目的 开发高性能、低成本的非贵金属催化剂能够大幅降低电解水制氢技术的氢气制取成本,以满足工业化应用的需求。硫化钼（MoS2）作为一种用于析氢反应的新兴催化材料,其催化活性与材料厚度密切相关。方法 采用单极性脉冲磁控溅射技术,在泡沫镍基材上制备出具有不同厚度的硫化钼涂层,研究涂层厚度对其结构及催化析氢反应性能的影响规律,并结合微观表征与电化学测试系统分析其变化原因。结果 在泡沫镍基材表面制备得到厚度分别0.5、3.8、5.5、11.4 μm的硫化钼涂层,涂层呈竖直生长取向,具有典型的蠕虫状结构,且随着厚度的逐渐增大,涂层表面发生由半导体相（2H- MoS2）向金属相（1T- MoS2）的转变。当涂层厚度为5.5 μm时,表现出最优的电化学析氢催化性能,其在10 mA/cm2和100 mA/cm2电流密度下的过电位分别为138.2 mV和218.2 mV,具有最低的电荷转移阻抗（Rct）。结论 不同厚度的硫化钼涂层展示出析氢反应性能的规律性,且厚度与催化活性呈非线性关系,存在性能拐点。当涂层厚度适中时,硫化钼涂层既呈竖直生长的优势取向,又具有金属相的优良电荷传输能力,其催化性能最佳;然而随着厚度进一步增大,电荷转移阻抗的升高对电荷传输过程产生抑制,导致电化学性能发生恶化。
Abstract
The development of noble-metal-free catalysts with high catalytic efficiency and low cost can greatly reduce the cost of hydrogen production in electrolytic water hydrogen production technology. In recent years, molybdenum disulfide (MoS2) has been widely used in hydrogen evolution, and the catalytic activity of MoS2 thin film is closely related to its thickness. This study presents an innovative investigation into the hydrogen evolution reaction (HER) performance of MoS2 coatings with precisely controlled thicknesses which are deposited on nickel foam (NF) substrates. The physical vapor deposition technique, a significant advancement over conventional methods like hydrothermal synthesis or chemical vapor deposition lack of reproducibility and scalability, was utilized. The effect of thickness, a key parameter, on the structural characteristics and electrochemical performance of MoS2 was explored. Four distinct thicknesses of 0.5 μm, 3.8 μm, 5.5 μm, and 11.4 μm were obtained by varying the deposition time while keeping other sputtering parameters constant, allowing for a direct correlation between coating thickness, microstructure, phase composition, and HER activity.
Structural analysis via XRD revealed that all coatings were largely amorphous but exhibited discernible diffraction peaks. Crucially, the (100) peak, indicative of a vertical growth orientation which exposed more active edge sites, became more pronounced with the increasing thickness, particularly in the 5.5 μm sample. Raman spectroscopy and TEM imaging provided a key finding: a phase transition from the semiconducting 2H-MoS2 phase (in the 0.5 and 3.8 μm samples) to a metallic 1T-MoS2 phase (in the 5.5 and 11.4 μm samples) on the coating surface. This transition, likely induced by interlayer sliding from plasma bombardment during sputtering, was critical as the 1T-phase offered superior electrical conductivity. SEM imaging showed that the morphology evolved from small clusters to a typical, porous "worm-like" structure at moderate thicknesses (3.8 and 5.5 μm), which then fractured and became more compact upon excessive thickening (11.4 μm) due to stacking compression and resputtering effects.
Electrochemical performance metrics demonstrated a non-linear relationship between thickness and HER activity, identifying a clear performance optimum. The 5.5 μm coating delivered exceptional HER performance, exhibiting the lowest overpotentials of 138.2 mV and 218.2 mV at current densities of 10 mA/cm2 and 100 mA/cm2, respectively, and the smallest Tafel slope of 76.5 mV/dec, indicating favorable reaction kinetics. This sample also had the lowest charge transfer resistance (Rct = 0.028 Ω), as determined by EIS, facilitating efficient electron transport. Although the thickest sample (11.4 μm) possessed the largest electrochemical active surface area (Cdl = 97.9 mF/cm2) and a metallic surface phase, its HER performance degraded due to a significant increase in Rct (0.1 Ω), caused by excessive electron transport distance and compact stacking.
The thickness-dependent behavior is analyzed from the perspective of three core HER steps (Volmer, electron transfer and desorption). An optimal thickness (~5.5 μm) provides an ideal balance: a porous, vertically-aligned morphology with abundant edge sites for efficient H* adsorption, a metallic 1T-phase surface for optimal adsorption energy, and a moderate thickness ensuring low-resistance electron pathways from the substrate. Conversely, overly thick coatings hinder electrolyte penetration, trap H2 bubbles, and increase internal resistance, disrupting the adsorption-desorption balance and impairing performance. This work provides profound new insights into the role of coating thickness in electrocatalyst design, establishing magnetron-sputtered MoS2 as a highly promising and tunable non-precious metal catalyst for sustainable hydrogen production.
关键词
电解水制氢 /
金属相硫化钼 /
电化学析氢催化 /
涂层厚度
Key words
electrolytic water hydrogen production /
1T-MoS2 /
hydrogen evolution reaction /
coating thickness
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基金
西物创新行动项目（202301XWCX003）; 乐山市科技局项目（23GZD014）
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