Substitutional Platinum‐Phosphorus Solid Solution by Phosphidation of Worm‐Like Pt Nanoparticles Using Tri‐n‐octylphosphine

Herein, the investigations into the phosphidation of platinum (Pt) nanoparticles are reported using tri-n-octylphosphine (TOP) at elevated temperature in an organic solvent, and identify a unique phenomenon not addressed before: The phosphorus (P) atoms can replace partial Pt atoms from their lattice points to form a substitutional Pt-P solid solution. The rationality is authenticated for forming substitutional Pt-P solid solution via P doping by various characterizations and density functional theory (DFT) calculations, both of which suggests that the maximum P content in the Pt-P solid solution is approximately ≈10% for maintaining the stability of the face-centered cubic crystal structure.