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Title: Metal-promoted Mo6S8 clusters: a platform for probing ensemble effects on the electrochemical conversion of CO2 and CO to methanol

Abstract

Presented in this paper is an investigation of a promising ternary metal sulfide catalyst that is capable of electrochemically converting CO2 to liquid and gas fuels such as methanol and hydrogen. When promoted by copper, an extended structure of Chevrel-phase Mo6S8 clusters is capable of reducing CO2 and CO to methanol in aqueous conditions with an overpotential of –0.4 V vs. RHE. H2 gas is simultaneously and preferentially evolved during this process, contributing to total current densities as high as 35 mA cm–2. It has been observed that Cu2Mo6S8 displays unique catalytic activity in terms of product selectivity, and we attribute this activity to molybdenum sulfide cluster units based on the results of structural, electronic, and electroanalytical characterization. Also discussed is the formulation of an interesting electronic structure–function correlation founded on the basis of X-ray absorption spectroscopic analyses and corroborated by the results of electroanalytical evaluation, where it has been observed that introduction of metal promoting species into the Chevrel-phase framework encourages charge transfer into cluster chalcogen sites.

Authors:
 [1];  [2];  [1];  [1];  [3];  [3];  [1];  [4]; ORCiD logo [1]
  1. Univ. of California, Davis, CA (United States)
  2. Univ. of California, Davis, CA (United States); Univ. of Puerto Rico, Cayey, PR (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  4. D’Youville College, Buffalo, NY (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); Chevron Corporation; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH), National Institute of General Medical Sciences (NIGMS)
OSTI Identifier:
1608983
Alternate Identifier(s):
OSTI ID: 1560279
Grant/Contract Number:  
AC02-76SF00515; 1560479; P41GM103393; ECCS-1542152; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Materials Horizons
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2051-6347
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Perryman, Joseph T., Ortiz-Rodríguez, Jessica C., Jude, Joshua W., Hyler, Forrest P., Davis, Ryan C., Mehta, Apurva, Kulkarni, Ambarish R., Patridge, Christopher J., and Velázquez, Jesús M. Metal-promoted Mo6S8 clusters: a platform for probing ensemble effects on the electrochemical conversion of CO2 and CO to methanol. United States: N. p., 2019. Web. https://doi.org/10.1039/c9mh00745h.
Perryman, Joseph T., Ortiz-Rodríguez, Jessica C., Jude, Joshua W., Hyler, Forrest P., Davis, Ryan C., Mehta, Apurva, Kulkarni, Ambarish R., Patridge, Christopher J., & Velázquez, Jesús M. Metal-promoted Mo6S8 clusters: a platform for probing ensemble effects on the electrochemical conversion of CO2 and CO to methanol. United States. https://doi.org/10.1039/c9mh00745h
Perryman, Joseph T., Ortiz-Rodríguez, Jessica C., Jude, Joshua W., Hyler, Forrest P., Davis, Ryan C., Mehta, Apurva, Kulkarni, Ambarish R., Patridge, Christopher J., and Velázquez, Jesús M. Wed . "Metal-promoted Mo6S8 clusters: a platform for probing ensemble effects on the electrochemical conversion of CO2 and CO to methanol". United States. https://doi.org/10.1039/c9mh00745h. https://www.osti.gov/servlets/purl/1608983.
@article{osti_1608983,
title = {Metal-promoted Mo6S8 clusters: a platform for probing ensemble effects on the electrochemical conversion of CO2 and CO to methanol},
author = {Perryman, Joseph T. and Ortiz-Rodríguez, Jessica C. and Jude, Joshua W. and Hyler, Forrest P. and Davis, Ryan C. and Mehta, Apurva and Kulkarni, Ambarish R. and Patridge, Christopher J. and Velázquez, Jesús M.},
abstractNote = {Presented in this paper is an investigation of a promising ternary metal sulfide catalyst that is capable of electrochemically converting CO2 to liquid and gas fuels such as methanol and hydrogen. When promoted by copper, an extended structure of Chevrel-phase Mo6S8 clusters is capable of reducing CO2 and CO to methanol in aqueous conditions with an overpotential of –0.4 V vs. RHE. H2 gas is simultaneously and preferentially evolved during this process, contributing to total current densities as high as 35 mA cm–2. It has been observed that Cu2Mo6S8 displays unique catalytic activity in terms of product selectivity, and we attribute this activity to molybdenum sulfide cluster units based on the results of structural, electronic, and electroanalytical characterization. Also discussed is the formulation of an interesting electronic structure–function correlation founded on the basis of X-ray absorption spectroscopic analyses and corroborated by the results of electroanalytical evaluation, where it has been observed that introduction of metal promoting species into the Chevrel-phase framework encourages charge transfer into cluster chalcogen sites.},
doi = {10.1039/c9mh00745h},
journal = {Materials Horizons},
number = 1,
volume = 7,
place = {United States},
year = {2019},
month = {8}
}

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