Electrochemical reduction of CO to highly valuable products is a promising way to reduce CO emissions. The shape and facets of metal nanocatalysts are the key parameters in determining the catalytic performance. However, the exposed crystal facets of ZnO with different morphologies and which facets achieve a high performance for CO reduction are still controversial. Here, we systematically investigate the effect of the facet-dependent reactivity of reduction of CO to CO on ZnO (nanowire, nanosheet, and flower-like). The ZnO nanosheet with exposed (110) facet exhibited prominent catalytic performance with a Faradaic efficiency of CO up to 84% and a current density of -10 mA cm at -1.2 V versus RHE, far outperforming the ZnO nanowire (101) and ZnO nanoflower (103). Based on detailed characterizations and kinetic analysis, the ZnO nanosheet (110) with porous architecture increased the exposure of active sites. Further studies revealed that the high CO selectivity originated from the enhancement of CO adsorption and activation on the ZnO (110) facet, which promoted the conversion of CO toward CO. This study provides a new way to tailor the activity and selectivity of metal catalysts by engineering exposed specific facets.
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