Porous Molybdenum Phosphide Nano‐Octahedrons Derived from Confined Phosphorization in UIO‐66 for Efficient Hydrogen Evolution

Abstract Herein, a series of porous nano‐structured carbocatalysts have been fused and decorated by Mo‐based composites, such as Mo 2 C, MoN, and MoP, to form a hybrid structures. Using the open porosity derived from the pyrolysis of metal–organic frameworks (MOFs), the highly dispersive MoO 2 small nanoparticles can be deposited in porous carbon by chemical vapor deposition (CVD). Undergoing different treatments of carbonization, nitridation, and phosphorization, the Mo 2 C‐, MoN‐, and MoP‐decorated carbocatalysts can be selectively prepared with un‐changed morphology. Among these Mo‐based composites, the MoP@Porous carbon (MoP@PC) composites exhibited remarkable catalytic activity for the hydrogen evolution reaction (HER) in 0.5 m H 2 SO 4 aqueous solution versus MoO 2 @PC, Mo 2 C@PC, and MoN@PC. This study gives a promising family of multifunctional lab‐on‐a‐particle architectures which shed light on energy conversion and fuel‐cell catalysis.