Over the last two decades, in parallel to the rise of ordered mesoporous silica, porous nanostructured polymer-silica composites have attracted the interest of material scientists due to their promising perspectives of application as sorbents, ion-exchangers, supports, and catalysts. While knowledge is available regarding their synthesis and applications, understanding and controlling their pore properties in order to rationalize their performances remain challenging tasks. Greater knowledge is therefore needed regarding their precise characterization, especially using gas adsorption. To this aim, mesoporous polymer-silica nanocomposites were synthesized from two ordered mesoporous silica materials using a pore-surface restricted polymerization technique. Hydrophobic polystyrene, PS, and hydrophilic poly(2-hydroxyethyl methacrylate), PHEMA, were specifically confined and polymerized in the pores of high-quality SBA-15 and KIT-6 silicas of different pore sizes. The physico-chemical characteristics of the resulting hybrid materials were probed in detail using gas physisorption at cryogenic temperatures (Ar at 87 K and N₂ at 77 K). The polymer loadings and the interactions between the silica host and the polymer were investigated using thermogravimetric analysis coupled with differential thermal analysis (TGA-DTA) and attenuated total reflection infrared spectroscopy (ATR-FTIR). The effects of the pore structure, mode pore size and presence or absence of intra-wall pores in the silica hosts on the final composite characteristics were assessed as a function of the polymer type and loading. Two different polymer filling mechanisms were identified as a function of the polymer-silica interactions, resulting in important changes on the pore topology of the composites. The results of this study allow a better understanding of the nature of the confined interactions between hydrophilic and hydrophobic polymers and large pore mesoporous silicas and shed some light on fundamental aspects regarding the design of silica-based composites.

在过去的二十年中，与有序介孔二氧化硅的兴起并行，多孔纳米结构的聚合物-二氧化硅复合材料因其作为吸附剂，离子交换剂，载体和催化剂的应用前景而备受材料科学家的关注。尽管可获得有关其合成和应用的知识，但了解和控制其孔隙性质以使其性能合理化仍然是一项艰巨的任务。因此，需要有关其精确表征的更多知识，尤其是使用气体吸附时。为此，使用孔表面受限聚合技术从两种有序介孔二氧化硅材料合成了介孔聚合物-二氧化硅纳米复合材料。疏水性聚苯乙烯PS和亲水性聚甲基丙烯酸2-羟乙酯PHEMA，被专门限制和聚合在不同孔径的高质量SBA-15和KIT-6二氧化硅的孔中。使用气体在低温下的物理吸附作用（Ar在87 K和N下）详细探测了所得杂化材料的理化特性。₂在77 K）。使用热重分析，差示热分析（TGA-DTA）和衰减全反射红外光谱（ATR-FTIR），研究了聚合物的负载量以及二氧化硅主体与聚合物之间的相互作用。根据聚合物类型和载量，评估了二氧化硅基质中孔结构，众数孔径以及壁内孔的存在与否对最终复合材料特性的影响。两种不同的聚合物填充机理被确定为聚合物-二氧化硅相互作用的函数，从而导致复合材料的孔拓扑发生重要变化。