Trends in low-temperature water?gas shift reactivity on transition metals

Schumacher, Nana Maria Pii; Boisen, Astrid; Dahl, Søren; Gokhale, Amit A.; Kandoi, Shampa; Grabow, Lars C.; Dumesic, James A.; Mavrikakis, Manos; Chorkendorff, Ib

doi:10.1016/j.jcat.2004.10.025

Cited by 217 publications

(156 citation statements)

References 29 publications

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“…46 According to the CO 2 -TPD results, Fe 3 O 4 shows higher adsorption capacity than Cu at 240-280 C, as well as stronger adsorption of CO 2 to its surface. [46][47][48] Additionally, H 2 -TPD results showed that between 240 and 280 C, dissociative adsorption of H 2 primarily occurred on Cu. In many DFT calculations, [47][48][49] it has been found that Cu-based catalyst that have been doped with transition metal oxide additives adsorb H 2 by dissociative adsorption onto Cu, while the transition metal oxides adsorb and activate CO 2 .…”

Section: Resultsmentioning

confidence: 98%

“…[46][47][48] Additionally, H 2 -TPD results showed that between 240 and 280 C, dissociative adsorption of H 2 primarily occurred on Cu. In many DFT calculations, [47][48][49] it has been found that Cu-based catalyst that have been doped with transition metal oxide additives adsorb H 2 by dissociative adsorption onto Cu, while the transition metal oxides adsorb and activate CO 2 . Subsequent CO 2 desorb from the metal oxide surface and adsorb to metallic Cu to allow the adsorbed species to react with dissociated H at the Cu site; this causes the deformation activation of O@C@O linear configurations.…”

Section: Resultsmentioning

confidence: 98%

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Experimental and theoretical study of the intrinsic kinetics for dimethyl ether synthesis from CO₂ over Cu–Fe–Zr/HZSM‐5

Qin

et al. 2015

AIChE Journal

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An intrinsic kinetics model was established for CO 2 hydrogenation to dimethyl ether (DME) with a Cu-Fe-Zr/HZSM-5 catalyst based on H 2 /CO 2 adsorption, simulation, and calculation of methanol synthesis from CO 2 intermediates and experimental data. H 2 /CO 2 -temperature programmed desorption results show a dissociative H 2 adsorption on Cu site; CO 2 was linearly adsorbed on Fe 3 O 4 weak base sites of the catalyst; the adsorbing capacity of H 2 and CO 2 increased after Zr-doping. Density functional theory analysis of methanol synthesis from CO 2 and H 2 revealed a formate pathway. Methanol synthesis was the rate-limiting step (173.72 kJÁmol 21 activation energy) of the overall CO 2 hydrogenation reaction, and formation of H 2 CO is the rate-determining step of methanol synthesis. Relative errors between calculated and experimental data of partial pressures of all components were less than 10%. Therefore, the kinetics model may be an accurate descriptor of intrinsic kinetics of CO 2 hydrogenation to DME.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 98%

Experimental and theoretical study of the intrinsic kinetics for dimethyl ether synthesis from CO₂ over Cu–Fe–Zr/HZSM‐5

Qin

et al. 2015

AIChE Journal

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“…Carbon monoxide is required by both Reactions (1) and (2) and conversion of CO can be expected to be rather high. Schumacher et al [7] also tested catalysts under forward WGS feed conditions. For the catalysts investigated on an aluminum oxide support the following experimental trend was found Cu > Co > Ru > Ni > Pt > Au > Fe > Pd > Rh > Ir.…”

Section: Experimental Datamentioning

confidence: 99%

“…Microkinetics modeling explores the detailed chemistry of the reaction. Although the WGS reaction involves only four simple molecules, the reaction mechanism is quite complex and depends on the catalyst and feed composition [6][7][8]. A direct experimental investigation of a particular mechanism for WGS reaction is difficult or impossible under realistic operating conditions.…”

Section: Introductionmentioning

confidence: 99%

Water–Gas Shift Reaction over Ni/CeO2 Catalysts

et al. 2017

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This paper reports the results of a study of a water-gas shift reaction over nickel-ceria catalysts with different metal loading. Within this study, the overall CO conversion and observed kinetic behavior were investigated over the temperature range of 250-550 • C in different reactor configurations (fixed-bed and microchannel reactors). The quasi-steady state kinetics of the CO water-gas shift reaction was studied for fractions of Ni-containing cerium oxide catalysts in fixed-bed experiments at lab-scale level using a very dilute gas (1% CO + 1.8% H 2 O in He). A set of experiments with a microchannel reactor was performed using the feed composition (CO:H 2 O:H 2 :N 2 = 1:2:2:2), representing a product gas from methane partial oxidation. The results were interpreted using computational models. The kinetic parameters were determined by regression analysis, while mechanistic aspects were considered only briefly. Simulation of the WGS reaction in the microreactor was also carried out by using the COMSOL Multiphysics program.

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“…-OH groups, interact with which specific methanol-derived C 1 -oxygenates to form the optimum CO 2 precursor species. For this reason the propensity of Cu or other metal surfaces [18] and of ZnO surfaces [19][20][21][22][23] for water dissociation, being an important aspect for all reforming reactions, has already been studied extensively. However, pure ZnO is unselective with respect to CO 2 formation and rather favors CO production [24].…”

Section: Introductionmentioning

confidence: 99%

Steam reforming of methanol on PdZn near-surface alloys on Pd(1 1 1) and Pd foil studied by in-situ XPS, LEIS and PM-IRAS

Rameshan

Weilach

Stadlmayr

et al. 2010

Journal of Catalysis

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The CO2-selectivity in methanol steam reforming was investigated for a "multilayer" PdZn 1:1 surface alloy (thickness of ~1.3 nm) and for a subsurface-Zn diluted "monolayer" PdZn surface alloy, both exhibiting a 1:1 composition in the surface layer. Despite having almost the same surface layer stoichiometry, these two types of near-surface alloys exhibit different corrugations and electronic structures. The CO2-selective multilayer alloy features a lowered density of states close to the Fermi edge and surface ensembles of PdZn exhibiting a "Zn-up/Pd-down" corrugation, acting as bifunctional active sites both for reversible water activation as ZnOH and for reaction of methanol (via formaldehyde + ZnOH) toward CO2. The thermochemical stability limit of the multilayer alloy at around 573 K was determined in-situ at elevated pressures of water, methanol and CO, applying in-situ XPS, PM-IRAS spectroscopy, LEIS and AES. Above 573 K, the coordination of the surface 1:1 PdZn layer with subsurfaceZn gradually decreased by bulk diffusion of Zn "escaping" from the second and deeper layers, resulting in a transition from the CO2-selective PdZn "multilayer" state to the unselective "monolayer" state, which only catalyses methanol dehydrogenation to CO.

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Trends in low-temperature water?gas shift reactivity on transition metals

Cited by 217 publications

References 29 publications

Experimental and theoretical study of the intrinsic kinetics for dimethyl ether synthesis from CO₂ over Cu–Fe–Zr/HZSM‐5

Experimental and theoretical study of the intrinsic kinetics for dimethyl ether synthesis from CO₂ over Cu–Fe–Zr/HZSM‐5

Water–Gas Shift Reaction over Ni/CeO2 Catalysts

Steam reforming of methanol on PdZn near-surface alloys on Pd(1 1 1) and Pd foil studied by in-situ XPS, LEIS and PM-IRAS

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Trends in low-temperature water?gas shift reactivity on transition metals

Cited by 217 publications

References 29 publications

Experimental and theoretical study of the intrinsic kinetics for dimethyl ether synthesis from CO2 over Cu–Fe–Zr/HZSM‐5

Experimental and theoretical study of the intrinsic kinetics for dimethyl ether synthesis from CO2 over Cu–Fe–Zr/HZSM‐5

Water–Gas Shift Reaction over Ni/CeO2 Catalysts

Steam reforming of methanol on PdZn near-surface alloys on Pd(1 1 1) and Pd foil studied by in-situ XPS, LEIS and PM-IRAS

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Experimental and theoretical study of the intrinsic kinetics for dimethyl ether synthesis from CO₂ over Cu–Fe–Zr/HZSM‐5

Experimental and theoretical study of the intrinsic kinetics for dimethyl ether synthesis from CO₂ over Cu–Fe–Zr/HZSM‐5