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Title: Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas

Abstract

Controlling selectivity is a key goal in the design of a heterogeneous catalyst. Herein, we present detailed characterization and activity of silica–supported cobalt catalysts modified by atomic layer deposition of ZnO. After reduction, the resulting catalysts exhibit substantial selectivity towards alcohol production during CO hydrogenation compared to catalysts containing only cobalt. The prepared catalysts have up to 46 % selectivity toward alcohols with 39 % of the alcohols corresponding to ethanol and other higher alcohols, albeit with reduced activity. In situ characterization of the catalyst by X–ray diffraction and X–ray absorption spectroscopy reveals details on the structural evolution in syngas, CO+H2, and shows that ZnO promotion of Co results in the formation of Co2C under catalytic conditions. A mechanism is proposed, supported by density functional theory calculations, which explains Co2C formation by the blocking of Co step sites by Zn species. The ZnO acts a dual promoter both by facilitating Co2C formation and by modifying the resulting Co2C. In conclusion, the Co2C formed from the ZnOpromoted Co catalysts displays improved thermal stability and selectivity compared with similar Co2C catalysts without Zn.

Authors:
 [1]; ORCiD logo [2];  [1];  [2];  [1];  [1];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Stanford Univ., Stanford, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Stanford Univ., Stanford, CA (United States); Technical Univ. of Denmark Kongens, Lyngby (Denmark)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1507160
Grant/Contract Number:  
AC02-76SF00515; DGE‐114747
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 11; Journal Issue: 2; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; higher alcohol synthesis; in situ characterization; EXAFS modelling; cobalt carbide; density functional theory

Citation Formats

Singh, Joseph A., Hoffman, Adam S., Schumann, Julia, Boubnov, Alexey, Asundi, Arun S., Nathan, Sindhu S., Nørskov, Jens, Bare, Simon R., and Bent, Stacey F. Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas. United States: N. p., 2018. Web. doi:10.1002/cctc.201801724.
Singh, Joseph A., Hoffman, Adam S., Schumann, Julia, Boubnov, Alexey, Asundi, Arun S., Nathan, Sindhu S., Nørskov, Jens, Bare, Simon R., & Bent, Stacey F. Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas. United States. doi:10.1002/cctc.201801724.
Singh, Joseph A., Hoffman, Adam S., Schumann, Julia, Boubnov, Alexey, Asundi, Arun S., Nathan, Sindhu S., Nørskov, Jens, Bare, Simon R., and Bent, Stacey F. Tue . "Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas". United States. doi:10.1002/cctc.201801724. https://www.osti.gov/servlets/purl/1507160.
@article{osti_1507160,
title = {Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas},
author = {Singh, Joseph A. and Hoffman, Adam S. and Schumann, Julia and Boubnov, Alexey and Asundi, Arun S. and Nathan, Sindhu S. and Nørskov, Jens and Bare, Simon R. and Bent, Stacey F.},
abstractNote = {Controlling selectivity is a key goal in the design of a heterogeneous catalyst. Herein, we present detailed characterization and activity of silica–supported cobalt catalysts modified by atomic layer deposition of ZnO. After reduction, the resulting catalysts exhibit substantial selectivity towards alcohol production during CO hydrogenation compared to catalysts containing only cobalt. The prepared catalysts have up to 46 % selectivity toward alcohols with 39 % of the alcohols corresponding to ethanol and other higher alcohols, albeit with reduced activity. In situ characterization of the catalyst by X–ray diffraction and X–ray absorption spectroscopy reveals details on the structural evolution in syngas, CO+H2, and shows that ZnO promotion of Co results in the formation of Co2C under catalytic conditions. A mechanism is proposed, supported by density functional theory calculations, which explains Co2C formation by the blocking of Co step sites by Zn species. The ZnO acts a dual promoter both by facilitating Co2C formation and by modifying the resulting Co2C. In conclusion, the Co2C formed from the ZnOpromoted Co catalysts displays improved thermal stability and selectivity compared with similar Co2C catalysts without Zn.},
doi = {10.1002/cctc.201801724},
journal = {ChemCatChem},
number = 2,
volume = 11,
place = {United States},
year = {2018},
month = {12}
}

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