Ni2P that was highly active in the hydrodesulfurization of dibenzothiophene was obtained by reduction of a phosphate precursor with a P/Ni molar ratio as low as 1.2 over cerium oxide-modified Al2O3 (CeAl2O3) and macromesoporous Al2O3 (M-Al2O3). Al-27 MAS NMR revealed that this is likely due to the low reactivity of pentahedrally coordinated Al3+ (Al(P)) with phosphorus oxide. Because the major Al species in Ce-Al2O3 and M-Al2O3 is Al(P), less phosphorus is consumed by the Al2O3 support upon calcination and thus more phosphorus is available for the formation of Ni2P during the reduction stage. (C) 2015 Elsevier Inc. All rights reserved.