We prepared higher surface area nickel phosphides than are normally found by reducing nickel phosphate. To do this, we hydrothermally synthesized Ni hydroxy phosphite precursors with low levels of molybdenum substitution. The molybdenum substitution increases the surface area of these precursors. During pretreatment in a sulfiding atmosphere ( such as H2S/H-2) dispersed islands of MoS2 segregate from the precursor and provide a pathway for H-2 dissociation that allows reduction of the phosphite precursor to nickel phosphide at substantially lower temperatures than in the absence of MoS2. The results reported here show that to create nickel phosphides with comparable activity to conventional supported sulfide catalysts, one would have to synthesize the phosphide with surface areas exceeding 400 m(2)/g (i.e. with nanoparticles less than 30 angstrom in lateral dimension). (C) 2014 Elsevier B.V. All rights reserved.