Amorphous Zr-OMS-2 Catalyst with Synergistic Lewis Acidity-Redox Sites for Efficient Ammoxidation of Benzyl Alcohol to Benzonitrile.

IF 6.6 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
ChemSusChem Pub Date : 2025-09-29 DOI:10.1002/cssc.202501355
Yu Zhang, Weitao Wang, Huan Wang, Jiaqi Zhu, Yuxin Chai, Zhen-Hong He, Yang Yang, Kuan Wang, Zhao-Tie Liu
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引用次数: 0

Abstract

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.

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。
醇的直接氨氧化反应是合成腈的重要途径。然而,在抑制对酰胺的过度反应的同时实现高腈选择性仍然是一个重大挑战。在本工作中,开发了一种zr掺杂的OMS-2催化剂,该催化剂在苯甲醇选择性氨氧化制苯腈方面表现出显著的效率。在优化条件下,以氨水为氮源,分子氧为氧化剂,收率为84.9%,选择性为89.9%。溶剂效应研究表明,对苯甲醇和苯腈的吸附对反应的活性和选择性有显著影响。动力学研究表明,该反应是一个连续三步的一级反应,其高腈选择性受到动力学控制。综合表征表明,Zr4+的掺入提高了OMS-2的Lewis酸度,增加了活性氧的数量,有效降低了活化能垒。对照实验详细阐明了反应机理。该催化剂具有优异的稳定性和广泛的底物通用性,可选择性地将多种芳香醇转化为相应的腈,收率高。这项工作为传统的氰基腈合成方法提供了一种强大而实用的替代方法。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
ChemSusChem
ChemSusChem 化学-化学综合
CiteScore
15.80
自引率
4.80%
发文量
555
审稿时长
1.8 months
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
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