Synergistically Coupling of Manganese-Doped CoP Nanowires Arrays with Highly Dispersed Ni(PO 3 ) 2 Nanoclusters toward Efficient Overall Water Splitting.

Co-based phosphides are considered to be highly promising electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, their electrocatalytic efficiencies are greatly limited by the weak water dissociation process and unsatisfactory adsorption ability toward reaction intermediates. Herein, novel Mn-doped CoP/Ni(PO 3 ) 2 heterostructure array electrocatalysts which are composed of highly dispersed Ni(PO 3 ) 2 nanoclusters that are tightly wrapped on Mn-doped CoP nanowire arrays are designed. An electrocatalytic performance test suggested that the heterostructure arrays exhibited competitive electrocatalytic performance toward both HER and OER, which needed overpotentials of 116 and 245 mV to drive a current of 10 mA/cm 2 , respectively. Encouragingly, a symmetric two electrode water splitting system constructed by the heterostructure arrays required an ultralow cell voltage, suggesting the potential in overall water splitting. First-principles calculations combined with experimental characterization were further performed to clarify the electrocatalytic mechanism. On the one hand, effective doping of Mn atoms could optimize the surface electronic structure of CoP and promote the intrinsic activity. On the other hand, the compact and abundant heterogeneous interface between Ni(PO 3 ) 2 and CoP not only made more active sites exposed but also promoted the effective adsorption of intermediate reaction species on the catalyst surface. This work provides a new strategy to improve electrocatalytic performance of Co-based phosphides through the synergistic coupling of metal-doping and phosphate surface decoration, which will greatly promote the development of highly efficient electrocatalysts for overall water splitting.