Towards High‐Efficiency Hydrogen Production through in situ Formation of Well‐Dispersed Rhodium Nanoclusters

Abstract Rh‐based materials have emerged as potential candidates for hydrogen revolution from electrolyzing water or ammonia borane (AB) hydrolysis. Nevertheless, most of the catalysts still suffer from the complex synthetic procedures combined with limited catalytic activity. Additionally, the facile syntheses of Rh catalysts with high efficiencies for both electrochemical water splitting and AB hydrolysis are still challenging. Herein, we develop a simple, green, and mass‐producible ion‐adsorption strategy to produce a Rh/C pre‐catalyst (pre‐Rh/C). The ultrafine and clean Rh nanoclusters immobilized on carbon are achieved via the in situ reduction of the pre‐Rh/C during the hydrogen‐evolution process. The resulting in situ Rh/C catalyst presents an outstanding electrocatalytic performance with low overpotentials of 8 and 30 mV at 10 mA cm −2 in 1.0 m KOH and 0.5 m H 2 SO 4 , respectively, outperforming the state‐of‐the‐art Pt catalysts. Furthermore, the in situ Rh/C is also highly active for AB hydrolysis to produce hydrogen with a high turnover frequency of 1246 mol mol Rh −1 min −1 at 25 °C. The in situ‐formed ultrafine Rh nanoclusters are responsible for the observed superior catalytic performance. This facile in situ strategy to realize a highly active catalyst shows promise for practical applications.