Chemical reconstruction of bismuth oxyiodides using bicarbonates is tried to selectively grow (BiO)2CO3 edge side. Orthorhombic o‐Bi5O7I undergoes a total reconstruction process by its phase transformation into tetragonal (BiO)2CO3 (BOC‐o) to form a well‐aligned nanosheet array with maximally exposing CO32− moiety at the edge side. The post‐reconstruction BOC‐o catalyst achieved 100 % Faradaic efficiency at −0.86 V vs. RHE for CO2‐to‐formate conversion. However, another conservative reconstruction of tetragonal t‐BiOI into tetragonal (BiO)2CO3 (BOC‐t) exposed majorly a less reactive [BiO]+ layer. At low overpotential regions, the catalytic cycle of BOC‐o begins with the initial conversion of the CO32− moiety into formate at the [−OBi−(CO3)−BiO−] site, but at high overpotential regions, the [BiO]+ layer undergoes reduction to metallic Bi and multi‐catalytic species proceed with CO2 reduction. Otherwise, the deactivation of Bi+ site by an organic molecule switched on another catalysis of proton reduction, preventing CO2 reduction.
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