Kohila Rani Karuppasamy, Xiao Yuan-Hui, Devasenathipathy Rajkumar, Gao Kun, Wang Jiazheng, Kang Xing, Zhu Chengcheng, Chen Haonan, Jiang Lu, Liu Qinghua, Qiao Furong, Li Zhuoyao, Wu De-Yin, Lu Gang
Key Laboratory of Flexible Electronics, School of Flexible Electronics (Future Technologies), and Institute of Advanced Materials, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, PR China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Xiamen University, Xiamen 361005, PR China.
ACS Appl Mater Interfaces. 2024 May 29;16(21):27831-27840. doi: 10.1021/acsami.4c01259. Epub 2024 May 17.
Electro-optical synergy has recently been targeted to improve the separation of hot carriers and thereby further improve the efficiency of plasmon-mediated chemical reactions (PMCRs). However, the electro-optical synergy in PMCRs needs to be more deeply understood, and its contribution to bond dissociation and product selectivity needs to be clarified. Herein, the electro-optical synergy in plasmon-mediated reduction of -bromothiophenol (PBTP) was studied on a plasmonic nanostructured silver electrode using in situ Raman spectroscopy and theoretical calculations. It was found that the electro-optical synergy-induced enhancements in the cleavage of carbon-bromine bonds, reaction rate, and product selectivity (4,4'-biphenyl dithiol vs thiophenol) were largely affected by the applied bias, laser wavelength, and laser power. The theoretical simulation further clarified that the strong electro-optical synergy is attributed to the matching of energy band diagrams of the plasmonic silver with those of the adsorbed PBTP molecules. A deep understanding of the electro-optical synergy in PBTP reduction and the clarification of the mechanism will be highly beneficial for the development of other highly efficient PMCRs.
最近，电光协同效应已成为改善热载流子分离从而进一步提高等离子体介导化学反应（PMCRs）效率的目标。然而，PMCRs中的电光协同效应需要更深入地理解，其对键解离和产物选择性的贡献也需要阐明。在此，利用原位拉曼光谱和理论计算，在等离子体纳米结构银电极上研究了等离子体介导的对溴苯硫酚（PBTP）还原反应中的电光协同效应。研究发现，电光协同效应引起的碳溴键裂解增强、反应速率和产物选择性（4,4'-联苯二硫醇与苯硫酚相比）在很大程度上受到施加偏压、激光波长和激光功率的影响。理论模拟进一步阐明，强电光协同效应归因于等离子体银与吸附的PBTP分子的能带图匹配。深入理解PBTP还原反应中的电光协同效应并阐明其机制将对其他高效PMCRs的发展非常有益。
