Heterogeneous catalysts often undergo structural transformations when they operate under thermal reaction conditions. These transformations are reflected in their evolving catalytic activity, and a fundamental understanding of the changing nature of active sites is vital for the rational design of solid materials for applications. Beyond thermal catalysis, both photocatalysis and electrocatalysis are topical because they can harness renewable energy to drive uphill reactions that afford commodity chemicals and fuels. Although structural transformations of photocatalysts and electrocatalysts have been observed in operando, the resulting implications for catalytic behaviour are not fully understood. In this Review, we summarize and compare the structural evolution of solid thermal catalysts, electrocatalysts and photocatalysts. We suggest that well-established knowledge of thermal catalysis offers a good basis to understand emerging photocatalysis and electrocatalysis research.
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