隨著能源需求持續增加，傳統化石燃料的大量消耗所造成的環境污染與碳排放問題日益受到重視。為因應能源轉型與減碳需求，氫能因具零碳排放潛力而被視為重要的潔淨能源。近年來，海水電解因可直接利用豐富海洋資源，成為具潛力的永續產氫技術，但仍面臨鹽類沉積、高腐蝕性及電極穩定性不足等挑戰。此外，析氫反應(HER)受限於緩慢的反應動力學，因此開發高效且耐久的電催化觸媒已成為重要研究方向。 本研究採用超聲震盪輔助濕化學法，成功製備可應用於0.5 M硫酸與鹼性模擬海水中的高效HER電催化觸媒，並以金屬有機框架(metal-organic frameworks， MOFs)衍生材料作為載體，建構以釕(Ru)為核心之催化系統。首先，以H3BTC(1，3，5-苯三甲酸)作為有機配體，搭配不同金屬比例合成NixAgy-BTC(x : y = 1:0、1:2、1:1、2:1、0:1)做為基材；隨後透過離子置換方式引入Ru，使其均勻分散於材料中，最後經鍛燒處理以增加孔洞數量與比表面積。Ru與Ni、Ag之協同作用可有效調控氫吸附自由能，而高導電性的Ag則有助於提升電子傳輸效率與反應動力學。此外，多孔結構能提供大量活性位點、優異的離子傳導能力與良好的結構穩定性，進一步提升HER催化活性。後續利用電化學工作站評估其HER性能，並結合X光繞射(XRD)、高解析度穿透式電子顯微鏡(HRTEM)、能量散射X射線光譜(EDS)、X光光電子能譜(XPS)與感應耦合電漿光學發射光譜(ICP-OES)等分析技術，探討材料之元素組成、晶體結構、晶格特徵與元素價態等性質。 在不同組成比例之Ru@NixAgy/C觸媒中，最佳化樣品Ru@Ni2Ag1/C於酸性與鹼性模擬海水中皆展現優異HER性能。在電流密度10 mA cm-2下，其過電位(η10)於酸性與鹼性條件中分別僅需35與12 mV，Tafel斜率則分別為24與18 mV dec¬¬¬-1；經5000圈加速劣化測試後，過電位仍僅增加至49與21 mV，Tafel斜率分別為33與26 mV dec-1，相較於純Ru/C對照組具有更佳之催化活性與穩定性，顯示其具備優異的抗腐蝕能力與長期操作潛力。 此外，透過HRTEM觀察Ru@Ni/C與Ru@Ni2Ag1/C之微觀形貌，可發現Ag元素導入後會驅動其向材料表面擴散，以降低整體表面能，進而改變材料成長方向，使原本「棒狀結構伴隨顆粒聚集」的形貌轉變為「鬆散分枝/海藻狀」結構。此現象屬於表面能驅動之形貌重構，不僅顯著增加反應表面積與活性位點數量，也與HER性能提升結果相互呼應。 綜合以上結果可知，本研究成功開發同時含有Ru、Ni與Ag之多元金屬觸媒系統，可藉由元素間的協同效應有效調控氫吸附行為。其中，Ag的導入除了提升電子傳輸與反應動力學外，亦能誘導形貌重構，大幅提高HER催化活性與穩定性。本研究成果為海水電解產氫技術提供了一項具潛力之觸媒設計策略，並展現未來潔淨能源應用之發展價值。
關鍵字：析氫反應、海水電解、金屬有機框架、鎳、銀、釕基觸媒;With the continuous growth in global energy demand， the extensive consumption of traditional fossil fuels has led to increasing concerns regarding environmental pollution and carbon emissions. To address the needs of energy transition and carbon reduction， hydrogen energy has been regarded as an important clean energy source due to its potential for zero carbon emissions. In recent years， seawater electrolysis has emerged as a promising sustainable hydrogen production technology because of the abundant availability of seawater resources. However， its practical application still faces several challenges， including salt precipitation， severe corrosion， and insufficient electrode stability. In addition， the hydrogen evolution reaction (HER) is intrinsically limited by sluggish reaction kinetics， making the development of highly efficient and durable electrocatalysts an important research focus. In this study， highly efficient HER electrocatalysts applicable to 0.5 M H2SO4 and alkaline simulated seawater were successfully synthesized using an ultrasonic-assisted wet chemical method. Metal–organic framework (MOF)-derived materials were employed as supports to construct a Ru-based catalytic system. First， H3BTC (1，3，5-benzenetricarboxylic acid) was used as the organic ligand， and NixAgy-BTC (x : y = 1:0， 1:2， 1:1， 2:1， and 0:1) precursors were synthesized using different metal ratios as substrates. Subsequently， Ru was introduced through an ion-exchange process to achieve uniform dispersion within the material， followed by calcination to increase the pore quantity and specific surface area. The synergistic interaction among Ru， Ni， and Ag effectively regulated the hydrogen adsorption free energy， while the highly conductive Ag enhanced electron transfer efficiency and reaction kinetics. Furthermore， the porous structure provided abundant active sites， excellent ion transport capability， and superior structural stability， thereby significantly improving HER catalytic activity. Electrochemical measurements were conducted to evaluate HER performance， while X-ray diffraction (XRD)， high-resolution transmission electron microscopy (HRTEM)， energy-dispersive X-ray spectroscopy (EDS)， X-ray photoelectron spectroscopy (XPS)， and inductively coupled plasma optical emission spectroscopy (ICP-OES) were employed to investigate the elemental composition， crystal structure， lattice characteristics， and valence states of the catalysts. Among the Ru@NixAgy/C catalysts with different compositions， the optimized Ru@Ni2Ag1/C sample exhibited outstanding HER performance in both acidic and alkaline simulated seawater. At a current density of 10 mA cm-2， the overpotentials (η10) were only 35 and 12 mV under acidic and alkaline conditions， respectively， while the corresponding Tafel slopes were 24 and 18 mV dec-1. After 5000 accelerated degradation cycles， the overpotentials increased only slightly to 49 and 21 mV， with Tafel slopes of 33 and 26 mV dec-1， respectively. Compared with the pure Ru/C reference catalyst， Ru@Ni2Ag1/C demonstrated superior catalytic activity and stability， indicating excellent corrosion resistance and long-term operational durability. Moreover， HRTEM observations of Ru@Ni/C and Ru@Ni2Ag1/C revealed that the introduction of Ag induced surface diffusion to reduce the overall surface energy， thereby altering the crystal growth direction. As a result， the morphology transformed from a “rod-like structure with aggregated particles” into a “loosely branched/seaweed-like structure.” This phenomenon can be attributed to surface-energy-driven morphological reconstruction， which significantly increased the reaction surface area and the number of active sites， consistent with the observed enhancement in HER performance. Overall， the results demonstrate that the developed multimetallic catalyst system containing Ru， Ni， and Ag can effectively regulate hydrogen adsorption behavior through synergistic effects among the constituent elements. The incorporation of Ag not only improves electron transfer and reaction kinetics but also induces morphological reconstruction， thereby greatly enhancing HER catalytic activity and stability. This study provides a promising catalyst design strategy for seawater electrolysis-based hydrogen production and highlights its potential for future clean energy applications.
