Bottom-up evolution of perovskite clusters into high-activity rhodium nanoparticles toward alkaline hydrogen evolution

Self-reconstruction has been considered an efficient means to prepare efficient electrocatalysts in various energy transformation process for bond activation and breaking. However, developing nano-sized electrocatalysts through complete in-situ reconstruction with improved activity remains challenging. Herein, we report a bottom-up evolution route of electrochemically reducing Cs₃Rh₂I₉ halide-perovskite clusters on N-doped carbon to prepare ultrafine Rh nanoparticles (~2.2 nm) with large lattice spacings and grain boundaries. Various in-situ and ex-situ characterizations including electrochemical quartz crystal microbalance experiments elucidate the Cs and I extraction and Rh reduction during the electrochemical reduction. These Rh nanoparticles from Cs₃Rh₂I₉ clusters show significantly enhanced mass and area activity toward hydrogen evolution reaction in both alkaline and chlor-alkali electrolyte, superior to liquid-reduced Rh nanoparticles as well as bulk Cs₃Rh₂I₉-derived Rh via top-down electro-reduction transformation. Theoretical calculations demonstrate water activation could be boosted on Cs₃Rh₂I₉ clusters-derived Rh nanoparticles enriched with multiply sites, thus smoothing alkaline hydrogen evolution.