Bulk and supported nickel phosphides were prepared by thermal treatment of a mechanical mixing of nickel chloride and sodium hypophosphite in a flowing N-2. The samples were characterized using thermogravimetric analysis, X-ray diffraction, and inductively coupled plasma. The effect of different aspects on the Ni2P formation was primarily investigated. A rational mechanism was proposed for the selective formation of Ni2P. SiO2-supported Ni2P exhibits excellent hydrodesulfurization (HDS) activity for dibenzothiophene (DBT). (C) 2011 Elsevier B.V. All rights reserved.