文献类型：期刊文献

中文题名：解析单颗粒电化学分步电子转移步骤用于识别电催化剂本征活性

英文题名：Clarifying sequential electron‐transfer steps in single‐nanoparticle electrochemical process for identifying the intrinsic activity of electrocatalyst

作者：孙泽晖[1];来壮壮[2];赵影影[1];陈建富[2];马巍[1]

机构：[1]华东理工大学化学与分子工程学院,材料生物学和动态化学前沿科学中心,先进材料重点实验室和费林加诺贝尔奖科学家联合研究中心国际合作联合实验室,上海200237;[2]华东理工大学计算化学中心和工业催化研究所,绿色化学工程与工业催化国家重点实验室,上海200237

年份：2024

卷号：60

期号：5

起止页码：262

中文期刊名：Chinese Journal of Catalysis

外文期刊名：催化学报（英文）

收录：CSTPCD;;EI(收录号：20242116130890);WOS:【SCI-EXPANDED(收录号:WOS:001271979200001)】；CSCD:【CSCD2023_2024】；

基金：This work was supported by the Major Research Project (92061108 , the National Natural Science Foundation of China (22272052 , and the Fundamental Research Funds for the Central Universities.

语种：中文

中文关键词：单颗粒;电催化剂;电子转移;决速步;本征活性

外文关键词：Single nanoparticle;Electrocatalyst;Electron transfer;Rate-determining step;Intrinsic activity

摘要：揭示电催化剂本征活性对于量化其构-效关系至关重要.传统的整体表征方法只能提供大量纳米颗粒(NP)的平均性能,并且通常难以排除添加剂的贡献.单颗粒碰撞电化学(SNCE)技术能够有效地在单NP水平上揭示电催化剂活性.尽管SNCE领域已取得了很大的研究进展,但目前人们对其反应中的电子转移过程认识尚不充分,难以提供NPs结构与活性之间的定量关系.本文以铂纳米颗粒(PtNPs)氧还原反应(ORR)作为SNCE过程的模型体系,通过构建功能化锥形碳微米电极(CNE)界面,有效地调控了ORR电催化过程,揭示了SNCE分步电子转移在调节单个PtNP表观ORR活性中的重要作用.分别采用化学刻蚀和元素功能化技术调控CNE界面的表面粗糙度和氮元素掺杂组成,构筑了光滑碳电极(s-CNE)、粗糙碳电极(r-CNE)、光滑氮掺杂碳电极(sN-CNE)和粗糙氮掺杂碳电极(rN-CNE)四种功能化电极界面.实验表明,单个PtNP在s-CNE、r-CNE、sN-CNE和rN-CNE这四种功能化CNE界面上产生的ORR电流强度依次增大(即s-CNESingle-nanoparticle collision electrochemistry(SNCE)is an effective method for determining the intrinsic activity of electrocatalysts at the single-nanoparticle(NP)level.Despite fruitful advancements in the SNCE field,determining a quantitative relationship between the NP structure and its activity has remained difficult because of an unclear understanding of SNCE.In this study,we successfully uncovered the essential roles of the sequential electron-transfer steps in the SNCE system in regulating the apparent electrocatalytic activity of single NPs.By monitoring the oxygen reduction reaction of individual Pt NPs,significantly distinct apparent activities were observed at different electrodes owing to the rate-determining step-controlled electron transfer process.Furthermore,a new theoretical model is proposed for treating the electrochemical current,which involves NP-electrode electron transfer,heterogeneous electron transfer,and mass transfer in solution as sequential steps in the SNCE system.The combination of theoretical simulations and high-resolution electrochemical measurements allows for the corresponding parameters(contact resistance,heterogeneous kinetic constants,and adsorption possibility)of sequential electron-transfer steps to be quantified,resulting in the identification of a rate-determining step for improving the intrinsic activity of electrocatalysts.This work provides a clear picture for determining the intrinsic activity of single NPs in SNCE measurements and introduces a new conceptual route for the quantification of structure-activity relationships,which ultimately guide the rational design and optimization of electrocatalytic nanomaterials.