The Predominance of Hydrogen Evolution on Transition Metal Sulfides and Phosphides under CO_2 Reduction Conditions: An Experimental and Theoretical Study
Abstract
A combination of experiment and theory has been used to understand the relationship between the hydrogen evolution reaction (HER) and CO_2 reduction (CO_2R) on transition metal phosphide and transition metal sulfide catalysts. Although multifunctional active sites in these materials could potentially improve their CO_2R activity relative to pure transition metal electrocatalysts, under aqueous testing conditions, these materials showed a high selectivity for the HER relative to CO_2R. Computational results supported these findings, indicating that a limitation of the metal phosphide catalysts is that the HER is favored thermodynamically over CO_2R. On Ni-MoS_2, a limitation is the kinetic barrier for the proton–electron transfer to *CO. These theoretical and experimental results demonstrate that selective CO_2R requires electrocatalysts that possess both favorable thermodynamic pathways and surmountable kinetic barriers.
Additional Information
© 2018 American Chemical Society. Received: February 9, 2018; Accepted: April 20, 2018; Publication Date (Web): May 31, 2018. This material is based, in part, on work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy, under Award No. DE-SC0004993. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy (under Contract No. DE-AC02-05CH11231). Part of this work was performed at the Stanford Nano Shared Facilities (SNSF) and the Stanford Nanofabrication Facility (SNF), supported by the National Science Foundation under Award ECCS-1542152. We also acknowledge assistance from the Stanford NMR Facility. M.F. and D.A.T. acknowledge a graduate fellowship through the National Science Foundation. S.A.F. acknowledges the Resnick Sustainability Institute at Caltech for a postdoctoral fellowship. The authors also thank J. Chance Crompton for assistance in synthesizing the nanoparticle electrocatalysts. The authors declare no competing financial interest.Attached Files
Supplemental Material - nz8b00237_si_001.pdf
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Additional details
- Alternative title
- The Predominance of Hydrogen Evolution on Transition Metal Sulfides and Phosphides under CO2 Reduction Conditions: An Experimental and Theoretical Study
- Eprint ID
- 86732
- Resolver ID
- CaltechAUTHORS:20180601-080239556
- Department of Energy (DOE)
- DE-SC0004993
- Department of Energy (DOE)
- DE-AC02-05CH11231
- NSF
- ECCS-1542152
- NSF Graduate Research Fellowship
- Resnick Sustainability Institute
- Created
-
2018-06-01Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field
- Caltech groups
- JCAP, Resnick Sustainability Institute