Ag@Pt等离激元复合纳米结构中热电子级联传输增强电催化反应  

Cascaded hot electron transfer within plasmonic Ag@Pt heterostructure for enhanced electrochemical reactions

作　　者：梁文凯 刘远兰 卞文逸 秦伟 王雅雯 郭为 李东 曾华杰 钟俊 孙迎辉 林海平 江林 Wenkai Liang;Yuanlan Liu;Wenyi Bian;Wei Qin;Yawen Wang;Wei Guo;Dong Li;Huajie Zeng;Jun Zhong;Yinghui Sun;Haiping Lin;Lin Jiang(Institute of Functional Nano and Soft Materials(FUNSOM),Jiangsu Key Laboratory for Carbon-Based Functional Materials&Devices,Soochow University,Suzhou 215123,China;College of Energy,Soochow Institute for Energy and Materials Innovations and Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province,Soochow University,Suzhou 215006,China;School of Physics and Information Technology,Shaanxi Normal University,Xi’an 710062,China)

机构地区：[1]Institute of Functional Nano and Soft Materials(FUNSOM),Jiangsu Key Laboratory for Carbon-Based Functional Materials&Devices,Soochow University,Suzhou 215123,China [2]College of Energy,Soochow Institute for Energy and Materials Innovations and Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province,Soochow University,Suzhou 215006,China [3]School of Physics and Information Technology,Shaanxi Normal University,Xi’an 710062,China

出　　处：《Science China Materials》2023年第6期2227-2234,共8页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(22072104 and 21822202);a project funded by Suzhou Key Laboratory of Functional Nano&Soft Materials;Suzhou Key Laboratory of Surface and Interface of Intelligent Matter(SZS2022011);the Collaborative Innovation Center of Suzhou Nano Science and Technology;the 111 project;the Joint International Research Laboratory of Carbon-Based Functional Materials and Devices。

摘　　要：将具有高催化活性的材料与等离激元金属纳米材料复合是制备局域表面等离激元共振增强电催化剂的常用策略.然而,这种复合方式不仅会降低等离激元材料的局域表面等离激元共振强度,同时会改变等离激元电磁场的逸散方式以及热电子在复合结构内部的传输途径,无法实现最佳的等离激元增强效果.在此,我们选择了简单的Ag@Pt双金属纳米立方体作为研究对象,深入探究了热电子在金属异质结构内部的激发和传输机制以及其在电化学析氢反应中的贡献.相应的实验和理论结果证实,Pt在Ag表面的复合会改变等离激元电磁场的逸散方式,促进激发产生更多热电子,同时热电子可以通过级联传输方式转移至复合结构表面,显著增强电催化反应.这项工作为等离激元金属异质结构催化剂的设计和应用提供了重要参考.A popular strategy for constructing localized surface plasmon resonance(LSPR)-enhanced plasmonic metal heterostructure catalysts is to fabricate a composite of highly active materials with plasmonic metal nanomaterials.However,this kind of combination not only decreases the LSPR response intensity but also changes the hot electron transport pathway inside the heterogeneous structure,which induces the ineffective transfer of plasmonic hot electrons to the surface of the heterostructures and hinders the effective enhancement of catalytic activity.Herein,simple Ag@Pt bimetallic nanocubes are selected to explore the mechanism of hot electrons from excitation and transmission within a plasmonic metal heterostructure and their contribution to the electrochemical hydrogen evolution reaction(HER).The corresponding experimental and theoretical results confirm that the hot electrons(holes)become a dominant plasmon decay pathway owing to the introduction of thin Pt shells and HER can be significantly enhanced by hot electrons via a cascaded manner,i.e.,first being excited in Ag,then pumped from Ag atoms to Pt atoms and accumulated on the surface of Pt.This work provides an important reference for the design and application of plasmonic metal heterostructure catalysts.

关 键 词：局域表面等离激元共振 电催化反应 等离激元 复合结构 纳米立方体 异质结构 复合纳米结构 金属纳米材料 

分 类 号：O643.36[理学—物理化学] TB383.1[理学—化学]