Microporous and Mesoporous Materials ( IF 4.8 ) Pub Date : 2023-12-01 , DOI: 10.1016/j.micromeso.2023.112923
Lucy Zhao , Joanna J. Mikolei , Marcelo Ceolin , Raheleh Pardehkhorram , Laura Czerwenka , Annette Andrieu-Brunsen
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Multistimuli-responsive, in-situ functionalized mesoporous silica films were fabricated by evaporation-induced self-assembly through physical entrapment of the functional template poly(ethylene oxide)-b-poly(2-nitrobenzyl acrylate) (PEO-b-PNBA). The light-cleavable and pH-responsive block copolymer PEO-b-PNBA simultaneously serves as structure-directing agent and for in-situ polymer functionalization of the generated mesopore space. The use of different PEO-b-PNBA compositions results in highly filled hybrid mesoporous silica films with different pore sizes, porosity, and polymer chain sequence within the mesopores. Based on these structural variations and the polymer chain sequence the ionic permselectivity of the silica-polymer hybrid thin films is adjusted. The side chains of the template PNBA block can be deprotected upon irradiation, hereby releasing pH-responsive carboxylic acid groups. The irradiation energy and irradiation time-dependent deprotection allows gradually controlled charge regulation in mesopores. This approach of in-situ functionalization using multistimuli-responsive PEO-b-PNBA block copolymers facilitates the fabrication of multi-responsive hybrid mesoporous silica films and bears high potential for the production of complex, hierarchical, multifunctional mesoporous materials. This fabrication method including direct functionalization of mesoporous structures is of high interest for many applications based on controlled molecular transport in nanoscale pores, such as sensing, separation, or catalysis.
中文翻译:

PEO-b-PNBA 原位功能化介孔二氧化硅薄膜及其光和 pH 控制的离子介孔可及性
通过物理捕获功能模板聚(环氧乙烷) -b-聚(2-硝基丙烯酸苄酯)(PEO- b -PNBA) ,通过蒸发诱导自组装制备了多刺激响应的原位功能化介孔二氧化硅薄膜。可光裂解且pH响应的嵌段共聚物PEO- b -PNBA同时充当结构导向剂并用于所生成的介孔空间的原位聚合物功能化。使用不同的PEO- b -PNBA组合物导致高度填充的杂化介孔二氧化硅薄膜,其具有不同的孔径、孔隙率和介孔内的聚合物链序列。基于这些结构变化和聚合物链序列,调节二氧化硅-聚合物杂化薄膜的离子选择性渗透性。模板 PNBA 嵌段的侧链可在辐射后脱保护,从而释放 pH 响应性羧酸基团。辐照能量和辐照时间依赖性脱保护允许逐渐控制中孔中的电荷调节。这种使用多刺激响应PEO- b -PNBA嵌段共聚物的原位功能化方法有利于多响应杂化介孔二氧化硅薄膜的制备,并且具有生产复杂、分级、多功能介孔材料的巨大潜力。这种包括介孔结构直接功能化的制造方法对于基于纳米级孔中受控分子传输的许多应用(例如传感、分离或催化)非常有意义。