From Ensemble Electrochemistry to Nano‐Impact Electrochemistry: Altered Reaction Selectivity.

Selective electrochemical production of valued chemicals is of significant importance but remains a great challenge in chemistry. Conventional approaches for enhancing reaction selectivity focus on the improvement of the catalysts themselves. In this work, we systematically studied the reaction kinetics and mass transport behavior of LaNiO3 nanocubes (LaNiO3 NCs) catalyzed hydrogen peroxide reduction reaction (HPRR) at ensemble and single nanoparticle levels using nano‐impact electrochemistry (NIE). We find that the selectivity of HPRR was altered at individual random‐walk nanoparticles as compared to their ensemble counterpart without changing the reaction kinetics, due to the significantly enhanced mass transport at single nanoparticles. This discovery offers the scope of new catalytic approaches for engineering electrochemical reactions in general. [ABSTRACT FROM AUTHOR]