Alcorn Francis M, Kumar Giri Sajal, Chattoraj Maya, Nixon Rachel, Schatz George C, Jain Prashant K
Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, IL 61801.
Department of Chemistry, Northwestern University, Evanston, IL 60208.
Proc Natl Acad Sci U S A. 2024 Oct 8;121(41):e2404433121. doi: 10.1073/pnas.2404433121. Epub 2024 Oct 2.
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 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 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. These results highlight the potential of optically generated electric fields for modulating pathways, switching reactivity on/off, and even directing outcomes.
众所周知，电化学反应活性由电催化剂 - 电解质界面的结构和组成决定。在此，我们表明该界面处光生电场能够影响电化学反应活性，甚至完全改变反应选择性。我们研究了一种由金 - 铜合金纳米颗粒组成的电催化剂，已知其对将CO还原为CO具有活性。然而，在金 - 铜合金纳米颗粒的等离子体激发产生的高度局域化电场作用下，水分解变得更有利，而以CO还原为代价。实时含时密度泛函紧束缚计算表明，光生电场优先促进由瞬态空穴转移驱动的水分子O─H键解离，而非由瞬态电子驱动的CO分子C─O键解离。这些结果凸显了光生电场在调节反应路径、开启/关闭反应活性甚至引导反应结果方面的潜力。
