subnanometer platinum clusters highly active and selective catalysts for the oxidative dehydrogenation of propane.

    SciTech Connect

    Vajda, S; Pellin, M. J.; Greeley, J. P.; Marshall, C. L.; Curtiss, L. A.; Ballentine, G. A.; Elam, J. W.; Catillon-Mucherie, S.; Redfern, P. C.; Mehmood, F.; Zapol, P.; Yale Univ.

    2009-03-01

    Small clusters are known to possess reactivity not observed in their bulk analogues, which can make them attractive for catalysis. Their distinct catalytic properties are often hypothesized to result from the large fraction of under-coordinated surface atoms. Here, we show that size-preselected Pt{sub 8-10} clusters stabilized on high-surface-area supports are 40-100 times more active for the oxidative dehydrogenation of propane than previously studied platinum and vanadia catalysts, while at the same time maintaining high selectivity towards formation of propylene over by-products. Quantum chemical calculations indicate that under-coordination of the Pt atoms in the clusters is responsible for the surprisingly high reactivity compared with extended surfaces. We anticipate that these results will form the basis for development of a new class of catalysts by providing a route to bond-specific chemistry, ranging from energy-efficient and environmentally friendly synthesis strategies to the replacement of petrochemical feedstocks by abundant small alkanes.

  15. Factors affecting activated carbon-based catalysts for selective hydrogen sulfide oxidation

    SciTech Connect

    Li, Huixing; Monnell, J.D.; Alvin, M.A.; Vidic, R.D.

    2008-09-01

    The primary product of coal gasification processes is synthesis gas (syngas), a mixture of CO, H2, CO2, H2O and a number of minor components. Among the most significant minor components in syngas is hydrogen sulfide (H2S). In addition to its adverse environmental impact, H2S poisons the catalysts and hydrogen purification membranes, and causes severe corrosion in gas turbines. Technologies that can remove H2S from syngas and related process streams are, therefore, of considerable practical interest. To meet this need, we work towards understanding the mechanism by which prospective H2S catalysts perform in simulated fuel gas conditions. Specifically, we show that for low-temperature gas clean-up (~1408C) using activated carbon fibers and water plays a significant role in H2S binding and helps to prolong the lifetime of the material. Basic surface functional groups were found to be imperative for significant conversion of H2S to daughter compounds, whereas metal oxides (La and Ce) did little to enhance this catalysis. We show that although thermal regeneration of the material is possible, the regenerated material has a substantially lower catalytic and sorption capacity.

  16. The active site of low-temperature methane hydroxylation in iron-containing zeolites.

    PubMed

    Snyder, Benjamin E R; Vanelderen, Pieter; Bols, Max L; Hallaert, Simon D; Böttger, Lars H; Ungur, Liviu; Pierloot, Kristine; Schoonheydt, Robert A; Sels, Bert F; Solomon, Edward I

    2016-08-18

    An efficient catalytic process for converting methane into methanol could have far-reaching economic implications. Iron-containing zeolites (microporous aluminosilicate minerals) are noteworthy in this regard, having an outstanding ability to hydroxylate methane rapidly at room temperature to form methanol. Reactivity occurs at an extra-lattice active site called α-Fe(ii), which is activated by nitrous oxide to form the reactive intermediate α-O; however, despite nearly three decades of research, the nature of the active site and the factors determining its exceptional reactivity are unclear. The main difficulty is that the reactive species-α-Fe(ii) and α-O-are challenging to probe spectroscopically: data from bulk techniques such as X-ray absorption spectroscopy and magnetic susceptibility are complicated by contributions from inactive 'spectator' iron. Here we show that a site-selective spectroscopic method regularly used in bioinorganic chemistry can overcome this problem. Magnetic circular dichroism reveals α-Fe(ii) to be a mononuclear, high-spin, square planar Fe(ii) site, while the reactive intermediate, α-O, is a mononuclear, high-spin Fe(iv)=O species, whose exceptional reactivity derives from a constrained coordination geometry enforced by the zeolite lattice. These findings illustrate the value of our approach to exploring active sites in heterogeneous systems. The results also suggest that using matrix constraints to activate metal sites for function-producing what is known in the context of metalloenzymes as an 'entatic' state-might be a useful way to tune the activity of heterogeneous catalysts. PMID:27535535

  17. The active site of low-temperature methane hydroxylation in iron-containing zeolites

    NASA Astrophysics Data System (ADS)

    Snyder, Benjamin E. R.; Vanelderen, Pieter; Bols, Max L.; Hallaert, Simon D.; Böttger, Lars H.; Ungur, Liviu; Pierloot, Kristine; Schoonheydt, Robert A.; Sels, Bert F.; Solomon, Edward I.

    2016-08-01

    An efficient catalytic process for converting methane into methanol could have far-reaching economic implications. Iron-containing zeolites (microporous aluminosilicate minerals) are noteworthy in this regard, having an outstanding ability to hydroxylate methane rapidly at room temperature to form methanol. Reactivity occurs at an extra-lattice active site called α-Fe(II), which is activated by nitrous oxide to form the reactive intermediate α-O; however, despite nearly three decades of research, the nature of the active site and the factors determining its exceptional reactivity are unclear. The main difficulty is that the reactive species—α-Fe(II) and α-O—are challenging to probe spectroscopically: data from bulk techniques such as X-ray absorption spectroscopy and magnetic susceptibility are complicated by contributions from inactive ‘spectator’ iron. Here we show that a site-selective spectroscopic method regularly used in bioinorganic chemistry can overcome this problem. Magnetic circular dichroism reveals α-Fe(II) to be a mononuclear, high-spin, square planar Fe(II) site, while the reactive intermediate, α-O, is a mononuclear, high-spin Fe(IV)=O species, whose exceptional reactivity derives from a constrained coordination geometry enforced by the zeolite lattice. These findings illustrate the value of our approach to exploring active sites in heterogeneous systems. The results also suggest that using matrix constraints to activate metal sites for function—producing what is known in the context of metalloenzymes as an ‘entatic’ state—might be a useful way to tune the activity of heterogeneous catalysts.

  18. SABER: A computational method for identifying active sites for new reactions

    PubMed Central

    Nosrati, Geoffrey R; Houk, K N

    2012-01-01

    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. PMID:22492397

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

    PubMed

    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. PMID:22492397

  20. Selectivity, activity, and metal-support interactions of Rh bimetallic catalysts. Progress report, 15 November 1981-15 August 1982

    SciTech Connect

    Haller, G L

    1982-08-01

    We report on a detailed investigation of the effect of TiO/sub 2/ support on Rh-Ag interaction as exhibited in catalytic activity. The temporal evolution of activity over Rh-Ag/TiO/sub 2/ for ethane hydrogenolysis and hydrogen chemisorption as a function of temperature, Ag to Rh ratio, the Rh particle size, Rh loading, and ambient gas were studied. Preliminary extended x-ray absorption fine structure (EXAFS) analysis of Rh/TiO/sub 2/ catalysts indicate that 100% exposed (dispersed) catalyst prepared by ion exchange may be atomically dispersed after low temperature reduction. 7 figures, 1 table.

  1. Catalyst by Design

    SciTech Connect

    Narula, Chaitanya Kumar; DeBusk, Melanie Moses

    2014-01-01

    The development of new catalytic materials is still dominated by trial and error methods. Although it has been successful, the empirical development of catalytic materials is time consuming and expensive with no guarantee of success. In our laboratories, we are developing a comprehensive catalysts by design that involves state-of-the-art first principle density functional theory calculations, experimental design of catalyst sites, and sub- ngstr m resolution imaging with an aberration-corrected electron microscope to characterize the microstructure. In this chapter, we focus on supported platinum cluster catalyst systems which are one of the most important industrial catalysts and attempt to demonstrate the feasibility of the catalyst by design concept.

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

    PubMed

    Hansen, Martin H; Stern, Lucas-Alexandre; Feng, Ligang; Rossmeisl, Jan; Hu, Xile

    2015-04-28

    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 (101̅0), (1̅1̅20), (112̅0), (112̅1) and (0001) facets of the hexagonal Ni2P crystal. In addition to the DFT results, we present experiments on Ni2P nanowires growing along the 〈0001〉 direction, which are shown as efficient hydrogen evolution catalysts. The experimental results add these nanowires to a variety of different morphologies of Ni2P, which are all active for HER. PMID:25812670

  3. The active site of ribulose-bisphosphate carboxylase/oxygenase

    SciTech Connect

    Hartman, F.C.

    1991-01-01

    The active site of ribulose-bisphosphate carboxylase/oxygenase requires interacting domains of adjacent, identical subunits. Most active-site residues are located within the loop regions of an eight-stranded {beta}/{alpha}-barrel which constitutes the larger C-terminal domain; additional key residues are located within a segment of the smaller N-terminal domain which partially covers the mouth of the barrel. Site-directed mutagenesis of the gene encoding the enzyme from Rhodospirillum rubrum has been used to delineate functions of active-site residues. 6 refs., 2 figs.

  4. Controlled leaching with prolonged activity for Co-LDH supported catalyst during treatment of organic dyes using bicarbonate activation of hydrogen peroxide.

    PubMed

    Jawad, Ali; Li, Yibing; Lu, Xiaoyan; Chen, Zhuqi; Liu, Weidong; Yin, Guochuan

    2015-05-30

    The effluents from industries are commonly non-biodegradable and produce various hazardous intermediate products by chemical reactions that have direct impact on environment. In the present investigation, a series of Co-Mg/AL ternary LDH catalysts with fixed Mg/Al ratio were prepared by co-precipitation method. The effect of Co on the activity of the catalyst was monitored on the degradation of methylene blue (MB) as model compound at batch level using bicarbonate activation of H2O2 (BAP) system. On bench level, the best CoMgAl-4 catalyst can completely decolorize both methylene blue (MB) and methylene orange (MO) in short time, while in fixed bed, the catalyst was found stable for over 300 h with nearly 100% decolorization and excellent chemical oxygen demand (COD) removal. No leaching of Co was detected for the entire fixed experiment which may be accounted for long life stability and good activity of the catalyst. The ternary LDH catalysts were characterized by AES, XRD, FTIR, BET, and SEM for its compositional, phase structure, optical properties, textural, and surface morphology respectively. The XRD analysis confirmed characteristic pattern of hydrotalcite like structures without impurity phases. The formation of superoxide and hydroxyl radical as ROS was proposed with CoMgAl-4 by radical's scavengers.

  5. Savannah River Site prioritization of transition activities

    SciTech Connect

    Finley, R.H.

    1993-11-01

    Effective management of SRS conversion from primarily a production facility to other missions (or Decontamination and Decommissioning (D&D)) requires a systematic and consistent method of prioritizing the transition activities. This report discusses the design of a prioritizing method developed to achieve systematic and consistent methods of prioritizing these activities.

  6. DOE site performance assessment activities. Radioactive Waste Technical Support Program

    SciTech Connect

    Not Available

    1990-07-01

    Information on performance assessment capabilities and activities was collected from eight DOE sites. All eight sites either currently dispose of low-level radioactive waste (LLW) or plan to dispose of LLW in the near future. A survey questionnaire was developed and sent to key individuals involved in DOE Order 5820.2A performance assessment activities at each site. The sites surveyed included: Hanford Site (Hanford), Idaho National Engineering Laboratory (INEL), Los Alamos National Laboratory (LANL), Nevada Test Site (NTS), Oak Ridge National Laboratory (ORNL), Paducah Gaseous Diffusion Plant (Paducah), Portsmouth Gaseous Diffusion Plant (Portsmouth), and Savannah River Site (SRS). The questionnaire addressed all aspects of the performance assessment process; from waste source term to dose conversion factors. This report presents the information developed from the site questionnaire and provides a comparison of site-specific performance assessment approaches, data needs, and ongoing and planned activities. All sites are engaged in completing the radioactive waste disposal facility performance assessment required by DOE Order 5820.2A. Each site has achieved various degrees of progress and have identified a set of critical needs. Within several areas, however, the sites identified common needs and questions.

  7. Safety Oversight of Decommissioning Activities at DOE Nuclear Sites

    SciTech Connect

    Zull, Lawrence M.; Yeniscavich, William

    2008-01-15

    The Defense Nuclear Facilities Safety Board (Board) is an independent federal agency established by Congress in 1988 to provide nuclear safety oversight of activities at U.S. Department of Energy (DOE) defense nuclear facilities. The activities under the Board's jurisdiction include the design, construction, startup, operation, and decommissioning of defense nuclear facilities at DOE sites. This paper reviews the Board's safety oversight of decommissioning activities at DOE sites, identifies the safety problems observed, and discusses Board initiatives to improve the safety of decommissioning activities at DOE sites. The decommissioning of former defense nuclear facilities has reduced the risk of radioactive material contamination and exposure to the public and site workers. In general, efforts to perform decommissioning work at DOE defense nuclear sites have been successful, and contractors performing decommissioning work have a good safety record. Decommissioning activities have recently been completed at sites identified for closure, including the Rocky Flats Environmental Technology Site, the Fernald Closure Project, and the Miamisburg Closure Project (the Mound site). The Rocky Flats and Fernald sites, which produced plutonium parts and uranium materials for defense needs (respectively), have been turned into wildlife refuges. The Mound site, which performed R and D activities on nuclear materials, has been converted into an industrial and technology park called the Mound Advanced Technology Center. The DOE Office of Legacy Management is responsible for the long term stewardship of these former EM sites. The Board has reviewed many decommissioning activities, and noted that there are valuable lessons learned that can benefit both DOE and the contractor. As part of its ongoing safety oversight responsibilities, the Board and its staff will continue to review the safety of DOE and contractor decommissioning activities at DOE defense nuclear sites.

  8. Gasification characteristics of an activated carbon catalyst during the decomposition of hazardous waste material in supercritical water

    SciTech Connect

    Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

    1996-12-31

    Recently, carbonaceous materials including activated carbon were proven to be effective catalysts for hazardous waste gasification in supercritical water. Using coconut shell activated carbon catalyst, complete decomposition of industrial organic wastes including methanol and acetic acid was achieved. During this process, the total mass of the activated carbon catalyst changes by two competing processes: a decrease in weight via gasification of the carbon by supercritical water, or an increase in weight by deposition of carbonaceous materials generated by incomplete gasification of the biomass feedstocks. The deposition of carbonaceous materials does not occur when complete gasification is realized. Gasification of the activated carbon in supercritical water is often favored, resulting in changes in the quality and quantity of the catalyst. To thoroughly understand the hazardous waste decomposition process, a more complete understanding of the behavior of activated carbon in pure supercritical water is needed. The gasification rate of carbon by water vapor at subcritical pressures was studied in relation to coal gasification and generating activated carbon.

  9. Electron donor properties of claus catalysts--1. Influence of NaOH on the catalytic activity of silica gel

    SciTech Connect

    Dudzik, Z.; George, Z.M.

    1980-05-01

    ESR spectroscopy showed that SO/sub 2/ adsorbed on silica gel impregnated with NaOH formed the SO/sub 2//sup -/ anion radical. With increasing NaOH concentration, the SO/sub 2/ adsorption and the activity for the reaction of H/sub 2/S with SO/sub 2/ (Claus reaction) went through a maximum at 1.0-1.4% NaOH. The SO/sub 2/ anion radical apparently formed by electron transfer from the catalyst surface and was a reaction intermediate which reacted rapidly with H/sub 2/S. The NaOH catalyst had similar stability and activity as commercial alumina catalyst in five-day tests under Claus conditions.

  10. Gasification characteristics of an activated carbon catalyst during the decomposition of hazardous waste materials in supercritical water

    SciTech Connect

    Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

    1996-10-01

    Recently, carbonaceous materials were proved to be effective catalysts for hazardous waste decomposition in supercritical water. Gasification of the carbonaceous catalyst itself is also expected, however, under supercritical conditions. Thus, it is essential to determine the gasification rate of the carbonaceous materials during this process to determine the active lifetime of the catalysts. For this purpose, the gasification characteristics of granular coconut shell activated carbon in supercritical water alone (600-650{degrees}C, 25.5-34.5 MPa) were investigated. The gasification rate at subatmospheric pressure agreed well with the gasification rate at supercritical conditions, indicating the same reaction mechanism. Methane generation under these conditions is via pyrolysis, and thus is not affected by the water pressure. An iodine number increase of 25% was observed as a result of the supercritical water gasification.

  11. Photoinduced Stepwise Oxidative Activation of a Chromophore–Catalyst Assembly on TiO2

    SciTech Connect

    Song, Wenjing; Glasson, Christopher R. K.; Luo, Hanlin; Hanson, Kenneth G.; Brennaman, Kyle M.; Concepcion, Javier J.; Meyer, Thomas J.

    2011-07-08

    To probe light-induced redox equivalent separation and accumulation, we prepared ruthenium polypyridyl molecular assembly [(dcb)2Ru(bpy-Mebim2py)Ru(bpy)(OH2)]4+ (RuaII–RubII–OH2) with Rua as light-harvesting chromophore and Rub as water oxidation catalyst (dcb = 4,4'-dicarboxylic acid-2,2'-bipyridine; bpy-Mebim2py = 2,2'-(4-methyl-[2,2':4',4''-terpyridine]-2'',6''-diyl)bis(1-methyl-1H-benzo[d]imidazole); bpy = 2,2'-bipyridine). When bound to TiO2 in nanoparticle films, it undergoes MLCT excitation, electron injection, and oxidation of the remote -RubII–OH2 site to give TiO2(e–)–RuaII–RubIII–OH23+ as a redox-separated transient. The oxidized assembly, TiO2–RuaII–RubIII–OH23+, similarly undergoes excitation and electron injection to give TiO2(e–)–RuaII–RubIV=O2+, with RubIV=O2+ a known water oxidation catalyst precursor. Injection efficiencies for both forms of the assembly are lower than those for [Ru(bpy)2(4,4'-(PO3H2)2bpy)]2+ bound to TiO2 (TiO2–Ru2+), whereas the rates of back electron transfer, TiO2(e–) → RubIII–OH23+ and TiO2(e–) → RubIV=O2+, are significantly decreased compared with TiO2(e–) → Ru3+ back electron transfer.

  12. Preliminary results from screening tests of commercial catalysts with potential use in gas turbine combustors. I - Furnace studies of catalyst activity

    NASA Technical Reports Server (NTRS)

    Anderson, D. N.

    1976-01-01

    Thirty commercially produced monolith and pellet catalysts were tested as part of a screening process to select catalysts suitable for use in a gas turbine combustor. The catalysts were contained in a 1.8 centimeter diameter quartz tube and heated to temperatures varying between 300 and 1200 K while a mixture of propane and air passed through the bed at space velocities of 44,000 to 70,000 per hour. The amount of propane oxidized was measured as a function of catalyst temperature. Of the samples tested, the most effective catalysts proved to be noble metal catalysts on monolith substrates.

  13. Preliminary results from screening tests of commercial catalysts with potential use in gas turbine combustors. Part 1: Furnace studies of catalyst activity

    NASA Technical Reports Server (NTRS)

    Anderson, D. N.

    1976-01-01

    Thirty commercially produced monolith and pellet catalysts were tested as part of a screening process to select catalysts suitable for use in a gas turbine combustor. The catalysts were contained in a 1.8 centimeter diameter quartz tube and heated to temperatures varying between 300 and 1,200 K while a mixture of propane and air passed through the bed at space velocities of 44,000 to 70,000/hour. The amount of propane oxidized was measured as a function of catalyst temperature. Of the samples tested, the most effective catalysts proved to be noble metal catalysts on monolith substrates.

  14. Mutations of fumarase that distinguish between the active site and a nearby dicarboxylic acid binding site.

    PubMed Central

    Weaver, T.; Lees, M.; Banaszak, L.

    1997-01-01

    Two mutant forms of fumarase C from E. coli have been made using PCR and recombinant DNA. The recombinant form of the protein included a histidine arm on the C-terminal facilitating purification. Based on earlier studies, two different carboxylic acid binding sites, labeled A- and B-, were observed in crystal structures of the wild type and inhibited forms of the enzyme. A histidine at each of the sites was mutated to an asparagine. H188N at the A-site resulted in a large decrease in specific activity, while the H129N mutation at the B-site had essentially no effect. From the results, we conclude that the A-site is indeed the active site, and a dual role for H188 as a potential catalytic base is proposed. Crystal structures of the two mutant proteins produced some unexpected results. Both mutations reduced the affinity for the carboxylic acids at their respective sites. The H129N mutant should be particularly useful in future kinetic studies because it sterically blocks the B-site with the carboxyamide of asparagine assuming the position of the ligand's carboxylate. In the H188N mutation at the active site, the new asparagine side chain still interacts with an active site water that appears to have moved slightly as a result of the mutation. PMID:9098893

  15. Redox properties and VOC oxidation activity of Cu catalysts supported on Ce₁-xSmxOδ mixed oxides.

    PubMed

    Konsolakis, Michalis; Carabineiro, Sónia A C; Tavares, Pedro B; Figueiredo, José L

    2013-10-15

    A series of Cu catalysts supported on Ce1-xSmxOδ mixed oxides with different molar contents (x=0, 0.25, 0.5, 0.75 and 1), was prepared by wet impregnation and evaluated for volatile organic compounds (VOC) abatement, employing ethyl acetate as model molecule. An extensive characterization study was undertaken in order to correlate the morphological, structural and surface properties of catalysts with their oxidation activity. The optimum performance was obtained with Cu/CeO2 catalyst, which offers complete conversion of ethyl acetate into CO2 at temperatures as low as 260°C. The catalytic performance of Cu/Ce1-xSmxOδ was interpreted on the basis of characterization studies, showing that incorporation of samarium in ceria has a detrimental effect on the textural characteristics and reducibility of catalysts. Moreover, high Sm/Ce atomic ratios (from 1 to 3) resulted in a more reduced copper species, compared to CeO2-rich supports, suggesting the inability of these species to take part in the redox mechanism of VOC abatement. Sm/Ce surface atomic ratios are always much higher than the nominal ratios indicating an impoverishment of catalyst surface in cerium oxide, which is detrimental for VOC activity. PMID:23995554

  16. Fe3-xCuxO4 as highly active heterogeneous Fenton-like catalysts toward elemental mercury removal.

    PubMed

    Zhou, Changsong; Sun, Lushi; Zhang, Anchao; Wu, Xiaofeng; Ma, Chuan; Su, Sheng; Hu, Song; Xiang, Jun

    2015-04-01

    A series of novel spinel Fe3-xCuxO4 (0active heterogeneous Fenton-like catalysts to remove elemental mercury (Hg0) from the simulated flue gases. Inductively coupled plasma-Atomic emission spectrometry (ICP-AES), X-ray diffraction patterns (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area, and X-ray photoelectron spectrometer (XPS) were used to characterize the catalysts. The catalysts were confirmed the presence of the redox pairs Fesurf2+/Fesurf3+ and Cusurf+/Cusurf2+ on the surface of the cubic structure. The performance of heterogeneous Fenton-like reactions for Hg0 removal was evaluated in a lab-scale bubbling reactor at the solution temperature of 50°C. The systematic studies on the effects of different catalysts, H2O2 concentration and solution pH values on Hg0 removal efficiencies were performed. The recycling of the Fe3-xCuxO4 catalysts in Fenton-like solution is stable and Hg0 removal efficiency remain above 90% after 3 cycles. The active hydroxyl radical (OH) generated during heterogeneous Fenton-like reactions was confirmed through electron spin resonance (ESR) spin-trapping technique. The Hg0 removal mechanism has been discussed based on the experimental and analytical results. PMID:25655441

  17. Noble metal ionic catalysts.

    PubMed

    Hegde, M S; Madras, Giridhar; Patil, K C

    2009-06-16

    Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NO(x), and unburned hydrocarbons-need to be fully converted to CO(2), N(2), and H(2)O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al(2)O(3) or SiO(2) promoted by CeO(2). However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce(1-x)M(x)O(2-delta) and Ce(1-x-y)Ti(y)M(x)O(2-delta) (M = Pt, Pd, Rh; x = 0.01-0.02, delta approximately x, y = 0.15-0.25) oxides in fluorite structure. In these oxide catalysts, Pt(2+), Pd(2+), or Rh(3+) ions are substituted only to the extent of 1-2% of Ce(4+) ion. Lower-valent noble metal ion substitution in CeO(2) creates oxygen vacancies. Reducing molecules (CO, H(2), NH(3)) are adsorbed onto electron-deficient noble metal ions, while oxidizing (O(2), NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NO(x) reduction (with >80% N(2) selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO(2) or Ce(1-x)Ti(x)O(2) were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the

  18. Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

    SciTech Connect

    Wang, Yanggang; Mei, Donghai; Glezakou, Vassiliki Alexandra; Li, Jun; Rousseau, Roger J.

    2015-03-04

    Ab initio Molecular Dynamics simulations and static Density Functional Theory calculations have been performed to investigate the reaction mechanism of CO oxidation on Au/CeO2 catalyst. It is found that under reaction condition CO adsorption significantly labializes the surface atoms of the Au cluster and leads to the formation of isolated Au+-CO species that resides on the support in the vicinity of the Au particle. In this context, we identified a dynamic single-atom catalytic mechanism at the interfacial area for CO oxidation on Au/CeO2 catalyst, which is a lower energy pathway than that of CO oxidation at the interface with the metal particle. This results from the ability of the single atom site to strongly couple with the redox properties of the support in a synergistic manner thereby lowering the barrier for redox reactions. We find that the single Au+ ion, which only exists under reaction conditions, breaks away from the Au cluster to catalyze CO oxidation and returns to the Au cluster after the catalytic cycle is completed. Generally, our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in a catalytic process.

  19. Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

    DOE PAGES

    Wang, Yanggang; Mei, Donghai; Glezakou, Vassiliki Alexandra; Li, Jun; Rousseau, Roger J.

    2015-03-04

    Ab initio Molecular Dynamics simulations and static Density Functional Theory calculations have been performed to investigate the reaction mechanism of CO oxidation on Au/CeO2 catalyst. It is found that under reaction condition CO adsorption significantly labializes the surface atoms of the Au cluster and leads to the formation of isolated Au+-CO species that resides on the support in the vicinity of the Au particle. In this context, we identified a dynamic single-atom catalytic mechanism at the interfacial area for CO oxidation on Au/CeO2 catalyst, which is a lower energy pathway than that of CO oxidation at the interface with themore » metal particle. This results from the ability of the single atom site to strongly couple with the redox properties of the support in a synergistic manner thereby lowering the barrier for redox reactions. We find that the single Au+ ion, which only exists under reaction conditions, breaks away from the Au cluster to catalyze CO oxidation and returns to the Au cluster after the catalytic cycle is completed. Generally, our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in a catalytic process.« less

  20. Ionizable Side Chains at Catalytic Active Sites of Enzymes

    PubMed Central

    Jimenez-Morales, David; Liang, Jie

    2012-01-01

    Catalytic active sites of enzymes of known structure can be well defined by a modern program of computational geometry. The CASTp program was used to define and measure the volume of the catalytic active sites of 573 enzymes in the Catalytic Site Atlas database. The active sites are identified as catalytic because the amino acids they contain are known to participate in the chemical reaction catalyzed by the enzyme. Acid and base side chains are reliable markers of catalytic active sites. The catalytic active sites have 4 acid and 5 base side chains, in an average volume of 1072 Å3. The number density of acid side chains is 8.3 M (in chemical units); the number density of basic side chains is 10.6 M. The catalytic active site of these enzymes is an unusual electrostatic and steric environment in which side chains and reactants are crowded together in a mixture more like an ionic liquid than an ideal infinitely dilute solution. The electrostatics and crowding of reactants and side chains seems likely to be important for catalytic function. In three types of analogous ion channels, simulation of crowded charges accounts for the main properties of selectivity measured in a wide range of solutions and concentrations. It seems wise to use mathematics designed to study interacting complex fluids when making models of the catalytic active sites of enzymes. PMID:22484856

  1. Low Cost Autothermal Diesel Reforming Catalyst Development

    SciTech Connect

    Shihadeh, J.; Liu, D.

    2004-01-01

    Catalytic autothermal reforming (ATR) represents an important step of converting fossil fuel to hydrogen rich reformate for use in solid oxide fuel cell (SOFC) stacks. The state-of-the-art reforming catalyst, at present, is a Rh based material which is effective but costly. The objective of our current research is to reduce the catalyst cost by finding an efficient ATR catalyst containing no rhodium. A group of perovskite based catalysts have been synthesized and evaluated under the reforming condition of a diesel surrogate fuel. Hydrogen yield, reforming efficiency, and conversion selectivity to carbon oxides of the catalyst ATR reaction are calculated and compared with the benchmark Rh based material. Several catalyst synthesis improvements were carried out including: 1) selectively doping metals on the A-site and B-site of the perovskite structure, 2) changing the support from perovskite to alumina, 3) altering the method of metal addition, and 4) using transition metals instead of noble metals. It was found that the catalytic activity changed little with modification of the A-site metal, while it displayed considerable dependence on the B-site metal. Perovskite supports performed much better than alumina based supports.

  2. Periodic trends in the hydrodenitrogenation activity of carbon-supported transition metal sulfide catalysts

    SciTech Connect

    Eijsbouts, S.; De Beer, V.H.J.; Prins, R.

    1988-01-01

    Periodic trends of transition metals for the catalysis of reactions such as hydrogenation, hydrogenolysis, isomerization and hydrogen oxidation have been well studied. When activity versus position of the transition metal in the periodic table is plotted, quite often these trends are manifested in the form of so-called volcano-type curves. In the present study, the authors have chosen the HDN of quinoline at moderately high pressure as a model reaction, and they have used the same carbon-supported transition metal sulfide catalysts studied by Vissers et al. Results are shown for the following transition metals: V, Cr, Mn, Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, and Pt. 9 references.

  3. The active component of vanadium-molybdenum catalysts for the oxidation of acrolein to acrylic acid

    SciTech Connect

    Andrushkevich, T.V.; Kuznetsova, T.G.

    1986-12-01

    The catalytic properties of the vanadium-molybdenum oxide system were investigated in the oxidation of acrolein to acrylic acid. The active component of the catalyst is the compound VMo/sub 3/O/sub 11/, the maximum amount of which is observed at a content of 7-15 mole% V/sub 2/O/sub 4/. The compound VMo/sub 3/O/sub 11/ is formed in the thermodecomposition of silicomolybdovanadium heteropoly acids or isopoly compounds, reduced with respect to vanadium, and contains V/sup 4 +/ and Mo/sup 6 +/. The optimum treatment for the formation of this compound is treatment in the reaction mixture at 400 degrees C.

  4. Active and Durable Hydrogen Evolution Reaction Catalyst Derived from Pd-Doped Metal-Organic Frameworks.

    PubMed

    Chen, Jitang; Xia, Guoliang; Jiang, Peng; Yang, Yang; Li, Ren; Shi, Ruohong; Su, Jianwei; Chen, Qianwang

    2016-06-01

    The water electrolysis is of critical importance for sustainable hydrogen production. In this work, a highly efficient and stable PdCo alloy catalyst (PdCo@CN) was synthesized by direct annealing of Pd-doped metal-organic frameworks (MOFs) under N2 atmosphere. In 0.5 M H2SO4 solution, PdCo@CN displays remarkable electrocatalytic performance with overpotential of 80 mV, a Tafel slope of 31 mV dec(-1), and excellent stability of 10 000 cycles. Our studies reveal that noble metal doped MOFs are ideal precursors for preparing highly active alloy electrocatalysts with low content of noble metal. PMID:27112733

  5. Oxygen reduction at carbon supported ruthenium-selenium catalysts: Selenium as promoter and stabilizer of catalytic activity

    NASA Astrophysics Data System (ADS)

    Schulenburg, Hendrik; Hilgendorff, Marcus; Dorbandt, Iris; Radnik, Jörg; Bogdanoff, Peter; Fiechter, Sebastian; Bron, Michael; Tributsch, Helmut

    Carbon supported ruthenium-based catalysts (Ru/C) for the oxygen reduction in acid electrolytes were investigated. A treatment of Ru/C catalysts with selenious acid had a beneficial effect on catalytic activity but no influence on intrinsic kinetic properties, like Tafel slope and hydrogen peroxide generation. Reasons for the increased activity of RuSe x/C catalysts are discussed. Potential step measurements suggest that at potentials around 0.8 V (NHE) a selenium or selenium-oxygen species protects the catalyst from formation of inactive RuO 2-films. This protective effect leads to an enhanced activity of RuSe x/C compared to Ru/C. No evidence was found for a catalytically active stoichiometric selenium compound. The active phase may be described as a ruthenium suboxide RuO x (x < 2) layer integrated in a RuSe y phase or RuSe yO v (y < 2, v < 2) layer at the particle surface.

  6. Effect of the detonation nanodiamond surface on the catalytic activity of deposited nickel catalysts in the hydrogenation of acetylene

    NASA Astrophysics Data System (ADS)

    Tveritinova, E. A.; Kulakova, I. I.; Zhitnev, Yu. N.; Kharlanov, A. N.; Fionov, A. V.; Chen, W.; Buyanova, I.; Lunin, V. V.

    2013-07-01

    A comparative study is performed of the catalytic activity of nanosized nickel deposited on detonation synthesis nanodiamond (DND) and coal (CSUG) produced by burning sugar and crystalline quartz in the hydrogenation of acetylene. Nanosized nickel is obtained through the thermal decomposition of nickel formate under a dynamic vacuum. The catalysts are studied by means of scanning electron and transmission electron microscopy, X-ray fluorescence, IR-spectroscopy, X-ray diffraction, and pulse microcatalytic method. It is shown that Ni/DND is an active catalyst of acetylene hydrogenation, considerably surpassing Ni/quartz and Ni/CSUG. The apparent activation energy of the hydrogenation of acetylene is calculated, and the region of the reaction are determined for all catalysts. It is found that the influence of the structure and nature of a functional coating of nanodiamond on the catalytic activity of Ni/DND deposited catalyst in the hydrogenation of acetylene. The ability of Ni/DND to hold active hydrogen is detected.

  7. Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst.

    PubMed

    Cao, Xinrui; Fu, Qiang; Luo, Yi

    2014-05-14

    The single atom alloy of extended surfaces is known to provide remarkably enhanced catalytic performance toward heterogeneous hydrogenation. Here we demonstrate from first principles calculations that this approach can be extended to nanostructures, such as bimetallic nanoparticles. The catalytic properties of the single-Pd-doped Cu55 nanoparticles have been systemically examined for H2 dissociation as well as H atom adsorption and diffusion, following the concept of single atom alloy. It is found that doping a single Pd atom at the edge site of the Cu55 shell can considerably reduce the activation energy of H2 dissociation, while the single Pd atom doped at the top site or in the inner layers is much less effective. The H atom adsorption on Cu55 is slightly stronger than that on the Cu(111) surface; however, a larger nanoparticle that contains 147 atoms could effectively recover the weak binding of the H atoms. We have also investigated the H atom diffusion on the 55-atom nanoparticle and found that spillover of the produced H atoms could be a feasible process due to the low diffusion barriers. Our results have demonstrated that facile H2 dissociation and weak H atom adsorption could be combined at the nanoscale. Moreover, the effects of doping one more Pd atom on the H2 dissociation and H atom adsorption have also been investigated. We have found that both the doping Pd atoms in the most stable configuration could independently exhibit their catalytic activity, behaving as two single-atom-alloy catalysts.

  8. Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst

    PubMed Central

    Oveisi, Ali R.; Zhang, Kainan; Khorramabadi-zad, Ahmad; Farha, Omar K.; Hupp, Joseph T.

    2015-01-01

    A new porphyrin-based porous organic polymer (POP) with BET surface area ranging from 780 to 880 m2/g was synthesized in free-base form via the reaction of meso-tetrakis(pentafluorophenyl) porphyrin and a rigid trigonal building block, hexahydroxytriphenylene. The material was then metallated with Fe(III) imparting activity for Lewis acid catalysis (regioselective methanolysis ring-opening of styrene oxide), oxidative cyclization catalysis (conversion of bis(2-hydroxy-1-naphthyl)methanes to the corresponding spirodienone), and a tandem catalytic processes: an in situ oxidation-cyclic aminal formation-oxidation sequence, which selectively converts benzyl alcohol to 2-phenyl-quinazolin-4(3H)-one. Notably, the catalyst is readily recoverable and reusable, with little loss in catalytic activity. PMID:26177563

  9. Catalyst poisoning during tar-sands bitumen upgrading

    SciTech Connect

    Carruthers, J.D.; Brinen, J.S.; Komar, D.A.; Greenhouse, S.

    1994-12-31

    A number of hydrotreating catalysts are used in commercial heavy oil upgrading facilities. One of these, a CoO/MoO{sub 3}/Al{sub 2}O{sub 3} catalyst has been evaluated in a pilot plant CSTR for Tar-Sands Bitumen upgrading. Following its use in a test of 200 hours duration, the catalyst was removed, de-oiled, regenerated by air-calcination to remove the coke, and then re-tested. Samples of the coked, fresh and regenerated catalyst were each examined using surface analytical techniques. ESCA and SIMS analysis of the coked and regenerated catalyst samples show, as expected, significant contamination of the catalyst with Ni and V. In addition, the SIMS analysis clearly reveals that the edges of the catalyst pellets are rich in Ca, Mg and Fe while the Ni, V and coke are evenly distributed. Regeneration of the catalyst by calcination removes the carbonaceous material but appears not to change the distribution of the metal contaminants. Retesting of the regenerated catalyst shows a performance similar to that of the fresh catalyst. These data serve to support the view that catalyst deactivation during early use is not due to the skin of Ca and Mg on the pellets but rather via the poisoning of active sites by carbonaceous species.

  10. Molecular dynamics explorations of active site structure in designed and evolved enzymes.

    PubMed

    Osuna, Sílvia; Jiménez-Osés, Gonzalo; Noey, Elizabeth L; Houk, K N

    2015-04-21

    This Account describes the use of molecular dynamics (MD) simulations to reveal how mutations alter the structure and organization of enzyme active sites. As proposed by Pauling about 70 years ago and elaborated by many others since then, biocatalysis is efficient when functional groups in the active site of an enzyme are in optimal positions for transition state stabilization. Changes in mechanism and covalent interactions are often critical parts of enzyme catalysis. We describe our explorations of the dynamical preorganization of active sites using MD, studying the fluctuations between active and inactive conformations normally concealed to static crystallography. MD shows how the various arrangements of active site residues influence the free energy of the transition state and relates the populations of the catalytic conformational ensemble to the enzyme activity. This Account is organized around three case studies from our laboratory. We first describe the importance of dynamics in evaluating a series of computationally designed and experimentally evolved enzymes for the Kemp elimination, a popular subject in the enzyme design field. We find that the dynamics of the active site is influenced not only by the original sequence design and subsequent mutations but also by the nature of the ligand present in the active site. In the second example, we show how microsecond MD has been used to uncover the role of remote mutations in the active site dynamics and catalysis of a transesterase, LovD. This enzyme was evolved by Tang at UCLA and Codexis, Inc., and is a useful commercial catalyst for the production of the drug simvastatin. X-ray analysis of inactive and active mutants did not reveal differences in the active sites, but relatively long time scale MD in solution showed that the active site of the wild-type enzyme preorganizes only upon binding of the acyl carrier protein (ACP) that delivers the natural acyl group to the active site. In the absence of bound ACP

  11. An active carbon catalyst prevents coke formation from asphaltenes during the hydrocracking of vacuum residue

    SciTech Connect

    Fukuyama, H.; Terai, S.

    2007-07-01

    Active carbons were prepared by the steam activation of a brown coal char. The active carbon with mesopores showed greater adsorption selectivity for asphaltenes. The active carbon was effective at suppressing coke formation, even with the high hydrocracking conversion of vacuum residue. The analysis of the change in the composition of saturates, aromatics, resins, and asphaltenes in the cracked residue with conversion demonstrated the ability of active carbon to restrict the transformation of asphaltenes to coke. The active carbon that was richer in mesopores was presumably more effective at providing adsorption sites for the hydrocarbon free-radicals generated initially during thermal cracking to prevent them from coupling and polycondensing.

  12. Effect of surface oxidation of the support on the thiophene hydrodesulfurization activity of Mo, Ni, and NiMo catalysts supported on activated carbon

    SciTech Connect

    Calafat, A. |; Lopez-Agudo, A.; Palacios, J.M.

    1996-08-01

    The present investigation attempts to provide a better understanding of the influence of the nature of the carbon support on the HDS activity of Mo, Ni, and NiMo catalysts. For this purpose a high purity activated carbon was subjected to oxidative treatments with HNO{sub 3} to modify its surface properties. NiMo catalysts supported on the resulting activated carbons were prepared and characterized by TPR, XRD, and SEM-EDX, and their activity for HDS of thiophene at 30 bars and 375{degrees}C was evaluated. The results obtained showed that oxidation of the carbon surface does not affect the HDS activity and other characteristics of the supported Mo phase. In contrast, the HDS activity of the Ni catalysts is enhanced by acid treatments of the carbon support. In this case, introduction of oxygen-containing functional groups (O{sub (s)}) leads to a strong interaction of O{sub (s)}-Ni during impregnation, which becomes essential to achieving and preserving high nickel dispersion. This effect on NiMo/C catalysts. The synergistic effect of the bimetallic catalysts is observed only when oxygen functional groups are present on the carbon surface, which are necessary for a good HDS activity, mainly because they enhance Ni-Mo interactions that produce the highly active Ni-Mo-S phase. A NiMoO{sub 4}-like phase formed during impregnation seems to be the precursor for the active sulfide phase over the present NiMo/C catalysts. 34 refs., 6 figs., 5 tabs.

  13. An in-depth understanding of the bimetallic effects and coked carbon species on an active bimetallic Ni(Co)/Al2O3 dry reforming catalyst.

    PubMed

    Liao, Xin; Gerdts, Rihards; Parker, Stewart F; Chi, Lina; Zhao, Yongxiang; Hill, Martyn; Guo, Junqiu; Jones, Martin O; Jiang, Zheng

    2016-06-29

    Ni/Al2O3, Co/Al2O3 and bimetallic Ni(Co)/Al2O3 catalysts were prepared using an impregnation method and employed in CO2 dry reforming of methane under coking-favored conditions. The spent catalysts were carefully characterized using typical characterization technologies and inelastic neutron scattering spectroscopy. The bimetallic catalyst exhibited a superior activity and anti-coking performance compared to Ni/Al2O3, while the most resistant to coking behavior was Co/Al2O3. The enhanced activity of the Ni(Co)/Al2O3 bimetallic catalyst is attributed to the reduced particle size of metallic species and resistance to forming stable filamentous carbon. The overall carbon deposition on the spent bimetallic catalyst is comparable to that of the spent Ni/Al2O3 catalyst, whereas the carbon deposited on the bimetallic catalyst is mainly less-stable carbonaceous species as confirmed by SEM, TPO, Raman and INS characterization. This study provides an in depth understanding of alloy effects in catalysts, the chemical nature of coked carbon on spent Ni-based catalysts and, hopefully, inspires the creative design of a new bimetallic catalyst for dry reforming reactions. PMID:27326792

  14. An in-depth understanding of the bimetallic effects and coked carbon species on an active bimetallic Ni(Co)/Al2O3 dry reforming catalyst.

    PubMed

    Liao, Xin; Gerdts, Rihards; Parker, Stewart F; Chi, Lina; Zhao, Yongxiang; Hill, Martyn; Guo, Junqiu; Jones, Martin O; Jiang, Zheng

    2016-06-29

    Ni/Al2O3, Co/Al2O3 and bimetallic Ni(Co)/Al2O3 catalysts were prepared using an impregnation method and employed in CO2 dry reforming of methane under coking-favored conditions. The spent catalysts were carefully characterized using typical characterization technologies and inelastic neutron scattering spectroscopy. The bimetallic catalyst exhibited a superior activity and anti-coking performance compared to Ni/Al2O3, while the most resistant to coking behavior was Co/Al2O3. The enhanced activity of the Ni(Co)/Al2O3 bimetallic catalyst is attributed to the reduced particle size of metallic species and resistance to forming stable filamentous carbon. The overall carbon deposition on the spent bimetallic catalyst is comparable to that of the spent Ni/Al2O3 catalyst, whereas the carbon deposited on the bimetallic catalyst is mainly less-stable carbonaceous species as confirmed by SEM, TPO, Raman and INS characterization. This study provides an in depth understanding of alloy effects in catalysts, the chemical nature of coked carbon on spent Ni-based catalysts and, hopefully, inspires the creative design of a new bimetallic catalyst for dry reforming reactions.

  15. A Single-Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms

    SciTech Connect

    Kistler, Joseph D.; Chotigkrai, Nutchapon; Xu, Pinghong; Enderle, Bryan; Praserthdam, Piyasan; Chen, Cong-Yan; Browning, Nigel D.; Gates, Bruce C.

    2014-07-01

    A stable site-isolated mononuclear platinum catalyst with a well-defined structure is presented. Platinum complexes supported in zeolite KLTL were synthesized from [Pt(NH3)4](NO3)2, oxidized at 633 K, and used to catalyze CO oxidation. Finally, IR and X-ray absorption spectra and electron micrographs determine the structures and locations of the platinum complexes in the zeolite pores, demonstrate the platinum-support bonding, and show that the platinum remained site isolated after oxidation and catalysis.

  16. [Preparation of Cu/ZrO2/S2O8(2-)/gamma-Al2O3 solid acid catalyst and its catalytic activity to selective reduction of NO].

    PubMed

    Guo, Xi-kun; Wang, Xiao-ming

    2008-06-01

    Cu/ZrO2/S2O8(2-)/gamma-Al2O3 solid acid catalyst was prepared by loading of (NH4)2S2O8, ZrOCl2, and Cu(NO3)2 onto gamma-Al2O3 step by step, which was obtained from calcining of pseudoboehmite. The catalytic property of Cu/ZrO2/S2O8(2-)/gamma-Al2O3 on the selective reduction of NO by C3H6 in excess oxygen was investigated. The relationship between the structure and the catalytic property of Cu/ZrO2/S2O8(2-)/gamma-Al2O3 catalyst was also explored by means of SEM, XRD, Py-IR and TPR. The experimental results of catalytic activity of the title catalyst indicated that the maximum conversion rate of NO could reach 82.9% in the absence of water and was up to 80.2% even in the presence of 10% water vapor. The results of the structural characterization toward the catalyst showed that S2O8(2-) and ZrO2 could restrain the sinteration of gamma-Al2O3 particles and the formation of CuAl2O4 spinelle, and also facilitate the formation of new acidic sites (Brönsted acid) and the enhance of the acidity on the surface of the catalyst. In addition, ZrO2 could increase the reducibility of Cu on the catalyst. Consequently, the catalytic activity and hydrothermal stability of the catalyst were improved effectively.

  17. Development of Hierarchical Polymer@Pd Nanowire‐Network: Synthesis and Application as Highly Active Recyclable Catalyst and Printable Conductive Ink

    PubMed Central

    Mir, Sajjad Husain

    2016-01-01

    Abstract A facile one‐pot approach for preparing hierarchical nanowire‐networks of hollow polymer@Pd nanospheres is reported. First, polymer@Pd hollow nanospheres were produced through metal‐complexation‐induced phase separation with functionalized graft copolymers and subsequent self‐assembly of PdNPs. The nanospheres hierarchically assembled into the nanowire‐network upon drying. The Pd nanowire‐network served as an active catalyst for Mizoroki–Heck and Suzuki–Miyaura coupling reactions. As low as 500 μmol % Pd was sufficient for quantitative reactions, and the origin of the high activity is ascribed to the highly active sites originating from high‐index facets, kinks, and coalesced structures. The catalyst can be recycled via simple filtration and washing, maintaining its high activity owing to the micrometer‐sized hierarchical structure of the nanomaterial. The polymer@Pd nanosphere also served as a printable conductive ink for a translucent grid pattern with excellent horizontal conductivity (7.5×105 S m−1). PMID:27551657

  18. Development of Hierarchical Polymer@Pd Nanowire-Network: Synthesis and Application as Highly Active Recyclable Catalyst and Printable Conductive Ink.

    PubMed

    Mir, Sajjad Husain; Ochiai, Bungo

    2016-06-01

    A facile one-pot approach for preparing hierarchical nanowire-networks of hollow polymer@Pd nanospheres is reported. First, polymer@Pd hollow nanospheres were produced through metal-complexation-induced phase separation with functionalized graft copolymers and subsequent self-assembly of PdNPs. The nanospheres hierarchically assembled into the nanowire-network upon drying. The Pd nanowire-network served as an active catalyst for Mizoroki-Heck and Suzuki-Miyaura coupling reactions. As low as 500 μmol % Pd was sufficient for quantitative reactions, and the origin of the high activity is ascribed to the highly active sites originating from high-index facets, kinks, and coalesced structures. The catalyst can be recycled via simple filtration and washing, maintaining its high activity owing to the micrometer-sized hierarchical structure of the nanomaterial. The polymer@Pd nanosphere also served as a printable conductive ink for a translucent grid pattern with excellent horizontal conductivity (7.5×10(5) S m(-1)). PMID:27551657

  19. Stabilizing and enhancing activity of Ag as a catalyst for oxygen redaction reaction on hydrogen fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Stolbov, Sergey; Alcantara Ortigoza, Marisol

    2013-03-01

    Progress in searching for cost-effective and highly active catalysts for the oxygen reduction reaction (ORR) on hydrogen fuel cell cathodes is hindered by the fact that only a few elements (expensive and scarce Pt, Ir, Au) do not dissolve in the reaction environment (acidic medium at the expected operating potential +0.8 to +1.0 V vs SHE). Yet, in this work, we explore silver as an active element for the ORR catalysts. Although the dissolution potential (DP) of elemental Ag is 0.8 V, we rely on our finding that binding of a metal monolayer (ML) to a reactive substrate can significantly increase its DP. Using our approach, we select Ag/Ru/W, Ag/Nb, and Ag/Ta as promising candidates for the ORR catalysts (where Ag and Ru are MLs). Our evaluation of DP within density functional theory (DFT) shows that, indeed, in the selected structures, DP of Ag significantly increases as compared to that of Ag(111) and, in the case of Ag/Nb, even exceeds that of Pt. The ORR free-energy diagrams calculated within DFT suggest that the above systems are more active toward ORR than Pt. We thus predict here three highly active and truly cost-effective ORR catalysts. This work was supported by NSF under Grant CBET-1249134

  20. Impact of carbon on the surface and activity of silica-carbon supported copper catalysts for reduction of nitrogen oxides

    NASA Astrophysics Data System (ADS)

    Spassova, I.; Stoeva, N.; Nickolov, R.; Atanasova, G.; Khristova, M.

    2016-04-01

    Composite catalysts, prepared by one or more active components supported on a support are of interest because of the possible interaction between the catalytic components and the support materials. The supports of combined hydrophilic-hydrophobic type may influence how these materials maintain an active phase and as a result a possible cooperation between active components and the support material could occur and affects the catalytic behavior. Silica-carbon nanocomposites were prepared by sol-gel, using different in specific surface areas and porous texture carbon materials. Catalysts were obtained after copper deposition on these composites. The nanocomposites and the catalysts were characterized by nitrogen adsorption, TG, XRD, TEM- HRTEM, H2-TPR, and XPS. The nature of the carbon predetermines the composite's texture. The IEPs of carbon materials and silica is a force of composites formation and determines the respective distribution of the silica and carbon components on the surface of the composites. Copper deposition over the investigated silica-carbon composites leads to formation of active phases in which copper is in different oxidation states. The reduction of NO with CO proceeds by different paths on different catalysts due to the textural differences of the composites, maintaining different surface composition and oxidation states of copper.

  1. Active low-valent niobium catalysts from NbCl5 and hydrosilanes for selective intermolecular cycloadditions.

    PubMed

    Satoh, Yasushi; Obora, Yasushi

    2011-10-21

    An active niobium catalyst was developed via a simple and nontoxic reduction method from NbCl(5)/hydrosilane and utilized for the selective [2 + 2 + 2] cycloaddition reaction of terminal alkynes and alkenes/α,ω-dienes, to give 1,3-cyclohexadiene derivatives in high yields with excellent chemo- and regioselectivity. PMID:21919436

  2. Combinatorial high-throughput screening for highly active Pd-Ir-Ce based ternary catalysts in electrochemical oxygen reduction reaction.

    PubMed

    Park, Sung Hyeon; Choi, Chang Hyuck; Koh, Jae Kang; Pak, Chanho; Jin, Seon-ah; Woo, Seong Ihl

    2013-11-11

    A combinatorial library having 66 different ternary compositions of Pd-Ir-Ce was prepared via the impregnation method to find the optimum ternary composition with the highest performance toward oxygen reduction reaction (ORR) in acid media. Its performance in ORR activity of the combinatorial array was evaluated through two different combinatorial high-throughput screening methods to gain validity: (1) multielectrode half-cell method and (2) optical screening method. From the combinatorial results, the spot at 79:12:9 for Pd-Ir-Ce (at. %) in the array showed the highest ORR activity. The electrochemical characterizations of the single catalyst demonstrates that the optimized Pd79Ir12Ce9/C catalyst shows 1.5 times the ORR activity compared to that of Pd/C catalyst at 0.85 V (vs. RHE). In the Pd-Ir-Ce based catalysts, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results reveal that Ir and Ce are present in the form of IrO2 and CeO2, respectively, and the electron configuration of Pd is effectively modified through the decoration with IrO2 and CeO2. From the results, we suggest that the electro-modification of Pd through strong metal-metal oxide interaction with IrO2-CeO2 was a reason for the enhanced ORR activity.

  3. Effects of plasmochemical treatments and cerium additions on the structural characteristics and activity of copper catalyst particles in isopropanol dehydrogenation

    NASA Astrophysics Data System (ADS)

    Platonov, E. A.; Lobanov, N. N.; Galimova, N. A.; Protasova, I. A.; Yagodovskii, V. D.

    2012-08-01

    The effect of the treatment of the 5 wt % Cu/SiO2 (I) and (5 wt % Cu + 0.5 wt % Ce)/SiO2 (II) catalysts with glow discharge plasma in O2, H2, and Ar on their structural characteristics was studied by X-ray phase analysis; the influence of cerium additions and plasmochemical treatments on the catalyst activity in isopropanol dehydrogenation was also investigated. Under the plasmochemical treatment, the diameters of Cu particles in catalyst I nearly doubled and microstresses in the metal particles also changed. Catalyst II was X-ray amorphous both before and after plasmochemical treatments. The activity of I after plasmochemical treatment increased because of the increase in the number of centers and changes in their composition. Growth of the activity of I compared with the activity of II was explained by the formation of new catalytic centers due to positive charging of the Ce+α adatom on the surface of the copper particle.

  4. Exceptional methanol electro-oxidation activity by bimetallic concave and dendritic Pt-Cu nanocrystals catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Ying-Xia; Zhou, Hui-Jing; Sun, Ping-Chuan; Chen, Tie-Hong

    2014-01-01

    PtCux (x = 1, 2 and 3) bimetallic nanocrystals with concave surface and dendritic morphology were prepared and used as electrocatalysts in methanol oxidation reaction (MOR) for polymer electrolyte membrane fuel cells. The bimetallic nanocrystals were synthesized via one-pot co-reduction of H2PtCl6 and Cu(acac)2 by oleylamine and polyvinyl pyrrolidone (PVP) in an autoclave at 180 °C. The concave dendritic bimetallic nanostructure consisted of a core rich in Cu and nanodendrites rich in Pt, which was formed via galvanic replacement of Cu by Pt. It was found that PVP played an important role in initiating, facilitating, and directing the replacement reaction. The electrochemical properties of the PtCux were characterized by cyclic voltammetry (CV) and chronoamperometry (CA). The concave dendritic PtCu2/C nanocrystals exhibited exceptionally high activity and strong poisoning resistance in MOR. At 0.75 V (vs. reversible hydrogen electrode, RHE) the mass activity and specific activity of PtCu2/C were 3.3 and 4.1 times higher than those of the commercial Pt/C catalysts, respectively. The enhanced catalytic activity could be attributed to the unique concave dendritic morphology of the bimetallic nanocrystals.

  5. A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

    PubMed Central

    Liu, Wen; Hu, Enyuan; Jiang, Hong; Xiang, Yingjie; Weng, Zhe; Li, Min; Fan, Qi; Yu, Xiqian; Altman, Eric I.; Wang, Hailiang

    2016-01-01

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm−2 and 100 mA cm−2 at overpotentials of 48 mV and 109 mV, respectively. Phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation. PMID:26892437

  6. Activity and selectivity control by niobium for the preferential oxidation of co on pt supported catalysts

    SciTech Connect

    Guerrero, S.; Miller, J.T.; Wolf, E.E.

    2010-10-22

    The promotional effect of Nb on Pt supported on alumina or on niobia, was studied for the preferential oxidation of CO (PROX) in hydrogen. The results show a unique effect of Nb as a promoter to Pt. At low Nb loadings on Pt/alumina, the CO oxidation activity and selectivity are significantly increased. The CO selectivity is 100% at conversions up to about 60%. For Pt supported on Nb{sub 2}O{sub 5}, however, the CO oxidation activity is strongly suppressed with low CO conversion but high H{sub 2} oxidation activity. Pt on niobia, therefore, is poorly selective for the PROX reaction, but is an active hydrogen oxidation catalyst, resistant to CO poisoning. For Pt supported on highly loaded Nb-alumina or Nb{sub 2}O{sub 5}, XPS indicate an increase in the Pt and Nb oxidation states. These surface changes also correlate with changes in the DRIFTS spectra suggesting that CO is more weakly adsorbed on Pt/Nb{sub 2}O{sub 5} compared to Pt/Al{sub 2}O{sub 3}, or Pt/Nb-Al{sub 2}O{sub 3}.

  7. A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

    NASA Astrophysics Data System (ADS)

    Liu, Wen; Hu, Enyuan; Jiang, Hong; Xiang, Yingjie; Weng, Zhe; Li, Min; Fan, Qi; Yu, Xiqian; Altman, Eric I.; Wang, Hailiang

    2016-02-01

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm-2 and 100 mA cm-2 at overpotentials of 48 mV and 109 mV, respectively. Phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.

  8. A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

    DOE PAGES

    Liu, Wen; Hu, Enyuan; Jiang, Hong; Xiang, Yingjie; Weng, Zhe; Li, Min; Fan, Qi; Yu, Xiqian; Altman, Eric I.; Wang, Hailiang

    2016-02-19

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superiormore » activity for hydrogen evolution, achieving current densities of 10 mA cm–2 and 100 mA cm–2 at overpotentials of 48 mV and 109 mV, respectively. Lastly, phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.« less

  9. Structure and Activity of Pt-Ni Catalysts Supported on Modified Al2O3 for Ethanol Steam Reforming.

    PubMed

    Navarro, R M; Sanchez-Sanchez, M C; Fierro, J L G

    2015-09-01

    Modification of alumina with La-, Ce-, Zr- and Mg-oxides was studied with the aim to use them as supports of bimetallic Pt-Ni catalysts for the steam reforming of ethanol. Activity results showed that modifications of Al2O3 support with the incorporation of La, Ce, Zr or Mg oxides play an essential role in the catalytic behaviour of PtNi catalysts. Bimetallic PtNi catalyst supported on bare Al2O3 showed evolution of the reaction products with time on stream consisting in the increase of C2H4 production with concomitant decrease of CH4 and CO2 production. The addition of Mg or Zr to γ-A1203 did not inhibit the appearance of ethylene but delayed its production. In the case of Ce- or La-supported catalysts, the product selectivities were stable with time-on-stream, with no changes being observed in the product distribution for 24 h. Characterization results showed that La- and Ce-containing supports improves the Pt and Ni metal exposure values. The better stability achieved for Ce and La containing catalysts was inferred to be related with a participation/assistance of lanthanum and cerium entities in the gasification of coke deposits together with a modification of Pt and Ni dispersion which lower the probability of the nucleation of coke precursors on their surfaces. PMID:26716216

  10. Hydrogenation of CO2 to methanol on CeOx/Cu(111) and ZnO/Cu(111) catalysts: Role of the metal-oxide interface and importance of Ce3+ sites

    DOE PAGES

    Sanjaya D. Senanayake; Ramirez, Pedro J.; Waluyo, Iradwikanari; Kundu, Shankhamala; Mudiyanselage, Kumudu; Liu, Zongyuan; Liu, Zhi; Axnanda, Stephanus; Stacchiola, Dario J.; Evans, Jaime; et al

    2016-01-06

    The role of the interface between a metal and oxide (CeOx–Cu and ZnO–Cu) is critical to the production of methanol through the hydrogenation of CO2 (CO2 + 3H2 → CH3OH + H2O). The deposition of nanoparticles of CeOx or ZnO on Cu(111), θoxi < 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeOx/Cu(111). The apparent activation energy for the CO2 → CH3OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111) and 13 kcal/mol on CeOx/Cu(111). The surface chemistry of the highlymore » active CeOx–Cu(111) interface was investigated using ambient pressure X-ray photoemission spectroscopy (AP-XPS) and infrared reflection absorption spectroscopy (AP-IRRAS). Both techniques point to the formation of formates (HCOO–) and carboxylates (CO2δ–) during the reaction. Our results show an active state of the catalyst rich in Ce3+ sites which stabilize a CO2δ– species that is an essential intermediate for the production of methanol. Furthermore, the inverse oxide/metal configuration favors strong metal–oxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.« less

  11. Production of biodiesel fuel from canola oil with dimethyl carbonate using an active sodium methoxide catalyst prepared by crystallization.

    PubMed

    Kai, Takami; Mak, Goon Lum; Wada, Shohei; Nakazato, Tsutomu; Takanashi, Hirokazu; Uemura, Yoshimitsu

    2014-07-01

    In this study, a novel method for the production of biodiesel under mild conditions using fine particles of sodium methoxide formed in dimethyl carbonate (DMC) is proposed. Biodiesel is generally produced from vegetable oils by the transesterification of triglycerides with methanol. However, this reaction produces glycerol as a byproduct, and raw materials are not effectively utilized. Transesterification with DMC has recently been studied because glycerol is not formed in the process. Although solid-state sodium methoxide has been reported to be inactive for this reaction, the catalytic activity dramatically increased with the preparation of fine catalyst powders by crystallization. The transesterification of canola oil with DMC was studied using this catalyst for the preparation of biodiesel. A conversion greater than 96% was obtained at 65°C for 2h with a 3:1M ratio of DMC and oil and 2.0 wt% catalyst. PMID:24813567

  12. Production of biodiesel fuel from canola oil with dimethyl carbonate using an active sodium methoxide catalyst prepared by crystallization.

    PubMed

    Kai, Takami; Mak, Goon Lum; Wada, Shohei; Nakazato, Tsutomu; Takanashi, Hirokazu; Uemura, Yoshimitsu

    2014-07-01

    In this study, a novel method for the production of biodiesel under mild conditions using fine particles of sodium methoxide formed in dimethyl carbonate (DMC) is proposed. Biodiesel is generally produced from vegetable oils by the transesterification of triglycerides with methanol. However, this reaction produces glycerol as a byproduct, and raw materials are not effectively utilized. Transesterification with DMC has recently been studied because glycerol is not formed in the process. Although solid-state sodium methoxide has been reported to be inactive for this reaction, the catalytic activity dramatically increased with the preparation of fine catalyst powders by crystallization. The transesterification of canola oil with DMC was studied using this catalyst for the preparation of biodiesel. A conversion greater than 96% was obtained at 65°C for 2h with a 3:1M ratio of DMC and oil and 2.0 wt% catalyst.

  13. Effect of a catalyst on the kinetics of reduction of celestite (SrSO{sub 4}) by active charcoal

    SciTech Connect

    Sonawane, R.S.; Kale, B.B.; Apte, S.K.; Dongare, M.K.

    2000-02-01

    Reduction of celestite (SrSO{sub 4}) powder with particles of active charcoal has been studied extensively in the absence and presence of catalysts. The optimum temperature at the charging zone has been optimized to get a maximum water-soluble strontium sulfide value. The strontium value has been analyzed using a chemical method, which was verified by the instrumental method using an inductively coupled plasma-optical emission spectrophotometer (ICP-OES). The conversion-time data have been analyzed by using a modified volume-reaction (MVR) model, and the effect of the catalyst on kinetic parameters has been elucidated. It was found that potassium carbonate, potassium dichromate, sodium carbonate, and sodium dichromate catalysts were found to enhance the reaction rate quite satisfactorily in the reduction of the celestite (SrSO{sub 4}).

  14. PEMFC catalyst layers: the role of micropores and mesopores on water sorption and fuel cell activity.

    PubMed

    Soboleva, Tatyana; Malek, Kourosh; Xie, Zhong; Navessin, Titichai; Holdcroft, Steven

    2011-06-01

    The effects of carbon microstructure and ionomer loading on water vapor sorption and retention in catalyst layers (CLs) of PEM fuel cells are investigated using dynamic vapor sorption. Catalyst layers based on Ketjen Black and Vulcan XC-72 carbon blacks, which possess distinctly different surface areas, pore volumes, and microporosities, are studied. It is found that pores <20 nm diameter facilitate water uptake by capillary condensation in the intermediate range of relative humidities. A broad pore size distribution (PSD) is found to enhance water retention in Ketjen Black-based CLs whereas the narrower mesoporous PSD of Vulcan CLs is shown to have an enhanced water repelling action. Water vapor sorption and retention properties of CLs are correlated to electrochemical properties and fuel cell performance. Water sorption enhances electrochemical properties such as the electrochemically active surface area (ESA), double layer capacitance and proton conductivity, particularly when the ionomer content is very low. The hydrophilic properties of a CL on the anode and the cathode are adjusted by choosing the PSD of carbon and the ionomer content. It is shown that a reduction of ionomer content on either cathode or anode of an MEA does not necessarily have a significant detrimental effect on the MEA performance compared to the standard 30 wt % ionomer MEA. Under operation in air and high relative humidity, a cathode with a narrow pore size distribution and low ionomer content is shown to be beneficial due to its low water retention properties. In dry operating conditions, adequate ionomer content on the cathode is crucial, whereas it can be reduced on the anode without a significant impact on fuel cell performance.

  15. Increasing FCC regenerator catalyst level

    SciTech Connect

    Wong, R.F. )

    1993-11-01

    A Peruvian FCC unit's operations were improved by increasing the regenerator's catalyst level. This increase resulted in lower stack losses, an improved temperature profile, increased catalyst activity and a lower catalyst consumption rate. A more stable operation saved this Peruvian refiner over $131,000 per year in catalyst alone. These concepts and data may be suitable for your FCC unit as well.

  16. Searching for active binary rutile oxide catalyst for water splitting from first principles.

    PubMed

    Chen, Dong; Fang, Ya-Hui; Liu, Zhi-Pan

    2012-12-28

    Water electrolysis is an important route to large-scale hydrogen production using renewable energy, in which the oxygen evolution reaction (OER: 2H(2)O → O(2) + 4H(+) + 4e(-)) causes the largest energy loss in traditional electrocatalysts involving Ru-Ir mixed oxides. Following our previous mechanistic studies on the OER on RuO(2)(110) (J. Am. Chem. Soc. 2010, 132, 18214), this work aims to provide further insight into the key parameters relevant to the activity of OER catalysts by investigating a group of rutile-type binary metal oxides, including RuNiO(2), RuCoO(2), RuRhO(2), RuIrO(2) and OsIrO(2). Two key aspects are focused on, namely the surface O coverage at the relevant potential conditions and the kinetics of H(2)O activation on the O-covered surfaces. The O coverage for all the oxides investigated here is found to be 1 ML at the concerned potential (1.23 V) with all the exposed metal cations being covered by terminal O atoms. The calculated free energy barrier for the H(2)O dissociation on the O covered surfaces varies significantly on different surfaces. The highest OER activity occurs at RuCoO(2) and RuNiO(2) oxides with a predicted activity about 500 times higher than pure RuO(2). On these oxides, the surface bridging O near the terminal O atom has a high activity for accepting the H during H(2)O splitting. It is concluded that while the differential adsorption energy of the terminal O atom influences the OER activity to the largest extent, the OER activity can still be tuned by modifying the electronic structure of surface bridging O.

  17. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    NASA Astrophysics Data System (ADS)

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date.

  18. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    DOE PAGES

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-19

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O₂ bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H₂O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH boundmore » structures have the highest calculated activity to date.« less

  19. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    SciTech Connect

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-19

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O₂ bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H₂O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date.

  20. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    PubMed Central

    Holby, Edward F.; Taylor, Christopher D.

    2015-01-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date. PMID:25788358