基于3D受限自组装构筑中空介孔氧化硅/碳复合微球  

Silica/Carbon Composite Hollow Mesoporous Microparticles by 3D Confined Self-assembly

作　　者：王勉 邓仁华 朱锦涛 Mian Wang;Ren-hua Deng;Jin-tao Zhu(Key Laboratory of Materials Chemistry for Energy Conversion and Storage of Ministry of Education(HUST),Hubei Key Laboratory of Materials Chemistry and Service Failure,School of Chemistry and Chemical Engineering,Huazhong University of Science and Technology,Wuhan 430074)

机构地区：[1]华中科技大学化学与化工学院,能量转换与存储材料化学教育部重点实验室,材料化学与服役失效湖北省重点实验室,武汉430074

出　　处：《高分子学报》2024年第5期604-613,共10页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52273010,52322314)资助项目。

摘　　要：发展简单、高效、可控的方法来制备中空介孔微球是介孔材料领域的研究热点.本工作结合嵌段共聚物的三维受限自组装(3D-CSA)和自模板碳化策略,建立了一种构筑中空介孔微球的新方法.首先,采用乳液-溶剂挥发法实现嵌段共聚物与全氟辛烷(PFO)在3D受限空间的分级组装,获得了核-壳结构微球,其中壳层由微相分离的嵌段共聚物构成.然后,在壳层的连续相选择性地复合氧化硅,既实现了无机框架的负载,又实现了对连续相聚合物链选择性交联.对复合微球进行煅烧处理后,实现了壳层连续相聚合物的选择性碳化,获得了中空介孔氧化硅/碳复合微球.本研究系统地阐述了核-壳型分级结构微球的形成机理和必备条件,研究了氧化硅前驱体添加量和嵌段共聚物分子量对中空介孔氧化硅/碳复合微球形貌的影响,为制备中空介孔微球材料提供了一种简便、可控的方法.Hollow mesoporous microparticles have attracted much attention because of their unique internal cavity structure and functional shell,which combines the physical and chemical properties of mesoporous materials.It is therefore of great interest to develop facile,effective,and controllable methods for the preparation of hollow mesoporous microspheres.This research proposes a new strategy for creating silica/carbon composite hollow mesoporous microparticles via the combination of three-dimensional confined self-assembly(3D-CSA)of block copolymer(BCP)and a self-template carbonization strategy.Firstly,using the 3D-CSA method,the BCP and perfluorooctane(PFO)underwent hierarchical self-assembly into core-shell microparticles.Notably,the shell was composed of BCP with mesostructures via microphase separation.Then,the continuous phase of the shell was selectively composited with silicon oxide on purpose of loading of the inorganic frame and cross-linking.Ultimately,the silica/carbon composite hollow mesoporous microspheres were generated by calcining the composite microparticles to selectively carbonize the continuous phase of the shell.The formation mechanism and necessary conditions of core-shell microparticles were systematically described.Additionally,the effects of the amount of precursors and the molecular weight of BCP on the morphology of hollow mesoporous microspheres were studied.This research provides a simple yet controllable method for the creation of novel hollow mesoporous microparticles.

关 键 词：嵌段共聚物 三维受限 自组装 中空微球 介孔微球 

分 类 号：TB332[一般工业技术—材料科学与工程]