The size modulation of catalyst particles represents a useful dimension to tune catalytic performances by impacting not only their surface areas but also local electronic structures. It, however, has remained inadequately explored and poorly elucidated. Here, we report the interesting size‐dependent selectivity of electrochemical CO2 reduction on In2O3 nanocrystals. 5‐nm nanoparticles and 15‐nm nanocubes with focused size distribution are prepared via a facile solvothermal reaction in oleylamine by carefully controlling a set of experimental parameters. They serve as the precatalysts, and are reduced to In nanocrystals while largely inherit the original size feature during electrochemical CO2 reduction. Catalyst derived from 15‐nm nanocubes exhibits greater formate selectivity (>95 %) at lower overpotential and negligible side reactions compared to bulk‐like samples (indium foil and 200‐nm cubes) as well as the catalyst derived from smaller 5‐nm nanoparticles. This unique size dependence is rationalized as a result of the competition among different reaction pathways by our theoretical computations. Smaller is not always better in the catalyst design.

The carbonylation reaction is an effective way to introduce CO or other carbonyl groups into organic compounds, and widely used in the preparation of aldehydes, ketones, amides, and esters. The replacement of conventional reaction approaches by greener electrochemical methods is appealing with great synthetic potential as well as inherent safety, owing to the avoidance of external oxidants or reductants and a more facile control in product selectivity. In this minireview, we give a summary of the recent development of carbonylation reactions via the electrochemical approach.

The size modulation of catalyst particles represents a useful dimension to tune catalytic performances by impacting not only their surface areas but also local electronic structures. It, however, has remained inadequately explored and poorly elucidated. Here, we report the interesting size‐dependent selectivity of electrochemical CO2 reduction on In2O3 nanocrystals. 5‐nm nanoparticles and 15‐nm nanocubes with focused size distribution are prepared via a facile solvothermal reaction in oleylamine by carefully controlling a set of experimental parameters. They serve as the precatalysts, and are reduced to In nanocrystals while largely inherit the original size feature during electrochemical CO2 reduction. Catalyst derived from 15‐nm nanocubes exhibits greater formate selectivity (>95 %) at lower overpotential and negligible side reactions compared to bulk‐like samples (indium foil and 200‐nm cubes) as well as the catalyst derived from smaller 5‐nm nanoparticles. This unique size dependence is rationalized as a result of the competition among different reaction pathways by our theoretical computations. Smaller is not always better in the catalyst design.