Revisiting the activity origin of the PtAu24(SR)18 nanocluster for enhanced electrocatalytic hydrogen evolution by combining first-principles simulations with the experimental in situ FTIR technique,Chemical Science

当前位置： X-MOL 学术 › Chem. Sci. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Revisiting the activity origin of the PtAu24(SR)18 nanocluster for enhanced electrocatalytic hydrogen evolution by combining first-principles simulations with the experimental in situ FTIR technique
Chemical Science ( IF 7.6 ) Pub Date : 2024-09-06 , DOI: 10.1039/d4sc04212c
Fang Sun ₁ , Lubing Qin ₂ , Zhenghua Tang ₂ , Qing Tang ₁

Affiliation

Thiolate-protected metal nanoclusters (NCs) have been widely used in various electrocatalytic reactions, yet the dynamic evolution of metal NCs during electrocatalysis has been rarely explored and the activity origin remains largely ambiguous. Herein, using a PtAu₂₄(SCH₃)₁₈ NC as a prototype model, we combined advanced first-principles calculations and attenuated total reflection surface-enhanced infrared spectroscopy (ATR-SEIRAS) to re-examine its active site and reaction dynamics in the hydrogen evolution reaction (HER). It has been previously assumed that the central Pt is the only catalytic center. However, differently, we observed the spontaneous desorption of thiolate ligands under moderate potential, and the dethiolated PtAu₂₄ exhibits excellent HER activity, which is contributed not only by the central Pt atom but also by the exposed bridged Au sites. Particularly, the exposed Au exhibits high activity even comparable to Pt, and the synergistic effect between them makes dethiolated PtAu₂₄ an extraordinary HER electrocatalyst, even surpassing the commercial Pt/C catalyst. Our predictions are further verified by electrochemical activation experiments and in situ FTIR (ATR-SEIRAS) characterization, where evident adsorption of Au–H* and Pt–H* bonds is monitored. This work detected, for the first time, the Au–S interfacial dynamics of the PtAu₂₄ nanocluster in electrocatalytic processes, and quantitatively evaluated the essential catalytic role of the exposed Au sites that has been largely overlooked in previous studies.

中文翻译：

通过将第一原理模拟与实验原位 FTIR 技术相结合，重新审视 PtAu24(SR)18 纳米团簇的活性起源，以增强电催化析氢

硫醇盐保护的金属纳米簇（NC）已广泛应用于各种电催化反应中，但金属纳米簇在电催化过程中的动态演化却很少被探索，而且活性起源仍然很模糊。在此，我们以PtAu ₂₄ (SCH ₃ ) ₁₈ NC为原型模型，结合先进的第一性原理计算和衰减全反射表面增强红外光谱(ATR-SEIRAS)，重新审视其活性位点和反应动力学。析氢反应（HER）。先前假设中心 Pt 是唯一的催化中心。然而，不同的是，我们观察到硫醇盐配体在中等电位下自发解吸，并且脱硫基PtAu ₂₄表现出优异的HER活性，这不仅由中心Pt原子贡献，而且还由暴露的桥接Au位点贡献。特别是，暴露的Au表现出与Pt相当的高活性，并且它们之间的协同效应使脱硫基PtAu ₂₄成为非凡的HER电催化剂，甚至超越了商业Pt/C催化剂。我们的预测通过电化学活化实验和原位FTIR (ATR-SEIRAS) 表征得到进一步验证，其中监测了 Au-H* 和 Pt-H* 键的明显吸附。这项工作首次检测到电催化过程中 PtAu ₂₄纳米团簇的 Au-S 界面动力学，并定量评估了暴露的 Au 位点的基本催化作用，而这在以前的研究中很大程度上被忽视了。

更新日期：2024-09-06

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南