Expedited Synthesis of Metal Phosphides Maximizes Dispersion, Air Stability, and Catalytic Performance in Selective Hydrogenation.

Metal phosphides have been hailed as potential replacements for scarce noble metal catalysts in many aspects of the hydrogen economy from hydrogen evolution to selective hydrogenation reactions. But the need for dangerous and costly phosphorus precursors, limited support dispersion, and low stability of the metal phosphide surface toward oxidation substantially lower the appeal and performance of metal phosphides in catalysis. We show here that a 1-step procedure that relies on safe and cheap precursors can furnish an air-stable NiP/AlO catalyst containing 3.2 nm nanoparticles. NiP/AlO is kinetically competitive with the palladium-based Lindlar catalyst in selective hydrogenation catalysis, and a loading corresponding to 4 ppm Ni was sufficient to convert 0.1 mol alkyne. The 1-step synthetic procedure alters the surface ligand speciation of NiP/AlO, which protects the nanoparticle surface from oxidation, and ensures that 85 % of the initial catalytic activity was retained after the catalyst was stored under air for 1.5 years. Preparation of NiP on a variety of supports (silica, TiO, SBA-15, ZrO, C and HAP) as well as CoP/AlO, CoP/TiO and bimetallic NiCoP/TiO demonstrates the generality with which supported metal phosphides can be accessed in a safe and straightforward fashion with small sizes and high dispersion.