Electrocatalytic activity and sorption behavior of hydrogen in nanosized Pd–Si–(Cu) metallic glass thin film and Pd thin film electrodes sputtered on a Si/SiO₂ substrate were investigated by linear sweep voltammetry, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrode MG4 (Pd₆₉Si₁₈Cu₁₃) exhibits the best performance with the highest electrocatalytic activity in the hydrogen evolution region with less than half of the Tafel slope of Pd thin film of the same thickness and lowest overpotential at 10 mA cm⁻². A new approach has been adopted by a nonlinear fitting of the entire region of the polarization curve (far- and near-equilibrium cathodic and anodic regions) to the Butler-Volmer model. α parameter is lowest for the MG2 electrode (Pd₇₉Si₁₆Cu₅), marking that nonequilibrium conditions change the reaction kinetics. Together with MG2, MG4 shows the lowest Bode magnitude values for hydrogen sorption and evolution regions, indicating that the bonding and release of hydrogen atoms to the electrode is easier. MG4 electrode shows a dramatic decrease of the overpotential after 100 cycles, yielding an increase in hydrogen activity. Besides, MG4 exhibits the sharpest current density drop in the HER region in cyclic voltammetry compared with other MG and Pd electrodes, indicating higher electrocatalytic activity towards hydrogen evolution. The findings highlight the influence of the selected metallic glasses for the design and development of metal catalysts with higher sorption kinetics and/or electrocatalytic turnover.

中文翻译：

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氢化钯金属玻璃纳米膜的电催化行为：Butler-Volmer，Tafel和阻抗分析

通过线性扫描伏安法，循环伏安法和电化学阻抗谱研究了纳米级Pd-Si-（Cu）金属玻璃薄膜和溅射在Si / SiO ₂衬底上的Pd薄膜电极中氢的电催化活性和吸附行为。电极MG4（Pd ₆₉ Si ₁₈ Cu ₁₃）在氢气析出区域表现出最好的性能，具有最高的电催化活性，且具有相同厚度的Pd薄膜的Tafel斜率不到一半，且在10 mA cm ^-2时的过电势最低。。通过将极化曲线的整个区域（远和近平衡的阴极和阳极区域）非线性拟合到Butler-Volmer模型，采用了一种新方法。α参数是最低为MG2电极（钯₇₉的Si ₁₆的Cu ₅），表明非平衡条件改变了反应动力学。MG4与MG2一起显示氢吸附和放出区域的最低Bode量值，表明氢原子与电极的键合和释放更容易。MG4电极在100次循环后显示出过电势的急剧下降，从而导致氢活度增加。此外，与其他MG和Pd电极相比，MG4在循环伏安法中在HER区的电流密度下降幅度最大，表明其对氢析出的电催化活性更高。这些发现突出了所选金属玻璃对具有更高吸附动力学和/或电催化转化率的金属催化剂的设计和开发的影响。