本研究成功利用微陽極導引電鍍法（MAGE），於陰極上製備出排列均勻之三維鎳鋅（Ni-Zn）合金微柱結構，並系統性探討其在1.0 M KOH 鹼性電解液中的陰極析氫反應（HER）動力學機制。在1.0 M KOH 鹼性電解液中歷經長時間循環伏安測試後，表面活潑的鋅原子發生電化學去合金化而選擇性浸出，驅使殘留的活性鎳原子於固－液界面進行擴散與形貌自組裝重組，相比於幾何表面積0.3067cm2最終構築出電化學有效表面積（ECSA）達115.75 cm2的高度互連網狀多孔骨架結構。由變溫極化曲線與交流阻抗頻譜（EIS）之交叉驗證得知，隨操作溫度由25°C升高至60°C，Tafel 斜率絕對值由93.05 mV/dec規律收斂至58.09 mV/dec，表觀電荷轉移阻抗（Rct，app）亦顯著衰減，在動力學上確認了速率決定步驟的轉變：低溫下反應主要受到Volmer 步驟的限制；高溫下熱能注入有效加速了水分子的解離活化，使速率決定步驟轉變為由Heyrovsky步驟主導。常溫變電位阻抗頻譜則顯示，在高過電位（η≧150 mV）時，阻抗譜中中低頻區域顯著下彎並跨越至第四象限，誘發出獨特的感抗弧特徵，具體反映了表面高密度吸附氫中間體因脫附速率滯後所產生的延遲響應，並證實高驅動力下部分吸附氫已克服擴散能障，開啟了向晶格內部擴散之亞表面氫滲透機制，展現了鎳鋅合金特有的優異動態儲放氫能力。最後，導入修正型電化學 BEP 線性自由能關係式逆推，由表觀速率常數（kapp）法求得之表觀活化能（43.77 kJ/mol）成功標定該材料之氫吸附自由能（△GH*）為＋0.066 eV，相較於純鎳（－0.27 eV）與純鋅，其熱力學X軸座標已近乎完美地向火山圖頂端之白金（Pt）理想活性區間靠攏。儘管在微觀縱軸維度上，受限於鋅的低本質活性，使系統在「幾何表面積的增加（位點擴展）」與「材料本質催化活性」之間存在著相互制約的折衷關係（Trade-off）；然而，本研究所設計之三維微柱結構，成功藉由巨大的有效活性表面積與鋅溶蝕產生之多孔結構展現出顯著的幾何增益，有效突破並化解了本質動力學受限的瓶頸，為高效能、低成本之工業級鹼性水電解陰極催化材料奠定了堅實的理論與設計基礎。;In this study， a well-aligned three-dimensional (3D) Ni–Zn alloy micropillar architecture was successfully fabricated on a cathode via micro-anode guided electroplating (MAGE). The hydrogen evolution reaction (HER) kinetics and underlying mechanisms were systematically investigated in 1.0 M KOH alkaline electrolyte.Following prolonged cyclic voltammetry (CV) activation， the electrochemically active Zn component underwent selective electrochemical dealloying and dissolution. This process drove the redistribution and self-assembly of the remaining Ni atoms at the solid–liquid interface， ultimately forming a highly interconnected porous network. As a result， across a geometric surface area of 0.3067 cm²， the electrochemically active surface area (ECSA) reached 115.75 cm². Temperature-dependent polarization measurements combined with electrochemical impedance spectroscopy (EIS) revealed a progressive decrease in the absolute Tafel slope from 93.05 mV dec⁻¹ at 25 °C to 58.09 mV dec⁻¹ at 60 °C， accompanied by a substantial reduction in apparent charge-transfer resistance (Rct，app). These results indicate a clear transition in the rate-determining step (RDS)， where the HER is primarily governed by the Volmer step at low temperatures， while enhanced water dissociation and hydrogen adsorption kinetics at elevated temperatures shift the reaction toward a Heyrovsky-controlled pathway. In addition，Potential-dependent EIS measurements further demonstrated that under high cathodic overpotentials (|η| ≥ 150 mV)， the impedance spectra exhibited a pronounced downward bending into the fourth quadrant， resulting in a characteristic inductive loop. This behavior is attributed to the delayed relaxation of adsorbed hydrogen intermediates (Hads) arising from desorption hysteresis. Moreover， the inductive response suggests that a fraction of adsorbed hydrogen may overcome the diffusion barrier and penetrate into the subsurface lattice， indicating the dynamic hydrogen storage and release capability of the Ni–Zn alloy. By applying a modified electrochemical Brønsted–Evans–Polanyi (BEP) relationship， the apparent activation energy derived from the apparent rate constant (kapp) method (43.77 kJ mol⁻¹) was successfully correlated with a hydrogen adsorption free energy (ΔGH*) of +0.066 eV. Compared with pure Ni (− 0.27 eV) and pure Zn， this value places the Ni–Zn alloy significantly closer to the apex of the HER volcano plot， approaching the thermodynamically optimal Pt region.Although the incorporation of Zn inevitably introduces a trade-off between intrinsic catalytic activity and active-site density， the hierarchical micropillar architecture developed in this work effectively compensates for this limitation through a substantial increase in accessible active surface area and the formation of a porous framework generated by selective Zn dissolution. Consequently， the synergistic integration of compositional tuning and three-dimensional structural engineering provides an effective strategy for developing high-performance， low-cost cathode materials for industrial alkaline water electrolysis.
