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

被引：2

作者：

Chen, Zhaohui ^{[1
]}

Deng, Jun ^{[1
]}

Zheng, Yanmei ^{[1
]}

Zhang, Wenjun ^{[1
]}

Dong, Lin ^{[1
]}

Chen, Zupeng ^{[1
]}

机构：

[1] Nanjing Forestry Univ, Coll Chem Engn, Jiangsu Coinnovat Ctr Efficient Proc & Utilizat Fo, Int Innovat Ctr Forest Chem & Mat, Nanjing 210037, Jiangsu, Peoples R China

来源：

CHINESE JOURNAL OF CATALYSIS | 2024年 / 61卷

基金：

中国博士后科学基金;

关键词：

Biomass valorization; Photocatalysis; Ketyl radical reactivity; Selectivity control; Adsorption energy; TOTAL-ENERGY CALCULATIONS; PHOTOCATALYTIC CONVERSION; LIGNOCELLULOSIC BIOMASS; BENZYL ALCOHOL; COCATALYST; OXIDATION; H-2;

D O I：

10.1016/S1872-2067(24)60045-8

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

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 Cd0.6Zn0.4S 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. (c) 2024, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved..

引用

页码：135 / 143

页数：9

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