Light tuning CO/H_(2)composition on Ag:Unraveling CO_(2)mass transfer and electron-phonon coupling in plasmon-enhanced electrocatalysis  

作　　者：Rui Lin Dong Fan Luca MBerger Thomas Possmayer Yu Zhou Jiexin Zhu Xingbao Chen Wen Luo Lars Allmendinger Andreas Tittl Leonardo de Souza Menezes Guillaume Maurin Shihe Yang and Stefan AMaier 

机构地区：[1]Nanoinstitute Munich,Faculty of Physics,Ludwig-Maximilians-Universität München,80539 Munich,Germany [2]Institut Charles Gerhardt Montpellier UMR 5253 CNRS ENSCM,UniversitéMontpellier,Place E.Bataillon,34090 Montpellier,France [3]Guangdong Provincial Key Lab of Nano-Micro Material Research,School of Advanced Materials,Peking University Shenzhen Graduate School,Shenzhen 518055,China [4]State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,Wuhan University of Technology,Wuhan 430070,China [5]Faculty of Chemistry and Pharmacy,Ludwig-Maximilians-Universität München,81377 Munich,Germany [6]Departamento de Física,Universidade Federal de Pernambuco,50670-901 Recife-PE,Brazil [7]School of Physics and Astronomy,Monash University Clayton Campus,Melbourne,Victoria 3800,Australia [8]Department of Physics,Imperial College London,SW72AZ London,UK

出　　处：《Nano Research》2025年第1期173-185,共13页纳米研究（英文版）

基　　金：support from Alexander von Humboldt foundation;the National Natural Science Foundation of China(Nos.21972006,U2001217 and 22261160370);the funding from Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)under grant numbers EXC 2089/1-390776260(Germany’s Excellence Strategy)and TI 1063/1(Emmy Noether Program),the Bavarian Program Solar Energies Go Hybrid(SolTech)and the Center for NanoScience(CeNS).Co-funded by the European Union(ERC,METANEXT,101078018);expressed are however those of the author(s)only and do not necessarily reflect those of the European Union or the European Research Council Executive Agency.Neither the European Union nor the granting authority can be held responsible for them.

摘　　要：Plasmon-enhanced electrocatalysis(PEEC)is an emerging approach to mitigate CO_(2)emissions.The mechanisms behind CO_(2)adsorption and reduction at the catalyst-electrolyte interface in PEEC still need to be further explored.Herein,we employ a well-defined Ag nanostructure to elucidate these pivotal issues.By shining light with wavelengths of 625,525,405 nm on Ag,an adjustable CO/H_(2)ratio from 35 to 1 can be obtained.The reaction pathway changing under plasmonic excitation does not originate from the lowered CO_(2)mass transfer in the vicinity of Ag,as the electrochemical quartz crystal microbalance results unravel that a slightly elevated temperature in bulk electrolyte caused by light irradiation cannot weaken the CO_(2)adsorption at the Ag catalyst-electrolyte interface.Theoretical calculations reveal that optical excitation towards shorter wavelengths leads to a progressive lowered energy barrier for H_(2)formation together with an enhanced energy barrier for^(*)COOH formation.Although thermodynamically suppressed,CO_(2)reduction can still be improved kinetically by optimizing the excitation wavelength and intensity,being accompanied with the enhanced photocurrent.Transient absorption spectroscopy results further correlate the higher photocurrent with a prolonged electron-phonon coupling time,verifying that the improvement of CO_(2)reduction kinetics in PEEC can be realized by hot electron harnessing.

关 键 词：plasmonic catalysis photoelectrochemical CO_(2)reduction CO/H_(2)ratio hot electron generation electronphonon coupling thermal effect 

分 类 号：O64[理学—物理化学]