Transition metal metaphosphates and noble metal phosphides prepared under similar conditions are potential hybrid catalysts for electrocatalytic water splitting, which is of great significance for H production. Herein, the structure and electrocatalytic activity of different noble metal species (i.e., Rh, Pd, Ir) on CoNiPO nanoarrays have been systematically studied. Due to the different formation energies of noble metal phosphides, the phosphides of Rh (RhP) and Pd (PdP) as well as the noble metal Ir are obtained under the same phosphorylation conditions perspectively. RhP/CoNiPO and PdP/CoNiPO exhibit much better HER activity than Ir/CoNiPO due to the advantages of phosphides. Density functional theory (DFT) calculations reveal that the extraordinary activity of RhP/CoNiPO originated from the strong affinity to HO and optimal adsorption for H*. The best RhP/CoNiPO only requires a low overpotential of 30 and 234 mV to deliver 10 mA cm for HER and OER, respectively, and therefore is effective for overall water splitting (requiring 1.57 V to achieve a current density of 10 mA cm). This work not only develops a novel RhP/CoNiPO electrocatalyst for overall water splitting but also provides deep insight into the formation mechanism of noble metal phosphides.
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