Department of Chemistry, State Key Laboratory of Molecular Engineering of Polymers, Shanghai Key Lab of Molecular Catalysis and Innovative Materials, iChEM, Fudan University , Shanghai 200433, PR China.
The Key Laboratory of Biomedical Information Engineering of Ministry of Education, School of Life Science and Technology, Xi'an Jiaotong University , Xi'an, Shaanxi 710049, PR China.
J Am Chem Soc. 2017 Feb 8;139(5):1706-1713. doi: 10.1021/jacs.6b11411. Epub 2017 Jan 25.
Ordered mesoporous materials (OMMs) have received increasing interest due to their uniform pore size, high surface area, various compositions and wide applications in energy conversion and storage, biomedicine and environmental remediation, etc. The soft templating synthesis using surfactants or amphiphilic block copolymers is the most efficient method to produce OMMs with tailorable pore structure and surface property. However, due to the limited choice of commercially available soft templates, the common OMMs usually show small pore size and amorphous (or semicrystalline) frameworks. Tailor-made amphiphilic block copolymers with controllable molecular weights and compositions have recently emerged as alternative soft templates for synthesis of new OMMs with many unique features including adjustable mesostructures and framework compositions, ultralarge pores, thick pore walls, high thermal stability and crystalline frameworks. In this Perspective, recent progresses and some new insights into the coassembly process about the synthesis of OMMs based on these tailor-made copolymers as templates are summarized, and typical newly developed synthesis methods and strategies are discussed in depth, including solvent evaporation induced aggregation, ligand-assisted coassembly, solvent evaporation induced micelle fusion-aggregation assembly, homopolymer assisted pore expanding and carbon-supported crystallization strategy. Then, the applications of the obtained large-pore OMMs in catalysis, sensor, energy conversion and storage, and biomedicine by loading large-size guest molecules (e.g., protein and RNA), precious metal nanoparticles and quantum dots, are discussed. At last, the outlook on the prospects and challenges of future research about the synthesis of large-pore OMMs by using tailor-made amphiphilic block copolymers are included.
有序介孔材料（OMM）由于其均匀的孔径、高的比表面积、多种组成以及在能源转换和存储、生物医学和环境修复等领域的广泛应用而受到越来越多的关注。使用表面活性剂或两亲嵌段共聚物的软模板合成是制备具有可调节孔结构和表面性能的 OMM 的最有效方法。然而，由于商业上可用的软模板选择有限，常见的 OMM 通常具有较小的孔径和无定形（或半结晶）骨架。最近，具有可控分子量和组成的定制两亲嵌段共聚物作为替代软模板出现，用于合成具有许多独特特征的新型 OMM，包括可调谐的介孔结构和骨架组成、超大孔、厚孔壁、高热稳定性和结晶骨架。在本综述中，总结了基于这些定制共聚物作为模板合成 OMM 的共组装过程的最新进展和一些新的见解，并深入讨论了典型的新开发的合成方法和策略，包括溶剂蒸发诱导聚集、配体辅助共组装、溶剂蒸发诱导胶束融合-聚集组装、均聚物辅助扩孔和碳负载结晶策略。然后，讨论了通过负载大尺寸客体分子（如蛋白质和 RNA）、贵金属纳米粒子和量子点，获得的大孔 OMM 在催化、传感器、能量转换和存储以及生物医学中的应用。最后，包括对使用定制两亲嵌段共聚物合成大孔 OMM 的未来研究的前景和挑战的展望。
