Li Meiling, Zhao Yingzhe, Yang Yisen, Zhang Renjie, Wang Yanyue, Teng Yunan, Su Zhuizhui, Zhang Jianling
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China.
Chem Asian J. 2024 Sep 2;19(17):e202400346. doi: 10.1002/asia.202400346. Epub 2024 Aug 5.
The photocatalytic oxidation of biomass-derived benzyl alcohol provides a promising way for the synthesis of benzoic acid, which is an important intermediate with wide applications. To improve the efficiency of photocatalytic benzyl alcohol oxidation to benzoic acid is of great interest. In this work, we propose the utilization of NH-UiO-66-ID-Fe catalyst for photocatalytic oxidation of benzyl alcohol to benzoic acid, where NH-UiO-66 is a typically used metal-organic framework, ID is indole-2,3-dione (ID) that has biocompatibility, light absorption property and can be covalently combined with amino-functionalized substances. The NH-UiO-66-ID-Fe catalyst exhibits improved light absorption and photo-generated electron-hole separation ability compared with NH-UiO-66. The photocatalytic performance of NH-UiO-66-ID-Fe was examined for the oxidation of bio-based benzyl alcohol under mild conditions of air atmosphere, room temperature and no additive or additional oxidant involved. The results show that the conversion of benzyl alcohol and the selectivity to benzoic acid could both reach over 99 % in 6 h, and the generation rate of benzoic acid per gram of catalyst is 3.36 mmol g h. The reaction mechanism was detected by radical trapping method and in situ electron paramagnetic resonance. This study presents an efficient and environmentally benign avenue for the synthesis of carboxylic acid compounds.
生物质衍生的苯甲醇的光催化氧化为苯甲酸的合成提供了一条很有前景的途径，苯甲酸是一种具有广泛应用的重要中间体。提高光催化苯甲醇氧化制苯甲酸的效率备受关注。在这项工作中，我们提出利用NH-UiO-66-ID-Fe催化剂将苯甲醇光催化氧化为苯甲酸，其中NH-UiO-66是一种常用的金属有机框架，ID是具有生物相容性、光吸收特性且能与氨基官能化物质共价结合的吲哚-2,3-二酮（ID）。与NH-UiO-66相比，NH-UiO-66-ID-Fe催化剂表现出更好的光吸收和光生电子-空穴分离能力。在空气气氛、室温且不添加任何添加剂或额外氧化剂的温和条件下，考察了NH-UiO-66-ID-Fe对生物基苯甲醇氧化的光催化性能。结果表明，苯甲醇的转化率和对苯甲酸的选择性在6小时内均能达到99%以上，每克催化剂的苯甲酸生成速率为3.36 mmol g⁻¹ h⁻¹。通过自由基捕获法和原位电子顺磁共振检测了反应机理。该研究为羧酸化合物的合成提供了一条高效且环境友好的途径。
