溶剂化效应对金属-有机骨架材料界面微环境催化性能的影响

doi:10.3969/j.issn.0438-1157.2014.05.014

化工学报

• 催化、动力学与反应器 • 上一篇下一篇

溶剂化效应对金属-有机骨架材料界面微环境催化性能的影响

应允攀¹, 曾凡平¹, 吴平易², 阳庆元¹, 刘大欢¹, 兰玲², 王少华³, 张轶³, 仲崇立¹

1 北京化工大学有机无机复合材料国家重点实验室, 北京 100029;
2 中国石油化工研究院, 北京 100195;
3 中国昆仑工程公司辽宁分公司, 辽宁辽阳 111003

收稿日期:2013-12-26 修回日期:2014-01-27 出版日期:2014-05-05 发布日期:2014-05-05
通讯作者: 兰玲,张轶
基金资助:
国家重点基础研究发展计划项目（2013CB733503）；国家自然科学基金项目（21136001，21276009）。

Solvent effect on catalytic properties of microstructures in metal-organic frameworks

YING Yunpan¹, ZENG Fanping¹, WU Pingyi², YANG Qingyuan¹, LIU Dahuan¹, LAN Ling², WANG Shaohua³, ZHANG Yi³, ZHONG Chongli¹

1 State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China;
2 Petrochemical Research Institute, PetroChna, Beijing 100195, China;
3 China Kunlun Contracting Engineering Corporation Liaoning Company, Liaoyang 111003, Liaoning, China

Received:2013-12-26 Revised:2014-01-27 Online:2014-05-05 Published:2014-05-05
Supported by:
supported by the National Basic Research Program of China ( 2013CB733503) and the National Natural Science Foundation of China ( 21136001,21276009).

摘要/Abstract

摘要： 金属-有机骨架材料（metal-organic frameworks，MOFs）的纳微结构可根据特定需求进行功能化调控，有望成为良好的工业催化材料。由于溶剂环境可对其界面微环境及催化性能产生较大影响，因此研究溶剂化效应对于MOF材料的影响具有重要的意义。以Cu-BTC和MOP-15两种典型MOF材料作为研究对象，采用密度泛函理论与COSMO溶剂模型相结合的方法，考察了溶剂效应对材料几何结构与电子稳定性的影响，并研究了不同溶剂对其Lewis酸性的影响。结果表明，溶剂环境可以使材料中的电子从不饱和配位金属处转移到有机配体上，进而使材料具有更强的Lewis酸性，并且电负性较大有机配体构成的MOF材料，受溶剂效应的影响更加显著。本工作将有助于深入理解溶剂化对调控MOF材料液相催化活性的影响。

关键词: 密度泛函理论, 催化, Lewis酸性位, 金属-有机骨架材料, 界面, 溶剂

Abstract: The nanoporous structures of metal-organic frameworks (MOFs) can be functionally regulated according to specific targets of interest, and thus such types of solids can be considered as promising industrial catalytic materials. Since interface microenvironments and catalytic properties of MOFs might be affected by the solvents, it is necessary to study the influence of solvent effects on their catalytic activities. Although MOFs with coordinatively unsaturated metal sites (CUMs) have shown promising applications in liquid-phase catalysis, the related solvent effects on the Lewis acid catalytic performance of these CUMs are seldom investigated. In this work, density functional theory calculations were conducted to investigate the solvent effects on the properties of the Lewis acid sites in two typical MOFs, Cu-BTC and MOP-15, where the COSMO (conductor-like solvent model) was used to mimic the dielectric response of the solvent environments. Different relative dielectric constants were considered, including in vacuum, toluene, ethyl acetate, 1, 2-dichloroethane and acetonitrile. Using CO as the probe molecule, the solvent effects were examined by exploring the geometry parameters, the Mulliken charges, and the vibrational frequency as well as the adsorption energy of CO molecule around those CUMs. The strengths of Lewis acid sites could be enhanced with the increase of the dielectric constant. Further, the solvent effects became more evident in CUMs when the organic linkers had higher electronegativity. These observations provide fundamental insights into the regulation of the liquid-phase catalytic activity of MOFs using specific solvents.

Key words: density functional theory, catalysis, Lewis acid site, metal-organic frameworks, interface, solvent

中图分类号:

TQ032.4

应允攀, 曾凡平, 吴平易, 阳庆元, 刘大欢, 兰玲, 王少华, 张轶, 仲崇立. 溶剂化效应对金属-有机骨架材料界面微环境催化性能的影响[J]. 化工学报, DOI: 10.3969/j.issn.0438-1157.2014.05.014.

YING Yunpan, ZENG Fanping, WU Pingyi, YANG Qingyuan, LIU Dahuan, LAN Ling, WANG Shaohua, ZHANG Yi, ZHONG Chongli. Solvent effect on catalytic properties of microstructures in metal-organic frameworks[J]. CIESC Journal, DOI: 10.3969/j.issn.0438-1157.2014.05.014.

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溶剂化效应对金属-有机骨架材料界面微环境催化性能的影响

Solvent effect on catalytic properties of microstructures in metal-organic frameworks

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