Switching of electrochemical selectivity due to plasmonic field-induced dissociation
[2];
[1];
[1];
[2];
[3]
- Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, IL 61801
- Department of Chemistry, Northwestern University, Evanston, IL 60208
- Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, IL 61801, Materials Research Laboratory, University of Illinois Urbana-Champaign, Urbana, IL 61801
Electrochemical reactivity is known to be dictated by the structure and composition of the electrocatalyst–electrolyte interface. Here, we show that optically generated electric fields at this interface can influence electrochemical reactivity insofar as to completely switch reaction selectivity. We study an electrocatalyst composed of gold–copper alloy nanoparticles known to be active toward the reduction of CO 2 to CO. However, under the action of highly localized electric fields generated by plasmonic excitation of the gold–copper alloy nanoparticles, water splitting becomes favored at the expense of CO 2 reduction. Real-time time-dependent density functional tight binding calculations indicate that optically generated electric fields promote transient-hole-transfer-driven dissociation of the O─H bond of water preferentially over transient-electron-driven dissociation of the C─O bond of CO 2 . These results highlight the potential of optically generated electric fields for modulating pathways, switching reactivity on/off, and even directing outcomes.
- Sponsoring Organization:
- USDOE
- Grant/Contract Number:
- SC0004752
- OSTI ID:
- 2452839
- Journal Information:
- Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 41 Vol. 121; ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of SciencesCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Similar Records
Interfacial Properties of Gold and Cobalt Oxyhydroxide in Plasmon-Mediated Oxygen Evolution Reaction
Formate-Induced Dissolution and Reprecipitation of a Copper Electrocatalyst during Electrochemical CO2 Reduction Reaction