AI 中文总结
本研究通过低能离子辐照制备亚稳态氢化铂薄膜，结合多种表征方法揭示了氢/氘在铂薄膜中的分布、动力学及热稳定性，为铂基相关领域的氢动力学研究提供了关键认识。
AI 中文摘要
氢（H）和氘（D）与过渡金属的相互作用在多相催化及氢相关技术中发挥核心作用。尽管氢-铂（H-Pt）的表面相互作用已被广泛研究，但由于氢在铂中的溶解度较低，直接探究氢在铂中的掺入与输运的研究仍较为有限。本研究通过低能离子辐照制备亚稳态$PtH(D)_x$薄膜，实现了远超平衡浓度的氢负载，以此探究H（D）的掺入与解吸动力学。核反应分析（NRA）显示氢的深度分布不均匀，存在两个富集区域：次表面和薄膜-基底界面。热解吸光谱（TDS）在190 K和230 K附近呈现两个解吸峰，与这两个位点的氢释放行为一致。采用双并联通道传导模型分析电阻弛豫测量结果，表明次表面氢与近界面氢的弛豫动力学存在差异。对平均氢浓度$x=0.15$的$PtH_x$进行阿伦尼乌斯分析，得到次表面氢的活化能为$130\textit{±}18$ meV，近界面氢的活化能为$164\textit{±}26$ meV。在140 K以上，相同注入剂量制备的$PtD_x$中，氘的弛豫速率更慢，对应的活化能分别为$117\textit{±}8$ meV和$121\textit{±}7$ meV。在实验不确定度范围内，活化势垒相近，但氘的指前因子显著降低，表明存在与同位素相关的尝试频率和零点能效应。基于波拉尼-维格纳（Polanyi-Wigner）形式主义的TDS模拟通过区分次表面与近界面的贡献，重现了实验解吸光谱，与NRA的分布结果一致。这些发现为铂基催化、传感及氢-金属相互作用领域中$PtH_x$的氢动力学提供了深入认识。
英文摘要
Hydrogen (H) and deuterium (D) interactions with transition metals play a central role in heterogeneous catalysis and hydrogen-related technologies. While H-Pt surface interactions have been extensively studied, direct investigations of hydrogen incorporation and transport in Pt remain limited due to its low solubility. Here, we study H(D) incorporation and desorption dynamics in metastable $PtH(D)_x$ thin films prepared by low-energy ion irradiation, enabling hydrogen loading far above equilibrium concentrations. Nuclear reaction analysis (NRA) reveals a nonuniform hydrogen depth profile with two accumulation regions: the subsurface and the film-substrate interface. Thermal desorption spectroscopy (TDS) exhibits two desorption peaks near 190 and 230 K, consistent with hydrogen release from these sites. Resistance relaxation measurements, analyzed within a two-parallel-channel conduction model, indicate different relaxation kinetics for subsurface and near-interface hydrogen. Arrhenius analysis reveals two thermally activated processes for $PtH_x$ with an average hydrogen concentration of $x = 0.15$, with activation energies of $130 \pm 18$ meV (subsurface) and $164 \pm 26$ meV (near interface). Above 140 K, D exhibits slower relaxation rates with activation energies of $117 \pm 8$ and $121 \pm 7$ meV for $PtD_x$ prepared under the same implantation dose. Within experimental uncertainty, the activation barriers remain comparable, while the prefactors are reduced significantly for D, indicating isotope-dependent attempt frequencies and zero-point energy effects. TDS simulations based on the Polanyi-Wigner formalism reproduce the experimental desorption spectra by resolving subsurface and near-interface contributions, in agreement with the NRA profile. These findings provide insight into hydrogen kinetics in $PtH_x$ for Pt-based catalysis, sensing, and hydrogen-metal interactions.
Comments35 pages, 6 figures, 1 table, including supplementary material
Journal refActa Materialia 317 (2026) 122531
DOI：10.1016/j.actamat.2026.122531
