氧化铝支撑的不对称硫代卟嗪钴光催化苯甲醇的选择性氧化作用

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis Pub Date : 2024-10-13 DOI:10.1016/j.mcat.2024.114608

Wenyao Zhou, Rongjiao Tan, Changjun Yang, Bingguang Zhang, Kejian Deng

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引用次数: 0

摘要

利用阳光将醇转化为相应的羧酸为精细化学合成提供了一条可行的途径。本研究合成了不对称三(2,3-双(丁硫基)马来腈)-(1,4-二硫鎓)卟嗪钴（CoPz(SBu)6(dtn)），并利用溶剂蒸发法进一步获得了其单晶。然后将不对称的 CoPz(SBu)6(dtn) 支持在中性 Al2O3 颗粒上，形成复合光催化剂 CoPz(SBu)6(dtn)@Al2O3，它具有很强的可见光吸收能力。在以绿色 H2O2 为氧化剂、K2CO3 为添加剂的条件下，复合光催化剂 CoPz(SBu)6(dtn)@Al2O3 在模拟太阳光照射下表现出优异的光催化活性，可将水中的苯甲醇选择性氧化为苯甲酸。在复合光催化剂 CoPz(SBu)6(dtn)@Al2O3 上，苯甲醇的转化率高达 53.8%，苯甲酸的选择性高达 99%。同时，该光催化体系具有基底通用性，对同时含有供电子和吸电子取代基的取代苄醇具有优异的光催化活性。复合光催化剂 CoPz(SBu)6(dtn)@Al2O3 具有优异的光催化耐久性，这一点在回收实验中得到了证实。这项工作表明，不对称硫代卟嗪作为光催化剂在实现太阳光驱动的选择性转化方面是可行的。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Selective oxidation of benzyl alcohols photocatalyzed by asymmetric cobalt thioporphyrazine supported on alumina

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Selective oxidation of benzyl alcohols photocatalyzed by asymmetric cobalt thioporphyrazine supported on alumina

The sunlight-powered transformation of alcohols to corresponding carboxylic acids offers a feasible route for fine chemical synthesis. In this work, the asymmetric cobalt tri(2,3-bis(butylthio)maleonitrile)-(1,4-dithiin) porphyrazine (CoPz(SBu)₆(dtn)) was synthesized, more importantly, its single crystal was further obtained by the solvent evaporation method. Then the asymmetric CoPz(SBu)₆(dtn) supported on neutral Al₂O₃ particles to form composite photocatalyst CoPz(SBu)₆(dtn)@Al₂O₃, which possessed strong visible light absorption. Under simulated sunlight irradiation using a xenon lamp, the composite photocatalyst CoPz(SBu)₆(dtn)@Al₂O₃ exhibited excellent photocatalytic activity for selective oxidation of benzyl alcohol to benzoic acid in water under conditions of green H₂O₂ as oxidant and K₂CO₃ as additive. The conversion of benzyl alcohol was up to 53.8 % together with 99 % selectivity of benzoic acid over composite photocatalyst CoPz(SBu)₆(dtn)@Al₂O₃. Meanwhile, this photocatalytic system had feasible substrate generalizability and excellent photocatalytic activity for substituted benzyl alcohols containing both electron-donating and electron-withdrawing substituents. The composite photocatalyst CoPz(SBu)₆(dtn)@Al₂O₃ exhibited excellent photocatalytic durability, which was confirmed by the recycling experiments. This work manifests the asymmetric thioporphyrazine as photocatalyst is feasible in implementing sunlight-powered selective transformation.

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来源期刊

Molecular Catalysis Chemical Engineering-Process Chemistry and Technology

CiteScore

6.90

自引率

10.90%

发文量

700

审稿时长

40 days

期刊介绍： Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods