Mechanistic insights and the role of spatial confinement in catalytic dimethyl ether carbonylation over SSZ-13 zeolite

IF 15.7 1区 化学 Q1 CHEMISTRY, APPLIED
Xiaomin Zhang , Kai Cai , Ying Li , Ji Qi , Yue Wang , Yunduo Liu , Mei-Yan Wang , Shouying Huang , Xinbin Ma
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引用次数: 0

Abstract

The SSZ-13 zeolite, which exhibits typical CHA topology characterized by 8-membered ring (8-MR) channels, has shown potential for catalyzing dimethyl ether (DME) carbonylation. However, current studies have yet to provide a comprehensive analysis of its catalytic mechanisms. In this study, we investigated the mechanism of SSZ-13-catalyzed DME carbonylation and the role of spatial confinement in this reaction. By exploiting the differences in the radii of the metal ions, we selectively replaced Brønsted acid sites (BAS) within specific channels, as confirmed by quantitative acidity analysis. Combining the activity data and the dissociation energies of the reactants on the BAS within different rings, we found that both the main and side reactions of DME carbonylation occurred on the 8-MR BAS of SSZ-13. Furthermore, the exchange of ions of different radii highlighted the confinement effect of the pore space in the SSZ-13 zeolite. Characterization of the deposits in spent catalysts, along with theoretical insights, revealed that the reduced cage space adversely affects the stabilization of side reaction intermediates, which in turn mitigates side reactions and improves the selectivity toward methyl acetate. This study presents an effective approach to modulate the acid site distribution and spatial confinement and provides critical insights into the determinants of the catalytic performance of SSZ-13. These findings offer valuable guidance for the future design and optimization of zeolites, aiming to enhance their efficacy in catalytic applications.

SSZ-13沸石催化二甲醚羰基化的机理认识和空间限制作用
SSZ-13 沸石具有典型的 CHA 拓扑结构,其特征为 8 元环(8-MR)通道,已显示出催化二甲醚(DME)羰基化的潜力。然而,目前的研究尚未对其催化机理进行全面分析。在本研究中,我们研究了 SSZ-13 催化二甲醚羰基化反应的机理以及空间限制在该反应中的作用。通过利用金属离子半径的差异,我们选择性地替换了特定通道内的布氏硬度酸位点(BAS),并通过定量酸度分析证实了这一点。结合活性数据和不同环内 BAS 上反应物的解离能,我们发现二甲醚羰基化的主反应和副反应都发生在 SSZ-13 的 8-MR BAS 上。此外,不同半径离子的交换凸显了 SSZ-13 沸石孔隙的约束效应。对废催化剂中沉积物的表征以及理论分析表明,笼状空间的减少会对副反应中间产物的稳定产生不利影响,从而减轻副反应并提高对醋酸甲酯的选择性。这项研究提出了一种调节酸位点分布和空间限制的有效方法,并对 SSZ-13 催化性能的决定因素提出了重要见解。这些发现为今后沸石的设计和优化提供了宝贵的指导,旨在提高其在催化应用中的功效。
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
Chinese Journal of Catalysis
Chinese Journal of Catalysis 工程技术-工程:化工
CiteScore
25.80
自引率
10.30%
发文量
235
审稿时长
1.2 months
期刊介绍: The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.
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