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Title: Theoretical and Experimental Studies of CoGa Catalysts for the Hydrogenation of CO2 to Methanol

Abstract

We report methanol is an important chemical compound which is used both as a fuel and as a platform molecule in chemical production. Synthesizing methanol, as well as dimethyl ether, directly from carbon dioxide and hydrogen produced using renewable electricity would be a major step forward in enabling an environmentally sustainable economy. We utilize density functional theory combined with microkinetic modeling to understand the methanol synthesis reaction mechanism on a model CoGa catalyst. A series of catalysts with varying Ga content are synthesized and experimentally tested for catalytic performance. The performance of these catalysts is sensitive to the Co:Ga ratio, whereby increased Ga content results in increased methanol and dimethyl ether selectivity and increased Co content results in increased selectivity towards methane. We find that the most active catalysts have up to 95% CO-free selectivity towards methanol and dimethyl ether during CO2 hydrogenation and are comparable in performance to a commercial CuZn catalyst. Finally, using in situ DRIFTS we experimentally verify the presence of a surface formate intermediate during CO2 hydrogenation in support of our theoretical calculations.

Authors:
 [1];  [2];  [2];  [2];  [2];  [2];  [1]
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  1. Stanford Univ., CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1490622
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Letters
Additional Journal Information:
Journal Volume: 148; Journal Issue: 12; Journal ID: ISSN 1011-372X
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Methanol; Carbon dioxide; Density functional theory

Citation Formats

Singh, Joseph A., Cao, Ang, Schumann, Julia, Wang, Tao, Nørskov, Jens K., Abild-Pedersen, Frank, and Bent, Stacey F. Theoretical and Experimental Studies of CoGa Catalysts for the Hydrogenation of CO2 to Methanol. United States: N. p., 2018. Web. doi:10.1007/s10562-018-2542-x.
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Singh, Joseph A., Cao, Ang, Schumann, Julia, Wang, Tao, Nørskov, Jens K., Abild-Pedersen, Frank, & Bent, Stacey F. Theoretical and Experimental Studies of CoGa Catalysts for the Hydrogenation of CO2 to Methanol. United States. https://doi.org/10.1007/s10562-018-2542-x
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Singh, Joseph A., Cao, Ang, Schumann, Julia, Wang, Tao, Nørskov, Jens K., Abild-Pedersen, Frank, and Bent, Stacey F. Fri . "Theoretical and Experimental Studies of CoGa Catalysts for the Hydrogenation of CO2 to Methanol". United States. https://doi.org/10.1007/s10562-018-2542-x. https://www.osti.gov/servlets/purl/1490622.
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@article{osti_1490622,
title = {Theoretical and Experimental Studies of CoGa Catalysts for the Hydrogenation of CO2 to Methanol},
author = {Singh, Joseph A. and Cao, Ang and Schumann, Julia and Wang, Tao and Nørskov, Jens K. and Abild-Pedersen, Frank and Bent, Stacey F.},
abstractNote = {We report methanol is an important chemical compound which is used both as a fuel and as a platform molecule in chemical production. Synthesizing methanol, as well as dimethyl ether, directly from carbon dioxide and hydrogen produced using renewable electricity would be a major step forward in enabling an environmentally sustainable economy. We utilize density functional theory combined with microkinetic modeling to understand the methanol synthesis reaction mechanism on a model CoGa catalyst. A series of catalysts with varying Ga content are synthesized and experimentally tested for catalytic performance. The performance of these catalysts is sensitive to the Co:Ga ratio, whereby increased Ga content results in increased methanol and dimethyl ether selectivity and increased Co content results in increased selectivity towards methane. We find that the most active catalysts have up to 95% CO-free selectivity towards methanol and dimethyl ether during CO2 hydrogenation and are comparable in performance to a commercial CuZn catalyst. Finally, using in situ DRIFTS we experimentally verify the presence of a surface formate intermediate during CO2 hydrogenation in support of our theoretical calculations.},
doi = {10.1007/s10562-018-2542-x},
journal = {Catalysis Letters},
number = 12,
volume = 148,
place = {United States},
year = {Fri Oct 05 00:00:00 EDT 2018},
month = {Fri Oct 05 00:00:00 EDT 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1007/s10562-018-2542-x
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Cited by: 11 works
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Figures / Tables:

Fig. 1 Fig. 1: Calculated turnover frequencies (TOF) relative to copper (TOFCu) as a function of oxygen ($Δ$EO) binding energies. Calculations were performed for 250  °C with 6.67  bar carbon dioxide, 23.33 bar hydrogen, 0.01 bar water, and 0 bar methane, methanol, and carbon monoxide
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    Works referencing / citing this record:

    Methanol Synthesis from CO 2 Hydrogenation
    journal, July 2019

    Hydrogenation of Carbon Dioxide to Value-Added Chemicals by Heterogeneous Catalysis and Plasma Catalysis
    journal, March 2019

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      Figures / Tables found in this record:

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      Fig. 4 (p. 5)figure
      Table 1 (p. 5)table
      Fig. 5 (p. 6)figure
      Fig. 6 (p. 7)figure
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