Selectively Growing a Highly Active Interface of Mixed Nb–Rh Oxide/2D Carbon for Electrocatalytic Hydrogen Production

Abstract Tailorable electron distribution of the active sites is widely regarded as the key issue to boost the catalytic activity and provide mechanistic insights into the structure–property–performance relationship. Here, a selective metal atom in situ growth strategy to construct highly active interface of mixed metal atom with different Nb_yRhO_x species on sp‐/sp²‐cohybridized graphdiyne (Nb_yRhO_x/GDY) is reported. With this innovative idea implemented, experimental results show that the asymmetric electron distribution and the variation of coordination environment of bimetallic species significantly improve the electrocatalytic activity of Nb_yRhO_x/GDY. Optimal hydrogen evolution reaction (HER) activity is achieved at the Nb/Rh ratio of 0.23, exhibiting excellent HER activity with the small overpotentials of 14 and 10 mV at 10 mA cm⁻² in alkaline and neutral electrolytes. The data show the strong potential for real‐system application of such catalysts, which outperform commercial Pt/C (20 wt%). These results shown in this study represent a platform for designing novel catalytic materials by selectively introducing metal atoms on different supports, which can be used as a general method extended to other catalytic systems.