A Theoretical and Experimental Approach for Correlating Nanoparticle Structure and Electrocatalytic Activity

作者：Rachel M. Anderson, David F. Yancey, Liang Zhang, Samuel T. Chill, Graeme Henkelman, Richard M. Crooks · 发表于：Accounts of Chemical Research · 年份：2015 · DOI：10.1021/acs.accounts.5b00125 · 被引用次数：92 · 研究领域：Electrocatalysts for Energy Conversion、Catalytic Processes in Materials Science、Catalysis and Hydrodesulfurization Studies

The objective of the research described in this Account is the development of high-throughput computational-based screening methods for discovery of catalyst candidates and subsequent experimental validation using appropriate catalytic nanoparticles. Dendrimer-encapsulated nanoparticles (DENs), which are well-defined 1-2 nm diameter metal nanoparticles, fulfill the role of model electrocatalysts. Effective comparison of theory and experiment requires that the theoretical and experimental models map onto one another perfectly. We use novel synthetic methods, advanced characterization techniques, and density functional theory (DFT) calculations to approach this ideal. For example, well-defined core@shell DENs can be synthesized by electrochemical underpotential deposition (UPD), and the observed deposition potentials can be compared to those calculated by DFT. Theory is also used to learn more about structure than can be determined by analytical characterization alone. For example, density functional theory molecular dynamics (DFT-MD) was used to show that the core@shell configuration of Au@Pt DENs undergoes a surface reconstruction that dramatically affects its electrocatalytic properties. A separate Pd@Pt DENs study also revealed reorganization, in this case a core-shell inversion to a Pt@Pd structure. Understanding these types of structural changes is critical to building correlations between structure and catalytic function. Indeed, the second principal focus of the work de...