全球淨零碳排趨勢與再生能源需求大幅增長的背景下，氫能作為清潔能源載體的需求日益迫切。相較於傳統電解水，直接海水電解技術有效緩解全球淡水資源稀缺的壓力。然而，海水環境中高濃度的氯離子及其誘發的副反應常造成觸媒腐蝕與活性降低，嚴重挑戰系統的穩定性。此外，傳統貴金屬觸媒成本昂貴，限制了其廣泛應用。因此，開發具備低成本、高活性及高穩定性的非貴重金屬析氫觸媒，已成為推動大規模綠氫生產的關鍵任務。 本研究設計用於鹼性海水中的高效析氫反應(hydrogen evolution reaction， HER)電催化觸媒，本研究利用簡易兩步法成功製備出原位生長於泡沫鎳之鎳鉬(NiMo)基觸媒。該材料具備獨特的合金/氧化物異質結構，可作為雙活性位點並產生協同作用，有效克服非貴金屬觸媒在鹼性環境中動力學遲緩的瓶頸。研究進一步鈰 (Ce) 摻雜策略，精確調控電子結構以優化氫吸附能，同時誘導產生的氧空位顯著提升了水解離能力。此外，碳包覆保護層的引入不僅增強了導電性，更確保了在長時間操作下的結構穩定性。其中，Ce-Ni4Mo(U)@C/NF 於鹼性模擬海水中，在 10 mA /cm2 下的過電位僅為 28 mV，塔佛(Tafel) 斜率為 28 mV/dec。並在 5，000 圈加速耐久性測試後仍維持高活性，證實其高效催化及具有長時間應用的潛力。 為深入探討觸媒的催化機制，進行了臨場X光吸收光譜(in-situ X-ray absorption spectroscopy， XAS)分析，以解析HER過程中的活性及穩定性機制。XAS 結果證實，Ce 的引入有效調控了電子結構，並優化了 NiMo 合金的析氫活性界面；同時，碳包覆層的保護作用確保了觸媒在海水電解反應中展現出卓越的整體結構穩定性。總結而言，本研究開發之 Ce-Ni4Mo(U)@C/NF 不僅備高經濟效益，其電催化活性更可比肩商用 Pt/C 觸媒。憑藉出色的長效穩定性，為未來大規模海水電解產氫提供了一套極具潛力的方案。;Driven by global net-zero emissions trends and the surging demand for renewable energy， hydrogen has become an increasingly vital clean energy carrier. Compared to conventional water electrolysis， seawater electrolysis significantly mitigates the pressure on global freshwater scarcity. However， the high concentration of chloride ions (Cl⁻) and their induced side reactions present severe challenges， including catalyst deactivation and corrosion， which threaten system stability. Furthermore， the high cost of commercial noble metal catalysts limits their widespread application. Therefore， developing low-cost， high-activity， and stable non-noble metal catalysts is crucial for large-scale green hydrogen production. In this study， a high-efficiency electrocatalyst for the hydrogen evolution reaction (HER) in alkaline seawater was designed. A NiMo-based catalyst was successfully grown in-situ on nickel foam via a facile two-step method. The resulting material features a unique alloy/oxide heterostructure that acts as synergistic dual-active sites， effectively overcoming the sluggish kinetics of non-noble metals in alkaline media. Furthermore， a Ce doping strategy was employed to modulate the electronic structure， optimizing the hydrogen adsorption energy while inducing the formation of oxygen vacancies to enhance water dissociation. Additionally， the introduction of a carbon coating not only improves electrical conductivity but also ensures structural stability during long-term operation. Notably， the Ce-Ni4Mo(U)@C/NF achieved an ultralow overpotential of 28 mV at 10 mA/cm2 with a Tafel slope of 28 mV/dec in alkaline simulated seawater. It maintained high activity after 5，000 accelerated durability test (ADT) cycles， confirming its potential for sustained， high-efficiency catalysis. To further elucidate the catalytic mechanism， in-situ X-ray absorption spectroscopy (XAS) was performed to analyze the active sites and stability during the HER process. XAS results confirm that Ce incorporation effectively tunes the electronic structure and optimizes the active interface of the NiMo alloy. Simultaneously， the protective carbon coating ensures superior overall structural stability during seawater electrolysis. In summary， the developed Ce-Ni4Mo(U)@C/NF catalyst is not only cost-effective but also exhibits catalytic activity comparable to commercial Pt/C catalysts. With its outstanding long-term stability， this work provides a promising low-cost technical solution for future large-scale seawater hydrogen production.
