Operando XAS and Raman Perspectives on Catalyst Design.

Driven by accelerating global warming and the imperative of carbon neutrality, the search for efficient electrochemical energy-conversion technologies has intensified. Recent advances in electrocatalysis have introduced strategies to overcome kinetic, selectivity, and stability constraints in the carbon dioxide reduction reaction, oxygen reduction reaction, and water splitting. These developments range from atomic-scale structural modulation to microenvironment engineering, yielding substantial gains in product selectivity, reduced overpotential, and enhanced operational durability. This review consolidates representative breakthroughs across these three reaction domains and emphasizing design principles that couple performance optimization with mechanistic insight through operando X-ray absorption spectroscopy (XAS) and Raman spectroscopy. XAS resolves chemical states and local coordination environments, while Raman tracks surface-bound intermediates; together, they enable a comprehensive elucidation of catalytic mechanisms. The review also outlines key directions for advancing efficient, robust, and scalable electrochemical energy-conversion systems.