Three-dimensional microstructured nickel phosphide (Ni2P) was fabricated by the reaction between foam nickel (Ni) and phosphorus red. The as-prepared Ni2P samples, as interconnected networks, maintained the original mesh structure of fciamed nickel. The crystal structure and morphology of the as-synthesized Ni2P were characterized by X-ray diffraction, scanning electron microscopy, automatic mercury porosimetry and X-ray photoelectron spectroscopy. The SEM study showed adjacent hollow branches were mutually interconnected to form sponge-like networks. The investigation on pore structure provided detailed information for the hollow microstructures. The growth mechanism for the threedimensionally structured Ni2P was postulated and discussed in detail. To investigate its catalytic properties, SiO2 supported three-dimensional Ni2P was prepared successfully and evaluated for the hydrodesulfurization (HDS) of dibenzothiophene (DBT). DBT molecules were mostly hydrogenated and then desulfurized by Ni2P/SiO2. (C) 2014 Elsevier Ltd. All rights reserved.