The development of high-efficiency and low-cost catalysts for hydrogen release from chemical hydrogen-storage materials is essential for the hydrogen-economy paradigm. Herein, we report a facile and controllable method to fabricate a series of Co-doped nickel phosphides and their corresponding nanohybrids with graphene oxide (GO) as highly efficient, robust and noble-metal-free catalysts for ammonia borane hydrolysis. The incorporation of Co into Ni₂P effectively optimizes the electronic structures of Ni_2−xCo_xP catalysts to enhance their interaction with AB and simultaneously facilitate the hydroxyl activation of AB, resulting in the reduction of the reaction energy barrier and thus substantial improvement of the catalytic rate.

Transition metal phosphide (CoP,Ni₂P,Cu₃P)/CdS hybrid catalysts were applied to heterogeneous photocatalytic hydrogen evolution and exhibited splendid photocatalytic activity with a H₂-production rate of up to 254 000 μmol h⁻¹ g⁻¹ and excellent stability in aqueous acidic media.