Citation: Yang Yan, Bin Ye, Mingshu Chen, Linfang Lu, Jian Yu, Yuheng Zhou, Yong Wang, Juanjuan Liu, Liping Xiao, Shihui Zou, Jie Fan. Site-specific deposition creates electron-rich Pd atoms for unprecedented C-H activation in aerobic alcohol oxidation[J]. Chinese Journal of Catalysis, ;2020, 41(8): 1240-1247. doi: 10.1016/S1872-2067(20)63535-5 shu

Site-specific deposition creates electron-rich Pd atoms for unprecedented C-H activation in aerobic alcohol oxidation

Yang Yan ^a, ,
Bin Ye ^a ,
Mingshu Chen ^b ,
Linfang Lu ^a ,
Jian Yu ^c ,
Yuheng Zhou ^a ,
Yong Wang ^c ,
Juanjuan Liu ^d ,
Liping Xiao ^a ,
Shihui Zou ^a ,
Jie Fan ^a

a Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, China;
b College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;
c School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China;
d College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310036, Zhejiang, China

Received Date: 26 November 2019
Revised Date: 26 December 2019

Fund Project: This work was supported by the National Natural Science Foundation of China (91545113, 91845203, 91645103, 21802122, 21703050) and the Shell Global Solutions International B.V. (PT71423, PT74557).

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.
- AuPd/TiO₂,
- Benzyl alcohol,
- Selective oxidation,
- C-H activation,
- Electronic structure
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