Minghui Liu , Huanling Zhang , Shipeng Song , Rong Fan , Mengqi Wang , Zhengchao Wang , Hao Yan , Guowei Wang , Xiang Feng , Chunyi Li , Chaohe Yang , Xiaolin Zhu
{"title":"MCM-22沸石上苯酚与甲醇催化甲基化直接生产p/m-甲酚:酸度效应和反应网络","authors":"Minghui Liu , Huanling Zhang , Shipeng Song , Rong Fan , Mengqi Wang , Zhengchao Wang , Hao Yan , Guowei Wang , Xiang Feng , Chunyi Li , Chaohe Yang , Xiaolin Zhu","doi":"10.1016/j.mcat.2025.115062","DOIUrl":null,"url":null,"abstract":"<div><div>The methylation of phenol with methanol is an environment-friendly and simple method for cresol production. In this work, the direct and selective production of p/m-cresol from phenol methylation was realized over the MCM-22 zeolite catalyst by sensitive regulation of the reaction temperature. On the one hand, the effect of zeolite acidity was investigated by varying SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratio, and the strong Bronsted acid sites were indicated to be crucial for phenol methylation reaction. The MCM-22 zeolite with strong acidity and moderate porosity exhibited outstanding and stable catalytic performance with high phenol conversion (∼40 %), excellent cresol selectivity (>95 %) and flexible product composition (p-cresol/cresols ∼40 % or m-cresol/cresols ∼50 %). On the other hand, the reaction network of phenol methylation was refined. It was demonstrated that, in addition to the direct production of cresols from C-alkylation of phenol, the cresols could also be produced by the transalkylation between phenol and anisole yield from phenol O-alkylation. This work not only develops a novel eco-friendly p/m-cresol production method, but also deepens people's knowledge of the reaction mechanism of phenol methylation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115062"},"PeriodicalIF":4.9000,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Direct production of p/m-cresol from catalytic methylation of phenol with methanol over MCM-22 zeolite: Acidity effect and reaction network\",\"authors\":\"Minghui Liu , Huanling Zhang , Shipeng Song , Rong Fan , Mengqi Wang , Zhengchao Wang , Hao Yan , Guowei Wang , Xiang Feng , Chunyi Li , Chaohe Yang , Xiaolin Zhu\",\"doi\":\"10.1016/j.mcat.2025.115062\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The methylation of phenol with methanol is an environment-friendly and simple method for cresol production. In this work, the direct and selective production of p/m-cresol from phenol methylation was realized over the MCM-22 zeolite catalyst by sensitive regulation of the reaction temperature. On the one hand, the effect of zeolite acidity was investigated by varying SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratio, and the strong Bronsted acid sites were indicated to be crucial for phenol methylation reaction. The MCM-22 zeolite with strong acidity and moderate porosity exhibited outstanding and stable catalytic performance with high phenol conversion (∼40 %), excellent cresol selectivity (>95 %) and flexible product composition (p-cresol/cresols ∼40 % or m-cresol/cresols ∼50 %). On the other hand, the reaction network of phenol methylation was refined. It was demonstrated that, in addition to the direct production of cresols from C-alkylation of phenol, the cresols could also be produced by the transalkylation between phenol and anisole yield from phenol O-alkylation. This work not only develops a novel eco-friendly p/m-cresol production method, but also deepens people's knowledge of the reaction mechanism of phenol methylation.</div></div>\",\"PeriodicalId\":393,\"journal\":{\"name\":\"Molecular Catalysis\",\"volume\":\"579 \",\"pages\":\"Article 115062\"},\"PeriodicalIF\":4.9000,\"publicationDate\":\"2025-03-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Molecular Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2468823125002482\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Molecular Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2468823125002482","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Direct production of p/m-cresol from catalytic methylation of phenol with methanol over MCM-22 zeolite: Acidity effect and reaction network
The methylation of phenol with methanol is an environment-friendly and simple method for cresol production. In this work, the direct and selective production of p/m-cresol from phenol methylation was realized over the MCM-22 zeolite catalyst by sensitive regulation of the reaction temperature. On the one hand, the effect of zeolite acidity was investigated by varying SiO2/Al2O3 ratio, and the strong Bronsted acid sites were indicated to be crucial for phenol methylation reaction. The MCM-22 zeolite with strong acidity and moderate porosity exhibited outstanding and stable catalytic performance with high phenol conversion (∼40 %), excellent cresol selectivity (>95 %) and flexible product composition (p-cresol/cresols ∼40 % or m-cresol/cresols ∼50 %). On the other hand, the reaction network of phenol methylation was refined. It was demonstrated that, in addition to the direct production of cresols from C-alkylation of phenol, the cresols could also be produced by the transalkylation between phenol and anisole yield from phenol O-alkylation. This work not only develops a novel eco-friendly p/m-cresol production method, but also deepens people's knowledge of the reaction mechanism of phenol methylation.
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