多金属氧酸盐TBA3[VW5O19]及TBA4[PVW11O40]的固体核磁共振研究

丁丽红1; 2; 刘小龙2; 王强2; 刘文涛1; 朱诚身1; 郑安民2; 邓风2*

doi:10.11938/cjmr20150302

波谱学杂志 >

2015 , Vol. 32 >Issue 3: 409 - 418

DOI: https://doi.org/10.11938/cjmr20150302

研究论文

多金属氧酸盐TBA₃[VW₅O₁₉]及TBA₄[PVW₁₁O₄₀]的固体核磁共振研究

丁丽红1 ,
2 ,
刘小龙2 ,
王强2 ,
刘文涛1 ,
朱诚身1 ,
郑安民2 ,
邓风2*

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1. 郑州大学材料科学与工程学院，河南郑州 450001; 2. 波谱与原子分子物理国家重点实验室，武汉磁共振中心(中国科学院武汉物理与数学研究所)，湖北武汉 430071

丁丽红(1988-)，女，河南郑州人，硕士研究生，高分子化学与物理专业. *通讯联系人：邓风，电话：027-87198820, E-mail: dengf@wipm.ac.cn.

收稿日期: 2014-06-27

修回日期: 2015-07-27

网络出版日期: 2015-09-05

基金资助

国家自然科学基金资助项目(21473246, 21303253).

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Solid-State NMR Studies of TBA₃[VW₅O₁₉] and TBA₄[PVW₁₁O₄₀]

DING Li-hong1 ,
2 ,
LIU Xiao-long2 ,
WANG Qiang2 ,
LIU Wen-tao1 ,
ZHU Cheng-shen1 ,
ZHENG An-min2 ,
DENG Feng2*

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1. School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China; 2. National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics (Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences), Wuhan 430071, China

*Corresponding author：DENG Feng, Tel: +86-027-87198820, E-mail: dengf@wipm.ac.cn.

Received date: 2014-06-27

Revised date: 2015-07-27

Online published: 2015-09-05

Supported by

国家自然科学基金资助项目(21473246, 21303253).

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摘要

多金属氧酸盐（简称多酸，Polyoxometalates，POMs)是由处于d⁰电子构型的前过渡金属元素通过共边或共角缩聚而成的金属-氧簇类化合物．由于其具有丰富的分子结构和独特的物理化学性质，已经被广泛应用于功能材料、催化化学和药物化学等领域．其中钒取代的多酸阴离子具有很好的催化活性，特别是对烃类的氧化，它的活性主要受钒取代的数目和钒中心的阴离子环境这两个因素影响．该文利用固体核磁技术分析了一取代钒的两类典型结构中⁵¹V的局域结构和化学环境，以及有机阳离子对多酸阴离子结构的影响，特别是对⁵¹V的化学环境的影响，为研究多酸的催化活性和催化机理提供基本的结构信息．

关键词： 多金属氧酸盐(POMs); 固体核磁共振; ⁵¹V核磁共振谱; 钨钒酸; 磷钨钒酸

本文引用格式

丁丽红1 , 2 , 刘小龙2 , 王强2 , 刘文涛1 , 朱诚身1 , 郑安民2 , 邓风2* . 多金属氧酸盐TBA₃[VW₅O₁₉]及TBA₄[PVW₁₁O₄₀]的固体核磁共振研究[J]. 波谱学杂志, 2015 , 32(3) : 409 -418 . DOI: 10.11938/cjmr20150302

Abstract

Polyoxometalates (POMs) are metal cluster compounds formed by transition metal atoms with d⁰ or d¹ electron configuration via edge or corner polycondensation. Because of their unique molecular structures and physical/chemical properties, POMs have been widely used in functional materials, catalytic chemistry and medicinal chemistry etc. Vanadium-substituted POMs often have high catalytic activities for hydrocarbon oxidation, and such activities are mainly related to the number of vanadium atom and the electron environment these atoms are in. Solid-state NMR, as one of the most important methods to characterize solid acid materials, has been widely applied to study POMs. In this paper, butanyl cations and vanadium atoms in Lindqvist and Keggin oxopolytungstates were characterized by ¹³C and ⁵¹V solid state NMR spectroscopy to obtain information on the local environment these cations and vanadium centers are in. Such information is important for understanding the oxidation catalytic mechanism. It is concluded that ⁵¹V solid state NMR spectroscopy can be a quick, convenient and nondestructive tool to study the local environment for vanadium atoms and the bulk morphologies of POMs.

Key words： polyoxometalates; solid-state NMR; ⁵¹V magic-angle-spinning spectroscopy; Lindqvist; Keggin

参考文献

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