Strongly Modified Scaling of CO Hydrogenation in Metal Supported TiO Nanostripes

Sandberg, Robert B.; Hansen, Martin H.; Nørskov, Jens K.; Abild-Pedersen, Frank; Bajdich, Michal

doi:10.1021/acscatal.8b03327

Title: Strongly Modified Scaling of CO Hydrogenation in Metal Supported TiO Nanostripes

Abstract

The boundary between a metal-oxide and its metal support (metal-oxide|support) provides an intriguing structural interface for heterogeneous catalysis. The hydrogenation of CO is a reaction step believed to be rate limiting in electro-chemical CO2 reduction. Density functional theory (DFT) calculations were performed to study this reaction step for a class of catalytic material: metal supported TiO nanostripe. The most stable adsorption sites were identified for all metal supports which showed a striking difference in adsorbate geometry between the strong and weak binding metal supports. The modified CO hydrogenation scaling shows a significant strengthening over (111) and (211) transition metal surfaces. Such enhancement can be attributed to a combination of geometrical effects and metal-oxide|support electronic interactions. A correlation analysis was performed to identify the key features needed to accurately predict *CO and *CHO adsorption energies on the TiO nanostripes and to further validate our physical analysis of the results. This structural motif seems to be a promising avenue to explore scaling modification in other metal-oxide materials and reactions.

Authors:

^[1];

^[2]; Nørskov, Jens K. ^[3];

^[2];

^[2]

Stanford Univ., Stanford, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark)

Publication Date:: 2018-10-03

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1490983

Alternate Identifier(s):: OSTI ID: 1490748

Grant/Contract Number:: AC02-76SF00515

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO hydrogenation; CO2 reduction; computational catalysis; DFT; metal-oxides; nanostripe; scaling relations; ultrathin overlayers

Citation Formats


                    Sandberg, Robert B., Hansen, Martin H., Nørskov, Jens K., Abild-Pedersen, Frank, and Bajdich, Michal. Strongly Modified Scaling of CO Hydrogenation in Metal Supported TiO Nanostripes.  United States: N. p., 2018. 
Web.  doi:10.1021/acscatal.8b03327.

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                    Sandberg, Robert B., Hansen, Martin H., Nørskov, Jens K., Abild-Pedersen, Frank, & Bajdich, Michal. Strongly Modified Scaling of CO Hydrogenation in Metal Supported TiO Nanostripes.  United States.  https://doi.org/10.1021/acscatal.8b03327

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                    Sandberg, Robert B., Hansen, Martin H., Nørskov, Jens K., Abild-Pedersen, Frank, and Bajdich, Michal. Wed .  
"Strongly Modified Scaling of CO Hydrogenation in Metal Supported TiO Nanostripes".  United States.  https://doi.org/10.1021/acscatal.8b03327.  https://www.osti.gov/servlets/purl/1490983.

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@article{osti_1490983,

  title        = {Strongly Modified Scaling of CO Hydrogenation in Metal Supported TiO Nanostripes},

  author       = {Sandberg, Robert B. and Hansen, Martin H. and Nørskov, Jens K. and Abild-Pedersen, Frank and Bajdich, Michal},

  abstractNote = {The boundary between a metal-oxide and its metal support (metal-oxide|support) provides an intriguing structural interface for heterogeneous catalysis. The hydrogenation of CO is a reaction step believed to be rate limiting in electro-chemical CO2 reduction. Density functional theory (DFT) calculations were performed to study this reaction step for a class of catalytic material: metal supported TiO nanostripe. The most stable adsorption sites were identified for all metal supports which showed a striking difference in adsorbate geometry between the strong and weak binding metal supports. The modified CO hydrogenation scaling shows a significant strengthening over (111) and (211) transition metal surfaces. Such enhancement can be attributed to a combination of geometrical effects and metal-oxide|support electronic interactions. A correlation analysis was performed to identify the key features needed to accurately predict *CO and *CHO adsorption energies on the TiO nanostripes and to further validate our physical analysis of the results. This structural motif seems to be a promising avenue to explore scaling modification in other metal-oxide materials and reactions.},

  doi          = {10.1021/acscatal.8b03327},

  journal      = {ACS Catalysis},

  number       = 11,

  volume       = 8,

  place        = {United States},

  year         = {2018},

  month        = {10}

}

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Figure 1: Energy of a free-standing TiO overlayer as a function of hexagonal lattice constant. Dashed lines show the corresponding metal-metal distances in ( ll l) surfaces offcc support metals used in this study. The two minima at 3.10 and 3.33 Å correspond to the original rocksalt and stretched TiOmore »

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