Probing and controlling Cu catalyst reconstruction during CO₂ electroreduction

The dynamic structural reconstruction of Cu-based catalysts profoundly influences activity, selectivity and stability during electrochemical CO₂ reduction (CO₂RR). However, it lacks standardized methodologies for probing and actively managing these transformations. Here we present a modular, reproducible Protocol that integrates electrochemical control, in situ/operando spectroscopy and mechanistic analysis to systematically investigate and regulate Cu catalyst reconstruction under CO₂RR conditions. This Protocol establishes a comprehensive 'reconstruction-understanding-intervention' workflow comprising (1) the identification and taxonomy of reconstruction phenomena, (2) quantification of electrochemical and environmental factors governing reconstruction, (3) correlation of structural dynamics with catalytic behavior through complementary in situ/operando Raman, infrared, X-ray absorption spectroscopy and quasi-in situ X-ray photoelectron spectroscopy measurements, and (4) development of rational reconstruction-control strategies that steer catalysts toward desired active states. A systematic approach is delineated to correlate reconstruction dynamics with catalytic performance and actively direct the process toward desired active states via three primary strategies: catalyst structure modulation, electrochemical operation regulation and reaction microenvironment management. The methodology is validated using representative Cu-based systems, including commercial Cu, oxide-derived Cu and bimetallic Cu-X catalysts, demonstrating enhanced performance and stability of CO₂RR. This workflow also provides an adaptable framework for investigating dynamic surface evolution in other electrocatalytic reactions. This Protocol provides useful framework for the rational development of adaptive, stable and selective electrocatalysts.