Switching of electrochemical selectivity due to plasmonic field- induced dissociation

• 成果类型: Article
• 署名作者: Alcorn, Francis M.; Giri, Sajal Kumar; Chattoraj, Maya; Nixon, Rachel; Schatz, George C.; Jain, Prashant K.
• 署名单位: University of Illinois System; University of Illinois Urbana-Champaign; Northwestern University; University of Illinois System; University of Illinois Urbana-Champaign
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-13209
• DOI: 10.1073/pnas.2404433121
• 发表日期: 2024-10-08
• 关键词: hollow nanocrystals; spectroscopy; oxidation; heat; nanoparticles; reduction

摘要

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 CO2 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 CO2 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 CO2. These results highlight the potential of optically generated electric fields for modulating pathways, switching reactivity on/off, and even directing outcomes.