A simple and efficient approach to the preparation of hollow or porous metal phosphide nanoparticles was presented. Bulk and supported Ni2P, CoP, FeP, and Cu3P were successfully synthesized by reducing metal pyrophosphate precursors in flowing hydrogen. The structural properties of these samples are investigated using X-ray powder diffraction, transmission electron microscopy, inductively coupled plasma and X-ray photoemission spectroscopy. The Ni2P/SiO2 catalysts were used for the gas phase catalytic hydrodesulfurization of dibenzothiophene. The hydrodesulfurization activity of the catalyst reached 99% when the reaction temperature was 340 degrees C. In the paper, a possible reaction mechanism was discussed to form Ni2P, CoP, FeP, and Cu3P. The route and mechanism could also be applied to the preparation of other metal phosphides. (C) 2013 Elsevier B.V. All rights reserved.