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Professor Matt Kanan's Research on CO2 Electroreduction Featured in Science

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Dec 1 2017

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Faculty, In the News

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

Ruperto G. Mariano, Kim McKelvey, Henry S. White, Matthew W. Kanan

Going with the grain boundaries

Bulk defects in a metal, such as grain boundaries, can create regions of increased strain at its surface that could affect its catalytic activity. Mariano et al. studied the electroreduction of CO2 to CO on polycrystalline gold films, a reaction that competes with H2 evolution. By annealing the films to create larger grains, they could change the types and distribution of grain boundaries at the surface. Scanning electrochemical cell microscopy revealed that the dislocation density correlated with CO2 electroreduction activity, but such defects had no effect on H2 evolution.


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.

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