Abstract Here, we demonstrate a photochemical strategy to site-specifically deposit Pd atoms on Au nanoparticles. The high-sensitivity low-energy ion scattering spectra combined with the X-ray photoelectron spectra reveal that the surface electronic structure of Pd can be continuously regulated by tailoring the Pd-to-Au molar ratio and the location of Pd atoms in AuPd nanoparticles. It is revealed that electron-rich Pd atoms are considerably more active than the net Pd atoms in aerobic alcohol oxidation. Remarkably, the catalyst with the most electron-rich Pd sites (binding energy downshift: 1.0 eV) exhibits an extremely high turnover frequency (˜500000 h−1 vs 12000 h−1 for that with net Pd atoms) for solvent-free selective oxidation of benzyl alcohol, which is, to the best of our knowledge, the highest value ever reported. Kinetic studies reveal that electron-rich Pd atoms can accelerate the oxidation of benzyl alcohol by facilitating C-H cleavage, as indicated by the significant reduction in the activation energy as compared to net Pd atoms.

中文翻译：

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位点特定沉积产生富电子 Pd 原子，用于有氧醇氧化中前所未有的 C−H 活化

摘要 在这里，我们展示了一种光化学策略，可以在 Au 纳米颗粒上进行位点特异性沉积 Pd 原子。高灵敏度低能离子散射光谱与 X 射线光电子光谱相结合表明，可以通过调整 Pd 与 Au 的摩尔比和 AuPd 纳米粒子中 Pd 原子的位置来连续调节 Pd 的表面电子结构。结果表明，富电子 Pd 原子比有氧醇氧化中的净 Pd 原子活跃得多。值得注意的是，具有最多富电子 Pd 位点（结合能下降：1.0 eV）的催化剂对于无溶剂选择性氧化表现出极高的周转频率（~500000 h-1 vs 12000 h-1 对于具有净 Pd 原子的催化剂）苯甲醇，据我们所知，这是有史以来报告的最高值。