有机卤化物在二氧化碳转化为环状碳酸盐过程中的解离对催化活性的作用:实验和计算研究

IF 7.2 2区 工程技术 Q1 CHEMISTRY, MULTIDISCIPLINARY
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引用次数: 0

摘要

能够清楚了解催化剂活性位点影响的系统性二氧化碳转化研究数量有限。因此,这项研究考察了 24 种由氯化物、溴化物或碘化物阴离子和咪唑鎓、铵或鏻阳离子组成的有机盐在利用二氧化碳合成己烯和苯乙烯碳酸盐过程中的催化活性,并得出了不同的产率。研究结果表明,高产率在很大程度上取决于催化剂在反应介质中的溶解度,但仅有溶解度并不能保证反应成功。这一发现支持了新的假设,即依赖于溶解度的催化剂解离是决定催化活性的关键因素。使用 COSMO-RS 方法计算得出的碳酸盐产量与催化剂的解离常数之间存在很强的相关性。这表明,较大的解离度反映了阳离子与阴离子之间较弱的相互作用,有利于阴离子对环氧化物的亲核攻击。此外,计算解离常数与实验离子电导率之间的关系也得到了成功验证。这凸显了有机盐解离对催化性能的重要影响,并验证了使用计算工具预测关键操作参数的有效性,从而加深了人们对将二氧化碳转化为环状碳酸盐的理解并优化了这一过程。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Dissociation role on the catalytic activity of organic halides in CO2 conversion to cyclic carbonates: Experimental and computational study

There is a limited number of systematic CO2 conversion studies that provide a clear understanding of the effect of the active sites of catalysts. Hence, this work examines the catalytic activity of 24 organic salts consisting of chloride, bromide or iodide anions and imidazolium, ammonium, or phosphonium-based cations, in the synthesis of hexylene and styrene carbonates from CO2, resulting in a diverse range of yields. The findings revealed that high yields depend heavily on catalyst solubility in the reaction medium, but solubility alone does not guarantee reaction success. This finding supports the new hypothesis that catalyst dissociation, reliant on solubility, is a critical factor in defining the catalytic activity. A strong correlation was observed between carbonate yields and the dissociation constants of catalysts, calculated using the COSMO-RS method. This suggests that greater dissociation, reflecting weaker cation-anion interactions, facilitates the anion nucleophilic attack on the epoxide. Also, the relationship between calculated dissociation constant and experimental ionic conductivity was successfully validated. This highlights the significance of organic salt dissociation on catalytic performance and validates the use of computational tools to predict key operational parameters, enhancing the understanding and optimization of CO2 conversion into cyclic carbonates.

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来源期刊
Journal of CO2 Utilization
Journal of CO2 Utilization CHEMISTRY, MULTIDISCIPLINARY-ENGINEERING, CHEMICAL
CiteScore
13.90
自引率
10.40%
发文量
406
审稿时长
2.8 months
期刊介绍: The Journal of CO2 Utilization offers a single, multi-disciplinary, scholarly platform for the exchange of novel research in the field of CO2 re-use for scientists and engineers in chemicals, fuels and materials. The emphasis is on the dissemination of leading-edge research from basic science to the development of new processes, technologies and applications. The Journal of CO2 Utilization publishes original peer-reviewed research papers, reviews, and short communications, including experimental and theoretical work, and analytical models and simulations.
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