Mechanistic Insights into the Synthesis of Higher Alcohols from Syngas on CuCo Alloys

doi:https://doi.org/10.1021/acscatal.8b01596

Title: Mechanistic Insights into the Synthesis of Higher Alcohols from Syngas on CuCo Alloys

Abstract

Synthesis gas (CO + H ₂) conversion is an important process in the transformation of coal, natural gas, or biomass into higher-value products. The explicit conversion into C ₂₊ oxygenates on transition-metal-based catalysts suffers from a low selectivity, being a consequence of an imperative integration of C–O bond splitting and C–C coupling reactions. Recently, it has been demonstrated that a bimetallic CuCo catalyst has high higher alcohol selectivity under mild reaction conditions, but the details of the reaction mechanism on the surface are still elusive. In this work, we studied the formation of methane, methanol, and ethanol from syngas on a close-packed (111) and a stepped (211) CuCo surface combining density functional theory (DFT) and microkinetic modeling. We found the CuCo alloy to be a promising candidate catalyst, displaying the required coverage of CO and CH _x on the surface to facilitate C–C coupling. In addition, we found the selectivity to be very structure sensitive: the CuCo (211) surface is selective toward ethanol under certain reaction conditions, while the (111) surface is selective toward methanol. As a result, we identified the much lower C–O dissociation barrier and the higher rate of CH _x–CO coupling as the reason for the highmore »« less

Authors:

^[1];

^[2]; Wang, Tao ^[2]; Zhang, Linan ^[2]; Xiao, Jianping ^[2]; Bothra, Pallavi ^[2];

^[3];

^[2]; Nørskov, Jens K. ^[2]

Tianjin Univ., Tianjin (People's Republic of China); SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
Tianjin Univ., Tianjin (People’s Republic of China)

Publication Date:: 2018-09-14

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

Sponsoring Org.:: USDOE

OSTI Identifier:: 1490982

Grant/Contract Number:: AC02-76SF00515

Resource Type:: Journal Article: 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:: 36 MATERIALS SCIENCE; CuCo alloy; DFT; higher alcohol synthesis; microkinetic modeling; synthesis gas conversion

Citation Formats


                    Cao, Ang, Schumann, Julia, Wang, Tao, Zhang, Linan, Xiao, Jianping, Bothra, Pallavi, Liu, Yuan, Abild-Pedersen, Frank, and Nørskov, Jens K. Mechanistic Insights into the Synthesis of Higher Alcohols from Syngas on CuCo Alloys.  United States: N. p., 2018. 
        Web.  doi:10.1021/acscatal.8b01596.

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                    Cao, Ang, Schumann, Julia, Wang, Tao, Zhang, Linan, Xiao, Jianping, Bothra, Pallavi, Liu, Yuan, Abild-Pedersen, Frank, & Nørskov, Jens K. Mechanistic Insights into the Synthesis of Higher Alcohols from Syngas on CuCo Alloys.  United States.  https://doi.org/10.1021/acscatal.8b01596

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                    Cao, Ang, Schumann, Julia, Wang, Tao, Zhang, Linan, Xiao, Jianping, Bothra, Pallavi, Liu, Yuan, Abild-Pedersen, Frank, and Nørskov, Jens K. Fri .  
        "Mechanistic Insights into the Synthesis of Higher Alcohols from Syngas on CuCo Alloys".  United States.  https://doi.org/10.1021/acscatal.8b01596.  https://www.osti.gov/servlets/purl/1490982.

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@article{osti_1490982,

  title        = {Mechanistic Insights into the Synthesis of Higher Alcohols from Syngas on CuCo Alloys},

  author       = {Cao, Ang and Schumann, Julia and Wang, Tao and Zhang, Linan and Xiao, Jianping and Bothra, Pallavi and Liu, Yuan and Abild-Pedersen, Frank and Nørskov, Jens K.},

  abstractNote = {Synthesis gas (CO + H2) conversion is an important process in the transformation of coal, natural gas, or biomass into higher-value products. The explicit conversion into C2+ oxygenates on transition-metal-based catalysts suffers from a low selectivity, being a consequence of an imperative integration of C–O bond splitting and C–C coupling reactions. Recently, it has been demonstrated that a bimetallic CuCo catalyst has high higher alcohol selectivity under mild reaction conditions, but the details of the reaction mechanism on the surface are still elusive. In this work, we studied the formation of methane, methanol, and ethanol from syngas on a close-packed (111) and a stepped (211) CuCo surface combining density functional theory (DFT) and microkinetic modeling. We found the CuCo alloy to be a promising candidate catalyst, displaying the required coverage of CO and CHx on the surface to facilitate C–C coupling. In addition, we found the selectivity to be very structure sensitive: the CuCo (211) surface is selective toward ethanol under certain reaction conditions, while the (111) surface is selective toward methanol. As a result, we identified the much lower C–O dissociation barrier and the higher rate of CHx–CO coupling as the reason for the high activity and selectivity toward ethanol on the (211) surface.},

  doi          = {10.1021/acscatal.8b01596},

  url          = {https://www.osti.gov/biblio/1490982},
  journal      = {ACS Catalysis},

  issn         = {2155-5435},

  number       = 11,

  volume       = 8,

  place        = {United States},

  year         = {2018},

  month        = {9}

}

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Works referencing / citing this record:

Strategies to break linear scaling relationships
journal, October 2019

Pérez-Ramírez, Javier; López, Núria
Nature Catalysis, Vol. 2, Issue 11
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Title: Mechanistic Insights into the Synthesis of Higher Alcohols from Syngas on CuCo Alloys

Abstract

Citation Formats

Strategies to break linear scaling relationships journal, October 2019

Strategies to break linear scaling relationships
journal, October 2019