固体酸催化剂结构与催化反应机理的核磁共振研究(英文)  

Solid-State NMR Characterization of the Structure and Catalytic Reaction Mechanism of Solid Acid Catalysts

作　　者：李申慧[1] 李静[1] 郑安民[1] 邓风[1] LI Shen-Hui LI Jing ZHENG An-Min DENG Feng(State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, P. R. China)

机构地区：[1]中国科学院武汉物理与数学研究所,波谱与原子分子物理国家重点实验室,武汉磁共振中心,武汉430071

出　　处：《物理化学学报》2017年第2期270-282,共13页Acta Physico-Chimica Sinica

基　　金：supported by the National Natural Science Foundation of China(21210005,21221064,21373265)~~

摘　　要：固体酸催化剂因具有环境友好、高产物选择性和易于分离等优点而广泛应用于现代石油化工领域的各种催化过程。固体核磁共振是一种研究功能材料结构和动力学性质的有力工具。本文将主要介绍固体核磁共振在表征固体酸催化剂的表面酸性以及多相催化反应机理方面的应用。具体来说,可以通过一系列探针分子(如吡啶、丙酮、三烷基氧磷和三甲基磷)的NMR化学位移实验观测值来定量测量酸强度;二维双量子魔角旋转(DQ MAS)固体核磁共振技术能够揭示催化剂上酸中心的空间临近性及协同效应。另外,原位固体核磁共振可以揭示多相催化反应过程中反应物、中间体、反应产物的演化,阐明催化反应机理。Solid acid catalysts have been widely used in advanced petrochemical processes because of their environmental friendliness, high product selectivity, and easy product separation. Solid-state nuclear magnetic resonance （NMIR） spectroscopy is a well-established tool for structure determination and dynamic study of various functional materials. In this review, we focus mainly on our research using solid-state NMR to characterize the acid properties and elucidate the catalytic reaction mechanism of solid acid catalysts. The acid strength of solid acids can be quantitatively measured from the chemical shifts of adsorbed probe molecules such as pyridine, acetone, trialkylphosphine oxides, and trimethylphosphine. The spatial proximity and synergetic effect of various acid sites on solid acid catalysts can be ascertained by two-dimensional （2D） double-quantum magic angle spinning （DQ MAS） NMR spectroscopy. Additionally, in situ solid-state NMR spectroscopy can be used to explore heterogeneous catalytic reaction mechanisms by monitoring the evolution of the reactants, intermediates, and products.

关 键 词：固体核磁共振 酸表征 固体酸催化剂 催化反应机理 主客体相互作用 

分 类 号：O643.36[理学—物理化学]