Selective increase in CO₂ electroreduction activity at grain-boundary surface terminations

Altering a material's catalytic properties requires identifying structural features that give rise to active surfaces. Grain boundaries create strained regions in polycrystalline materials by stabilizing dislocations and may provide a way to create high-energy surfaces for catalysis that are kinetically trapped. Although grain-boundary density has previously been correlated with catalytic activity for some reactions, direct evidence that grain boundaries create surfaces with enhanced activity is lacking. We used a combination of bulk electrochemical measurements and scanning electrochemical cell microscopy with submicrometer resolution to show that grain-boundary surface terminations in gold electrodes are more active than grain surfaces for electrochemical carbon dioxide (CO₂) reduction to carbon monoxide (CO) but not for the competing hydrogen (H₂) evolution reaction. The catalytic footprint of the grain boundary is commensurate with its dislocation-induced strain field, providing a strategy for broader exploitation of grain-boundary effects in heterogeneous catalysis.