Sequential *CO management via controlling in situ reconstruction for efficient industrial-current-density CO-to-C electroreduction.

Sequentially managing the coverage and dimerization of *CO on the Cu catalysts is desirable for industrial-current-density CO reduction (COR) to C, which required the multiscale design of the surface atom/architecture. However, the oriented design is colossally difficult and even no longer valid due to unpredictable reconstruction. Here, we leverage the synchronous leaching of ligand molecules to manipulate the seeding-growth process during COR reconstruction and construct Cu arrays with favorable (100) facets. The gradient diffusion in the reconstructed array guarantees a higher *CO coverage, which can continuously supply the reactant to match its high-rate consumption for high partial current density for C. Sequentially, the lower energy barriers of *CO dimerization on the (100) facets contribute to the high selectivity of C. Profiting from this sequential *CO management, the reconstructed Cu array delivers an industrial-relevant FE of 86.1% and an FE of 60.8% at 700 mA cm. Profoundly, the atomic-molecular scale delineation for the evolution of catalysts and reaction intermediates during COR can undoubtedly facilitate various electrocatalytic reactions.