Deciphering the Local Environment of Electrocatalytic Metal Sites with X‐ray Absorption Fine Structure

Abstract

Electrocatalysis plays a pivotal role in energy conversion and holds significant promise for the development of new energy sources. Understanding the intricate atomic‐level interplay between active sites and electrocatalytic activity is essential for comprehending catalytic behavior and advancing high‐performance catalysts. In this review, an overview of the recent advances in X‐ray absorption fine structure (XAFS) is provided for deciphering the local environment of electrocatalytic metal sites. The application of XAFS in disclosing the electronic interaction and coordination environment of metal sites is summarized, offering insights into the correlation between ligand arrangement and catalytic activity. Special attention is given to advanced XAFS techniques for exploring active species, including determining the actual active sites, monitoring the local structure transformation, and deciphering metal sites–catalysis relationship. The limitations of traditional XAFS have naturally prompted the development of high‐spatiotemporal‐resolution and high‐energy‐resolution techniques as well as in‐situ/operando methods to better understand the entire catalytic process. This review is anticipated to provide a comprehensive understanding of the capabilities of XAFS in exploring the fine structure of electrocatalysts, with implications for the design of advanced catalytic materials.