新型两亲性嵌段共聚物导向合成有序大孔径介孔材料的研究进展

doi:10.15541/jim20160297

无机材料学报 ›› 2017, Vol. 32 ›› Issue (1): 1-10.DOI: 10.15541/jim20160297 CSTR: 32189.14.10.15541/jim20160297

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新型两亲性嵌段共聚物导向合成有序大孔径介孔材料的研究进展

罗维^1,2, 魏晶³, 邓勇辉³, 李宇慧³, 王连军¹, 赵涛¹, 江莞¹

(1. 东华大学纤维材料改性国家重点实验室, 材料科学与工程学院, 上海201620; 2. 中国科学院上海硅酸盐研究所, 上海200050; 3.复旦大学化学系, 上海200433)

收稿日期:2016-05-10 修回日期:2016-06-14 出版日期:2017-01-20 网络出版日期:2016-12-15
作者简介:罗维(1983–), 男, 博士, 讲师. E-mail: wluo@dhu.edu.cn
基金资助:
国家自然科学基金(51402049, 51432004);上海市科委项目(14ZR1400600);高等学校学科创新引智计划(111-2-04);中央高校基本科研业务费(2232015D3-06)

Progress on the Fabrication of Ordered Mesoporous Materials with Large Pores by Using Novel Amphiphilic Block Copolymers as Templates

LUO Wei^1,2, WEI Jing³, DENG Yong-Hui³, LI Yu-Hui³, WANG Lian-Jun¹, ZHAO Tao¹, JIANG Wan¹

(1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China; 2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China; 3. Department of Chemistry, Fudan University, Shanghai 200433, China)

Received:2016-05-10 Revised:2016-06-14 Published:2017-01-20 Online:2016-12-15
About author:LUO Wei. E-mail: wluo@dhu.edu.cn
Supported by:
National Natural Science Foundation of China (51402049, 51432004);Shanghai Committee of Science and Technology, China (14ZR1400600);Programme of Introducing Talents of Discipline to Universities (111-2-04);Fundamental Research Funds for the Central Universities (2232015D3-06)

摘要/Abstract

摘要：

自从1992年首次报道介孔氧化硅分子筛M41S系列以来, 人们采用各种商业化表面活性剂为模板, 合成了多种骨架组成、丰富的有序介观结构、不同孔径尺寸的介孔材料, 并将其应用在能源、环境、催化等诸多领域。然而, 由于常规商业化模板剂的分子量大小有限, 合成的介孔材料具有较小的孔径(< 8.0 nm), 从而极大地限制了其面对大尺寸客体分子的相关应用。此外, 利用常规模板剂难以合成出具有晶化墙壁的介孔金属氧化物材料。近年来, 大分子量两亲性嵌段共聚物相继被报道用来合成新型介孔材料, 本文将综述基于这种嵌段共聚物为模板剂合成各种具有大孔径和晶化墙壁介孔材料的研究进展。

关键词: 介孔材料, 嵌段共聚物, 软模板, 自组装, 综述

Abstract:

Ever since mesoporous silica M41S were reported in 1992, various mesoporous materials with diverse frameworks, abundant ordered mesostructures and different pore size have been synthesized by using commercial surfactants as template, due to their great potential for applications in energy storage and conversion, environmental remedy, catalysis. However, these mesoporous materials usually have pore sizes of less than 8.0 nm resulting from the low molecule weight of commercial templates, which greatly limit their applications in large guest objects. Moreover, these commercial templates are hard to synthesize ordered mesoporous metal oxides with high crystallinity. Recently, various amphiphilic copolymers with high molecule weight were reported to fabricate novel mesoporous materials, the recent research advances about their templated ordered mesoporous materials with large pore size and highly crystallized framework was reviewd in this paper.

Key words: mesoporous material, block copolymer, soft template, self-assembly, review

中图分类号:

TQ174

罗维, 魏晶, 邓勇辉, 李宇慧, 王连军, 赵涛, 江莞. 新型两亲性嵌段共聚物导向合成有序大孔径介孔材料的研究进展[J]. 无机材料学报, 2017, 32(1): 1-10.

LUO Wei, WEI Jing DENG Yong-Hui, LI Yu-Hui, WANG Lian-Jun, ZHAO Tao, JIANG Wan. Progress on the Fabrication of Ordered Mesoporous Materials with Large Pores by Using Novel Amphiphilic Block Copolymers as Templates[J]. Journal of Inorganic Materials, 2017, 32(1): 1-10.

图/表 9

图1 大孔径有序介孔氧化硅的透射电镜照片[42]

Fig. 1 TEM images of ordered mesoporous silica with large pores[42]

图2 EIAA法合成有序介孔氧化硅的机理示意图(a)和扫描电镜照片(b)[36]

Fig. 2 Schematic illustration of the formation process (a) and SEM image of mesoporous silica via EIAA approach (b)[36]

图3 以PS-b-P4VP为模板合成有序介孔碳材料的机理示意图(a)和扫描电镜照片(b)[43]

Fig. 3 Schematic illustration of the formation process of mesoporous carbon by using amphiphilic PS-b-P4VP copolymers as template (a) and its corresponding SEM image (b)[43]

图4 PEO-b-PMMA-b-PS为模板剂合成孔径与墙壁厚度可调的有序介孔碳材料示意图[46]

Fig. 4 Schematic illustration of the formation process of mesoporous carbon with tunable pore size and wall thickness by using amphiphilic PEO-b-PMMA-b-PS copolymers as template[46]

图5 选用KLE或P123为模板剂得到介孔二氧化钛材料的晶化过程示意图[50]

Fig. 5 Schematic illustration of the crystallization process of mesoporous titania by using KLE or P123 as templates[50]

图6 利用软-硬模板共组装(CASH)的方法合成高度晶化的介孔二氧化钛示意图[51]

Fig. 6 Schematic illustration of the formation process of mesoporous titania with high crystallinity via CASH approach[51]

图7 利用嵌段共聚物PEO-b-PS为模板剂合成具有简单立方介观结构的大孔径有序介孔氧化钛机理图[52]

Fig. 7 Schematic illustration of the formation process of mesoporous titania with large pores and simple cubic structure by using amphiphilic PEO-b-PS copolymers as template[52]

图8 以PEO-b-PS为模板剂通过RA-EISA法合成介孔氧化铌微球的场发射扫描电镜照片(a, b)和透射电镜照片(c, d)[18]

Fig. 8 SEM (a,b) and TEM (c,d) images of mesoporous niobia spheres via RA-EISA approach by using amphiphilic PEO-b-PS copolymers as template[18]

图9 介孔氧化钨材料的场发射扫描电镜照片(a, b)和透射电镜照片(c~f)[55]

Fig. 9 SEM (a,b) and TEM (c-f) images of mesoporous WO3[55]

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新型两亲性嵌段共聚物导向合成有序大孔径介孔材料的研究进展

Progress on the Fabrication of Ordered Mesoporous Materials with Large Pores by Using Novel Amphiphilic Block Copolymers as Templates

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