Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory

Liu, P

doi:10.1063/1.3506897

Title: Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory

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Abstract

Developing improved catalysts based on a fundamental understanding of reaction mechanism has become one of the grand challenges in catalysis. A theoretical understanding and screening the metal-oxide composite catalysts for the water-gas shift (WGS) reaction is presented here. Density functional theory was employed to identify the key step for the WGS reaction on the Au, Cu-oxide catalysts, where the calculated reaction energy for water dissociation correlates well with the experimental measured WGS activity. Accordingly, the calculated reaction energy for water dissociation was used as the scaling descriptor to screen the inverse model catalysts, oxide/Cu(111), for the better WGS activity. Our calculations predict that the WGS activity increases in a sequence: Cu(111), ZnO/Cu(111) < TiO{sub 2}/Cu(111), ZrO{sub 2}/Cu(111) < MoO{sub 3}/Cu(111). Our results imply that the high performances of Au, Cu-oxide nanocatalysts in the WGS reaction rely heavily on the direct participation of both oxide and metal sites. The degree that the oxide is reduced by Cu plays an important role in determining the WGS activity of oxide/Cu catalysts. The reducible oxide can be transformed from the fully oxidized form to the reduced form due to the interaction with Cu and, therefore, the transfer of electron density from Cu, which helpsmore »« less

Authors:: Liu, P

Publication Date:: Sun Nov 28 00:00:00 EST 2010

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Sponsoring Org.:: DOE - OFFICE OF SCIENCE

OSTI Identifier:: 1020862

Report Number(s):: BNL-93961-2011-JA
Journal ID: ISSN 0021-9606; R&D Project: CO-027; KC0302010; TRN: US201116%%888

DOE Contract Number:: DE-AC02-98CH10886

Resource Type:: Journal Article

Journal Name:: The Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 133; Journal Issue: 20; Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 30 DIRECT ENERGY CONVERSION; CATALYSIS; CATALYSTS; COPPER; DISSOCIATION; ELECTRON DENSITY; FUNCTIONALS; OXIDES; REACTION KINETICS; SCREENS; WATER; WATER GAS; density functional theory; catalyst screening; water-gas shift; functional nanomaterials

Citation Formats


                    Liu, P. Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory.  United States: N. p., 2010. 
        Web.  doi:10.1063/1.3506897.

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                    Liu, P. Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory.  United States.  https://doi.org/10.1063/1.3506897

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                    Liu, P. 2010.  
        "Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory".  United States.  https://doi.org/10.1063/1.3506897.

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@article{osti_1020862,

  title        = {Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory},

  author       = {Liu, P},

  abstractNote = {Developing improved catalysts based on a fundamental understanding of reaction mechanism has become one of the grand challenges in catalysis. A theoretical understanding and screening the metal-oxide composite catalysts for the water-gas shift (WGS) reaction is presented here. Density functional theory was employed to identify the key step for the WGS reaction on the Au, Cu-oxide catalysts, where the calculated reaction energy for water dissociation correlates well with the experimental measured WGS activity. Accordingly, the calculated reaction energy for water dissociation was used as the scaling descriptor to screen the inverse model catalysts, oxide/Cu(111), for the better WGS activity. Our calculations predict that the WGS activity increases in a sequence: Cu(111), ZnO/Cu(111) < TiO{sub 2}/Cu(111), ZrO{sub 2}/Cu(111) < MoO{sub 3}/Cu(111). Our results imply that the high performances of Au, Cu-oxide nanocatalysts in the WGS reaction rely heavily on the direct participation of both oxide and metal sites. The degree that the oxide is reduced by Cu plays an important role in determining the WGS activity of oxide/Cu catalysts. The reducible oxide can be transformed from the fully oxidized form to the reduced form due to the interaction with Cu and, therefore, the transfer of electron density from Cu, which helps in releasing the bottleneck water dissociation and, therefore, facilitating the WGS reaction on copper.},

  doi          = {10.1063/1.3506897},

  url          = {https://www.osti.gov/biblio/1020862},
  journal      = {The Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 20,

  volume       = 133,

  place        = {United States},

  year         = {Sun Nov 28 00:00:00 EST 2010},

  month        = {Sun Nov 28 00:00:00 EST 2010}

}

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