Modulation of ketyl radical reactivity to mediate the selective synthesis of coupling and carbonyl compounds

doi:10.1016/S1872-2067(24)60045-8

Abstract

Abstract:

The importance of selective synthesis of high-value-added chemicals from renewable resources is paramount but remains a crucial challenge in organic synthesis and chemical reformation. Herein, we report the selective photosynthesis of C-C coupling products and carbonyl compounds from biomass-derived alcohols. The key to ensuring high end-to-end selectivity is the modulation of the reactivity of ketyl radical (*RCHOH) intermediates by employing different metal co-catalysts (Au, Pt, Pd, Ru) supported on Cd_0.6Zn_0.4S solid solution (CZS) photocatalysts. In particular, the C-C coupling product, hydrobenzion, and fully oxidized benzaldehyde were obtained from benzyl alcohol with high selectivity (> 98%) over Au-CZS and Ru-CZS, respectively. Combined experimental and theoretical analyses demonstrated that the affinity of *RCHOH for the surface of metals governs their subsequent transformations, in which weak and strong radical adsorption on Au and Ru results in C-C coupling products and carbonyl compounds, respectively.

Key words: Biomass valorization, Photocatalysis, Ketyl radical reactivity, Selectivity control, Adsorption energy

Zhaohui Chen, Jun Deng, Yanmei Zheng, Wenjun Zhang, Lin Dong, Zupeng Chen. Modulation of ketyl radical reactivity to mediate the selective synthesis of coupling and carbonyl compounds[J]. Chinese Journal of Catalysis, 2024, 61: 135-143.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60045-8

https://www.cjcatal.com/EN/Y2024/V61/I6/135

Figures/Tables 7

Fig. 1. General steps for photocatalytic oxidation of biomass-derived alcohols.

Fig. 2. (a) Schematic diagram for the synthesis of M-CZS photocatalysts. (b) The photocatalytic performance of hydrogen production and selective photosynthesis of HBN or BAD from BA. The time profiles for Au-CZS (c) and Ru-CZS (d). (e) Control experiments for Au-CZS. The stability tests for Au-CZS (f) and Ru-CZS (g). (h) The scale-up experiment of Au-CZS was done on a gram scale. The bar graphs represent the production rates (r) of HBN (purple) and BAD (green); and the red circle and blue square represent the selectivity (S) towards HBN and BAD, respectively.

Fig. 3. Scope evaluation of Au-CZS and Ru-CZS photocatalysts for the photocatalytic oxidation of various biomass-derived alcohols. The bar graphs represent the production rates (r) of HBN (purple) or BAD (green), and the red circle and blue square represent the selectivity (S) towards HBN and BAD, respectively.

Fig. 4. Representative TEM (a,d) and HR-TEM (b,e) images of Au-CZS (a,b) and Ru-CZS (d,e). High-resolution XPS spectra of Au 4f of Au-CZS (c) and Ru 3d for Ru-CZS (f).

Fig. 5. Influence of different scavengers on Au-CZS (a) and Ru-CZS (b). (c) The EPR spectra of CZS, Au-CZS, and Ru-CZS photocatalysts. The bar graphs represent the production rates (r) of HBN (purple) or BAD (green), and the red circle and blue square represent the selectivity (S) towards HBN and BAD, respectively.

Fig. 6. DFT results of the reaction energy profile of the benzyl alcohol oxidation reaction on different metal surfaces of Au-CZS (a) and Ru-CZS (b).

Fig. 7. Proposed mechanism of the photocatalytic reaction.

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