Yu Zhang, Weitao Wang, Huan Wang, Jiaqi Zhu, Yuxin Chai, Zhen-Hong He, Yang Yang, Kuan Wang, Zhao-Tie Liu
{"title":"具有协同路易斯酸-氧化还原位点的无定形Zr-OMS-2催化剂用于苯甲醇氨氧化制苯腈。","authors":"Yu Zhang, Weitao Wang, Huan Wang, Jiaqi Zhu, Yuxin Chai, Zhen-Hong He, Yang Yang, Kuan Wang, Zhao-Tie Liu","doi":"10.1002/cssc.202501355","DOIUrl":null,"url":null,"abstract":"<p><p>The direct ammoxidation of alcohols represents a crucial synthetic pathway for nitrile production. However, achieving high nitrile selectivity while suppressing over-reaction to amides remains a significant challenge. In the present work, a Zr-doped OMS-2 catalyst that demonstrated remarkable efficiency for the selective ammoxidation of benzyl alcohol to benzonitrile is developed. Under optimized conditions, an impressive yield of 84.9% and selectivity of 89.9% are achieved, using aqueous ammonia as the nitrogen source and molecular oxygen as the oxidant. Solvent effect studies reveal that the adsorption of benzyl alcohol and benzonitrile significantly influences the activity and selectivity of the reaction. Kinetic investigations reveal that the reaction proceeded through a three-step consecutive first-order mechanism, with the high nitrile selectivity being kinetically controlled. Comprehensive characterization demonstrates that the incorporation of Zr<sup>4+</sup> enhances the Lewis acidity of OMS-2, increases the population of active oxygen species, and effectively lowers the activation energy barrier. Controlled experiments elucidate the reaction mechanism in detail. The catalyst exhibits excellent stability and broad substrate generality, selectively converting a wide range of aromatic alcohols to their corresponding nitriles with high yields. This work provides a robust and practical alternative to conventional cyanide-based nitrile synthesis methodologies.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501355"},"PeriodicalIF":6.6000,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Amorphous Zr-OMS-2 Catalyst with Synergistic Lewis Acidity-Redox Sites for Efficient Ammoxidation of Benzyl Alcohol to Benzonitrile.\",\"authors\":\"Yu Zhang, Weitao Wang, Huan Wang, Jiaqi Zhu, Yuxin Chai, Zhen-Hong He, Yang Yang, Kuan Wang, Zhao-Tie Liu\",\"doi\":\"10.1002/cssc.202501355\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The direct ammoxidation of alcohols represents a crucial synthetic pathway for nitrile production. However, achieving high nitrile selectivity while suppressing over-reaction to amides remains a significant challenge. In the present work, a Zr-doped OMS-2 catalyst that demonstrated remarkable efficiency for the selective ammoxidation of benzyl alcohol to benzonitrile is developed. Under optimized conditions, an impressive yield of 84.9% and selectivity of 89.9% are achieved, using aqueous ammonia as the nitrogen source and molecular oxygen as the oxidant. Solvent effect studies reveal that the adsorption of benzyl alcohol and benzonitrile significantly influences the activity and selectivity of the reaction. Kinetic investigations reveal that the reaction proceeded through a three-step consecutive first-order mechanism, with the high nitrile selectivity being kinetically controlled. Comprehensive characterization demonstrates that the incorporation of Zr<sup>4+</sup> enhances the Lewis acidity of OMS-2, increases the population of active oxygen species, and effectively lowers the activation energy barrier. Controlled experiments elucidate the reaction mechanism in detail. The catalyst exhibits excellent stability and broad substrate generality, selectively converting a wide range of aromatic alcohols to their corresponding nitriles with high yields. This work provides a robust and practical alternative to conventional cyanide-based nitrile synthesis methodologies.</p>\",\"PeriodicalId\":149,\"journal\":{\"name\":\"ChemSusChem\",\"volume\":\" \",\"pages\":\"e202501355\"},\"PeriodicalIF\":6.6000,\"publicationDate\":\"2025-09-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemSusChem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/cssc.202501355\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemSusChem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cssc.202501355","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Amorphous Zr-OMS-2 Catalyst with Synergistic Lewis Acidity-Redox Sites for Efficient Ammoxidation of Benzyl Alcohol to Benzonitrile.
The direct ammoxidation of alcohols represents a crucial synthetic pathway for nitrile production. However, achieving high nitrile selectivity while suppressing over-reaction to amides remains a significant challenge. In the present work, a Zr-doped OMS-2 catalyst that demonstrated remarkable efficiency for the selective ammoxidation of benzyl alcohol to benzonitrile is developed. Under optimized conditions, an impressive yield of 84.9% and selectivity of 89.9% are achieved, using aqueous ammonia as the nitrogen source and molecular oxygen as the oxidant. Solvent effect studies reveal that the adsorption of benzyl alcohol and benzonitrile significantly influences the activity and selectivity of the reaction. Kinetic investigations reveal that the reaction proceeded through a three-step consecutive first-order mechanism, with the high nitrile selectivity being kinetically controlled. Comprehensive characterization demonstrates that the incorporation of Zr4+ enhances the Lewis acidity of OMS-2, increases the population of active oxygen species, and effectively lowers the activation energy barrier. Controlled experiments elucidate the reaction mechanism in detail. The catalyst exhibits excellent stability and broad substrate generality, selectively converting a wide range of aromatic alcohols to their corresponding nitriles with high yields. This work provides a robust and practical alternative to conventional cyanide-based nitrile synthesis methodologies.
期刊介绍:
ChemSusChem
Impact Factor (2016): 7.226
Scope:
Interdisciplinary journal
Focuses on research at the interface of chemistry and sustainability
Features the best research on sustainability and energy
Areas Covered:
Chemistry
Materials Science
Chemical Engineering
Biotechnology