摘要：Sluggish water dissociation kinetics severely limits the rate of alkaline electrocatalytic hydrogen evolution reaction(HER).Therefore,finding highly active electrocatalysts and clarifying the mechanism of water dissociation are challenging but *** this study,we report an integrated nanoporous nickel(np-Ni)catalyst with high alkaline HER performance and the origin of the corresponding enhanced catalytic *** 1 mol L^(-1) KOH solution,this np-Ni electrode shows an HER overpotential of 20 mV at 10 mA cm^(-2),along with fast water dissociation *** excellent performance is not only attributed to the large surface area provided by the three-dimensional interconnected conductive network but also from the enhanced intrinsic activity induced by the unique surface *** studies reveal that the types of oxygen species that naturally form on the Ni surface play a key role in water ***,when the lattice oxygen almost disappears,the Ni surface terminates with_(ads)orbed oxygen(O_(ads)),exhibiting the fastest water dissociation *** functional theory calculation suggests that when O_(ads)acts as the surface termination of Ni metal,the orientation and configuration of polar water molecules are strongly affected by O_(ads).Finally,the H–OH bond of interfacial water molecules is effectively activated in a manner similar to hydrogen *** work not only identifies a high-performance and low-cost electrocatalyst but also provides new insights into the chemical processes underlying water dissociation,thus benefiting the rational design of electrocatalysts.