Interfacial Electron Transfer Strategy to Improve the Hydrogen Evolution Catalysis of CrP Heterostructure

Abstract Though several Pt‐free hydrogen evolution reaction (HER) catalysts have been reported, their employment for industry is challenging. Here, a facile pyrolysis method to obtain phase‐pure CrP nanoparticles supported on N, P dual‐doped carbon (CrP/NPC) is reported to be tuned toward industrial HER. Interestingly, CrP/NPC exhibits excellent HER activity that requires an overpotential of 34 mV to attain a current density of 10 mA cm⁻², which is only 1 mV positive to commercial Pt/C and a potential of 55 mV to achieve a current density of 200 mA cm⁻² which is better than Pt/C. In addition, the long‐term durability of CrP/NPC is far superior to Pt/C due to the strong interaction between CrP and C support, restricting any agglomeration or leaching. Density functional theory (DFT) calculations suggest that electronic modulation at the interface (CrP/NPC) optimizes the hydrogen adsorption energy. The Cr–Cr bridge site with required density of states near the Fermi level is found to be the active site. Overall, this report provides a practical scheme to synthesize rarely investigated CrP based materials along with a computational mechanistic guideline for electrocatalysis that can be utilized to explore other phosphides for various applications.