Light tuning CO/H2 composition on Ag: Unraveling CO2 mass transfer and electron-phonon coupling in plasmon-enhanced electrocatalysis

被引：0

作者：

Lin, Rui ^{[1
]}

Fan, Dong ^{[2
]}

Berger, Luca M. ^{[1
]}

Possmayer, Thomas ^{[1
]}

Zhou, Yu ^{[3
]}

Zhu, Jiexin ^{[4
]}

Chen, Xingbao ^{[4
]}

Luo, Wen ^{[4
]}

Allmendinger, Lars ^{[5
]}

Tittl, Andreas ^{[1
]}

Menezes, Leonardo de Souza ^{[1
,6
]}

Maurin, Guillaume ^{[2
]}

Yang, Shihe ^{[3
]}

Maier, Stefan A. ^{[7
,8
]}

机构：

[1] Ludwig Maximilians Univ Munchen, Fac Phys, Nanoinst Munich, D-80539 Munich, Germany

[2] Univ Montpellier, Inst Charles Gerhardt Montpellier, CNRS, UMR 5253,ENSCM, Pl E Bataillon, F-34090 Montpellier, France

[3] Peking Univ, Shenzhen Grad Sch, Sch Adv Mat, Guangdong Prov Key Lab Nanomicro Mat Res, Shenzhen 518055, Peoples R China

[4] Wuhan Univ Technol, State Key Lab Adv Technol Mat Synth & Proc, Wuhan 430070, Peoples R China

[5] Ludwig Maximilians Univ Munchen, Fac Chem & Pharm, D-81377 Munich, Germany

[6] Univ Fed Pernambuco, Dept Fis, BR-50670901 Recife, PE, Brazil

[7] Monash Univ, Sch Phys & Astron, Clayton Campus, Melbourne, Vic 3800, Australia

[8] Imperial Coll London, Dept Phys, London SW7 2AZ, England

来源：

NANO RESEARCH | 2025年 / 18卷 / 01期

基金：

中国国家自然科学基金;

关键词：

plasmonic catalysis; photoelectrochemical CO2 reduction; CO/H2; ratio; hot electron generation; electron- phonon coupling; thermal effect; HOT-ELECTRONS; ELECTROCHEMICAL REDUCTION; CARBON-DIOXIDE; CARRIER; ELECTROREDUCTION; SELECTIVITY; CONVERSION; SCIENCE; SURFACE; DESIGN;

D O I：

10.26599/NR.2025.94907042

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Plasmon-enhanced electrocatalysis (PEEC) is an emerging approach to mitigate CO2 emissions. The mechanisms behind CO2 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/H2 ratio from 35 to 1 can be obtained. The reaction pathway changing under plasmonic excitation does not originate from the lowered CO2 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 CO2 adsorption at the Ag catalyst-electrolyte interface. Theoretical calculations reveal that optical excitation towards shorter wavelengths leads to a progressive lowered energy barrier for H2 formation together with an enhanced energy barrier for *COOH formation. Although thermodynamically suppressed, CO2 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 CO2 reduction kinetics in PEEC can be realized by hot electron harnessing.

引用

页数：13

共 83 条

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