物理化学学报 >> 2017, Vol. 33 >> Issue (2): 270-282.doi: 10.3866/PKU.WHXB201611022

论文 上一篇    下一篇

固体酸催化剂结构与催化反应机理的核磁共振研究

李申慧,李静,郑安民,邓风*()   

  • 收稿日期:2016-09-23 发布日期:2017-01-12
  • 通讯作者: 邓风 E-mail:dengf@wipm.ac.cn
  • 基金资助:
    国家自然科学基金(21210005, 21221064, 21373265)

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

Shen-Hui LI,Jing LI,An-Min ZHENG,Feng DENG*()   

  • Received:2016-09-23 Published:2017-01-12
  • Contact: Feng DENG E-mail:dengf@wipm.ac.cn
  • About author:LI Shen-Hui,obtained his Ph.D.in 2008 from Wuhan Institute of Physics and Mathematics,Chinese Academy of Sciences.He was appointed as a postdoctoral research fellow at Iowa State University during 2008-2010 and joined WIPM as an associate research fellow since 2010.His current research interests are the development of solid-state NMR methodology for heterogeneous catalysts and materials sciences|LI Jing,received her B.S.degree from Liaocheng University in 2014.She is currently a joint graduate student under the supervision of Prof.YU Ning-Ya at Hunan Normal University and Dr.LI Shen-Hui at Wuhan Institute of Physics and Mathematics (WIPM),CAS.Her research focuses on solid state NMR studies of host-guest interaction in MOFs|ZHENG An-Min,obtained his Ph.D.(2005) from Wuhan Institute of Physics and Mathematics,Chinese Academy of Sciences under the supervision of Prof.DENG Feng and has been affiliated with the same institute afterwards.Then he joined Prof.DENG Feng's group.In 2007,he was a visiting research fellow in Prof.LIU Shang-Bin's lab at Institute of Atomic and Molecular Sciences,Academia Sinica,Taiwan.In 2012,he was promoted to a professor.His past and current research interest has been focusing on studies of structure and reaction mechanism of the solid acid catalysts by using experimental solid-state NMR and theoretical quantum chemical calculations|DENG Feng,obtained his Ph.D.(1996) from WIPM,CAS.After his postdoctoral research (1997-1998) at the Department of Chemistry,Texas A&M University (with Prof.James F.Haw),he has worked at WIPM,CAS as a professor (1999-present).His research interests include solid-state NMR methodology and its application to heterogeneous catalysis,Email:dengf@wipm.ac.cn;Tel:+86-27-87198820
  • Supported by:
    The project was 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。

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

Abstract:

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 (NMR) 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.

Key words: Solid-state NMR, Acidity characterization, Solid acid catalyst, Reaction mechanism, Host-guest interaction

MSC2000: 

  • O643