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The growing demand for sustainable energy has led to in-depth research on hydrogen production from electrolyzed water, where the development of electrocatalysts is a top priority. We here report a controllable strategy for preparing the cobalt-nickel alloy nanoparticles encapsulated in nitrogen-doped porous carbon by annealing a bimetal-organic framework. The delicately tailored hierarchical Co2Ni@NC nanoparticles effectively realize abundant synergistic active sites and fast mass transfer for the oxygen evolution reaction (OER). Remarka