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Electrochemical-phosphorization as a cost-effective and ecofriendly approach is proposed to fabricate an amorphous Ni–P shell partially covering the surface of ordered porous Ni (p-Ni) for the first time. The obtained Ni–P/p-Ni shows superior catalytic activity for the hydrogen evolution reaction (HER), compared with the Ni2P/p-Ni prepared by a traditional solid-phosphorization process at high temperature. Such enhanced catalytic activity for the Ni–P/p-Ni is contributed to by the high intrinsic activity from a synergistic effect of amorphous Ni–P and the neighbouring nickel containing hydroxides/oxides. [ABSTRACT FROM AUTHOR]