Polygonal mesopores microflower catalysts for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene to 2-nitro-4-methylsulfonylbenzoic acid in a continuous-flow microreactor

doi:10.1016/j.cjche.2024.04.025

Chinese Journal of Chemical Engineering ›› 2024, Vol. 73 ›› Issue (9): 212-221.DOI: 10.1016/j.cjche.2024.04.025

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Polygonal mesopores microflower catalysts for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene to 2-nitro-4-methylsulfonylbenzoic acid in a continuous-flow microreactor

Jianzhi Wang, Xugen Li, Cheng Zhang, Yuan Pu, Jiawu Liu, Jie Liu, Yanping Liu, Xiao Lin, Faquan Yu

Key Laboratory for Green Chemical Process of Ministry of Education, Hubei Key Laboratory for Novel Reactor and Green Chemistry Technology, Hubei Engineering Research Center for Advanced Fine Chemicals, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430073, China

Received:2023-08-14 Revised:2024-04-10 Accepted:2024-04-11 Online:2024-06-18 Published:2024-11-21
Contact: Faquan Yu,E-mail:fyu@wit.edu.cn
Supported by:
This research was supported by the National Natural Science Foundation of China (22078251), Hubei Province Key Research and Development Program (2023DJC167) and the research project of Hubei Provincial Department of Education (D20191504).

Polygonal mesopores microflower catalysts for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene to 2-nitro-4-methylsulfonylbenzoic acid in a continuous-flow microreactor

Jianzhi Wang, Xugen Li, Cheng Zhang, Yuan Pu, Jiawu Liu, Jie Liu, Yanping Liu, Xiao Lin, Faquan Yu

Key Laboratory for Green Chemical Process of Ministry of Education, Hubei Key Laboratory for Novel Reactor and Green Chemistry Technology, Hubei Engineering Research Center for Advanced Fine Chemicals, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430073, China

通讯作者: Faquan Yu,E-mail:fyu@wit.edu.cn
基金资助:
This research was supported by the National Natural Science Foundation of China (22078251), Hubei Province Key Research and Development Program (2023DJC167) and the research project of Hubei Provincial Department of Education (D20191504).

Abstract

Abstract: The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) to 2-nitro-4-methylsulfonyl benzoic acid (NMSBA) with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry. Here, we report the synthesis of FeOOH/Fe₃O₄/metal-organic framework (MOF) polygonal mesopores microflower templated from a MIL-88B(Fe) at room temperature, which exposes polygonal mesopores with atomistic edge steps and lattice defects. The obtained FeOOH/Fe₃O₄/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor. In the alkaline environment, oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA, showing impressive performance. This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture. The position and type of substituent critically affect the products. Additionally, this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities. Finally, the reactions can be conducted in a pressure reactor, which can conserve oxygen and prevent solvent loss. Moreover, compared with the traditional batch reactor, the self-built microchannel reactor can accelerate the reaction rate, shorten the reaction time, and enhance the selectivity of catalytic oxidation reactions. This approach contributes to environmental protection and holds potential for industrial applications.

Key words: 2-nitro-4-methylsulfonylbenzoic, 2-nitro-4-methylsulfonyltoluene, FeOOH/Fe₃O₄/MOF, Catalyst, Microreactor, Oxidation

摘要： The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) to 2-nitro-4-methylsulfonyl benzoic acid (NMSBA) with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry. Here, we report the synthesis of FeOOH/Fe₃O₄/metal-organic framework (MOF) polygonal mesopores microflower templated from a MIL-88B(Fe) at room temperature, which exposes polygonal mesopores with atomistic edge steps and lattice defects. The obtained FeOOH/Fe₃O₄/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor. In the alkaline environment, oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA, showing impressive performance. This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture. The position and type of substituent critically affect the products. Additionally, this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities. Finally, the reactions can be conducted in a pressure reactor, which can conserve oxygen and prevent solvent loss. Moreover, compared with the traditional batch reactor, the self-built microchannel reactor can accelerate the reaction rate, shorten the reaction time, and enhance the selectivity of catalytic oxidation reactions. This approach contributes to environmental protection and holds potential for industrial applications.

关键词: 2-nitro-4-methylsulfonylbenzoic, 2-nitro-4-methylsulfonyltoluene, FeOOH/Fe₃O₄/MOF, Catalyst, Microreactor, Oxidation

Jianzhi Wang, Xugen Li, Cheng Zhang, Yuan Pu, Jiawu Liu, Jie Liu, Yanping Liu, Xiao Lin, Faquan Yu. Polygonal mesopores microflower catalysts for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene to 2-nitro-4-methylsulfonylbenzoic acid in a continuous-flow microreactor[J]. Chinese Journal of Chemical Engineering, 2024, 73(9): 212-221.

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Polygonal mesopores microflower catalysts for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene to 2-nitro-4-methylsulfonylbenzoic acid in a continuous-flow microreactor

Polygonal mesopores microflower catalysts for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene to 2-nitro-4-methylsulfonylbenzoic acid in a continuous-flow microreactor

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