通过调节碳自由基的反应活性调控偶联反应产物和羰基化合物的选择性合成

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

催化学报 ›› 2024, Vol. 61: 135-143.DOI: 10.1016/S1872-2067(24)60045-8

通过调节碳自由基的反应活性调控偶联反应产物和羰基化合物的选择性合成

陈朝辉, 邓军, 郑燕梅, 张文君, 董琳, 陈祖鹏^*()

南京林业大学化学工程学院, 江苏省林业资源高效加工利用协同创新中心, 林产化学与材料国际创新高地, 江苏南京 210037

收稿日期:2024-02-26 出版日期:2024-06-18 发布日期:2024-06-20
通讯作者: * 电子信箱: czp@njfu.edu.cn (陈祖鹏).
基金资助:
国家重点研发计划(2023YFD2200505);国家自然科学基金(22202105);国家自然科学基金(22205113);国家自然科学基金(22002043);江苏省自然科学基金(BK20210608);江苏省自然科学基金(BK20210626);江苏省高等学校自然科学基金(21KJA150003);江苏省高等学校自然科学基金(21KJB150027);中国博士后科学基金(2022M711645)

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

Zhaohui Chen, Jun Deng, Yanmei Zheng, Wenjun Zhang, Lin Dong, Zupeng Chen^*()

Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China

Received:2024-02-26 Online:2024-06-18 Published:2024-06-20
Contact: * E-mail: czp@njfu.edu.cn (Z. Chen).
Supported by:
National Key Research and Development Program of China(2023YFD2200505);National Natural Science Foundation of China(22202105);National Natural Science Foundation of China(22205113);National Natural Science Foundation of China(22002043);Natural Science Foundation of Jiangsu Province(BK20210608);Natural Science Foundation of Jiangsu Province(BK20210626);Natural Science Foundation of Jiangsu Higher Education Institutions of China(21KJA150003);Natural Science Foundation of Jiangsu Higher Education Institutions of China(21KJB150027);China Postdoctoral Science Foundation(2022M711645)

摘要/Abstract

摘要：

在温和条件下, 生物质(例如, 生物质衍生醇、葡萄糖、木糖和木质素)通过光催化转化为高附加值化学品受到了广泛关注. 目前, 光催化氧化生物质衍生醇的主要产物是羰基化合物, 即醛类化合物. 相比之下, 生物质衍生醇的C-C偶联产物(如氢化苯偶姻和乙二醇)是制药和合成化学领域重要的中间体和原料, 具有较大的应用价值. 然而, 由于对反应机理的理解不足, 生物质衍生醇的选择性光催化氧化生成对应的C-C偶联产物和羰基化合物仍然具有挑战性.
本文合成了不同金属助催化剂(Au, Pt, Pd和Ru)负载的Cd_0.6Zn_0.4S复合光催化剂(M-CZS)用于光催化生物质衍生醇的选择性氧化. 高分辨透射电镜和X射线光电子能谱结果证明了M-CZS复合光催化剂的成功合成. 紫外-可见漫反射光谱结果表明, 金属Au和Ru引入后, 催化剂可见光的吸收能力增强. 采用光致发光光谱、时间分辨光致发光光谱、光电流强度曲线和电化学阻抗曲线研究了催化剂的载流子分离和重组行为, 结果表明, 金属Au和Ru的引入促进了光生载流子的分离. 所制Au-CZS催化剂生成C-C偶联产物(氢化苯偶姻)的速率为40 mmol g_cat.^‒1 h^‒1, 选择性大于98%. Ru-CZS催化剂生成羰基化合物(苯甲醛)的速率为21 mmol g_cat.^‒1 h^‒1, 选择性高达99%. 催化剂稳定性测试结果表明, Au-CZS和Ru-CZS催化剂具有良好的光催化稳定性. 此外, 所制Au-CZS和Ru-CZS催化剂对各种生物质衍生醇具有良好的光催化活性和较高的选择性. 电子顺磁共振谱与中间体捕获实验结果表明, 反应过程中主要的反应中间体是苯甲醇C_α-H键断裂产生的碳自由基中间体. 通过密度泛函理论计算研究了Au-CZS和Ru-CZS光催化生物质衍生醇选择性氧化合成偶联产物和羰基化合物过程中, 每一步所需的热力学自由能, 结果表明, 碳自由基中间体在Au和Ru的弱和强吸附, 分别导致了C-C偶联产物和羰基化合物的选择性合成.
综上, 本文报道了一种在Cd_0.6Zn_0.4S固溶体中引入不同金属助催化剂的策略, 通过调节相应碳自由基中间体的反应活性, 实现生物质衍生醇的选择性氧化, 为生物质衍生醇的高选择性转化提供了新见解.

关键词: 生物质增值, 光催化, 碳自由基反应性, 选择性控制, 吸附能

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

陈朝辉, 邓军, 郑燕梅, 张文君, 董琳, 陈祖鹏. 通过调节碳自由基的反应活性调控偶联反应产物和羰基化合物的选择性合成[J]. 催化学报, 2024, 61: 135-143.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60045-8

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

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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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通过调节碳自由基的反应活性调控偶联反应产物和羰基化合物的选择性合成

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

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