A novel bifunctional electrocatalyst for water splitting was constructed with the CoSe/MoSe2 heterojunction encapsulated within a nitrogen-doped carbon matrix (Co1Mo2Se/Co-N-C). This catalyst was synthesized via a facile one-step high-temperature calcination process. By optimizing the molar ratio of n(Co)/n(Mo) and the calcination temperature, a unique architecture was achieved featuring uniformly dispersed nanoparticles, well-defined heterointerfaces, and isolated Co atoms embedded in the carbon layer. Such structural features facilitated efficient transfer of electrons and maximized exposure of active sites. Electrochemical evaluations in 1.0 mol·L−1 KOH demonstrated that Co1Mo2Se/Co-N-C exhibited excellent hydrogen evolution reaction performance, requiring an overpotential of only 63 mV to reach 10 mA·cm−2 with a Tafel slope of 60 mV·dec−1, comparable to that of commercial Pt/C. For oxygen evolution reaction, the catalyst achieved an overpotential of 328 mV at 10 mA·cm−2 and a Tafel slope of 97 mV·dec−1. Furthermore, a full water splitting cell based on this catalyst reached 10 mA·cm−2 at an applied voltage of 1.623 V. These results highlight synergistic effects of the heterojunction and the nitrogen-doped carbon matrix, offering a promising strategy for the sustainable hydrogen production.
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