The electronic structure tuning of heterogeneous nanocatalysts is considered as one of the most effective ways of enhancing the catalytic activity of different chemical reactions. Herein, we demonstrate an effective way of tuning the electronic structure of networked PdAg nanowires (NWs) using polyvinylpyrrolidine imine (PVPI) as a new ligand to achieve more efficient hydrogen generation from formic acid (FA) decomposition. The PVPI-capped Pd₅Ag₅ NWs show the highest activity for the dehydrogenation catalysis of FA with an initial turnover frequency (TOF) of 242 h⁻¹ among all the reported catalysts, and an increased TOF of 312 h⁻¹ under 365 nm light irradiation at room temperature. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy studies reveal that there is an interfacial electron transfer from PVPI to the PdAg NW surface, which is the key factor in boosting the dehydrogenation catalysis of FA herein. Density functional theory calculations suggest that the high catalytic activity primarily stems from both electronegative Pd active centers and the imino group (CN) in PVPI for efficiently deprotonating FA to Pd-formate intermediates and subsequently for promoting the cleavage of C–H. The PVPI-capped Pd₅Ag₅ NWs are very stable and reusable for FA dehydrogenation catalysis.

中文翻译：

---

在亚氨基聚合物覆盖的PdAg纳米线网络上增强了电子转移和光吸收，可实现室温下甲酸的高效脱氢†

异质纳米催化剂的电子结构调节被认为是增强不同化学反应的催化活性的最有效方法之一。在本文中，我们演示了一种有效的方法，该方法可使用聚乙烯吡咯烷亚胺（PVPI）作为新的配体来调节网络化PdAg纳米线（NWs）的电子结构，从而实现从甲酸（FA）分解产生更高效的氢。在所有报道的催化剂中，PVPI封端的Pd ₅ Ag ₅ NW表现出最高的FA脱氢催化活性，初始周转频率（TOF）为242 h ^-1，TOF增加为312 h ^-1在室温下在365 nm光下照射。X射线光电子能谱和傅里叶变换红外光谱研究表明，存在从PVPI到PdAg NW表面的界面电子转移，这是促进此处FA脱氢催化的关键因素。密度泛函理论计算表明，高催化活性主要来自于PVPI中的负电Pd活性中心和亚氨基（C N），以有效地使FA质子化为Pd形成的中间体，并随后促进CH的裂解。PVPI封端的Pd ₅ Ag ₅ NW非常稳定，可用于FA脱氢催化。