Triblock Siloxane Copolymer Surfactant: Template for Spherical Mesoporous Silica with a Hexagonal Pore Ordering

• Published in: Langmuir 2013-02, Vol.29 (5), p.1618-1626
• Main Authors: Stébé, M. J, Emo, M, Forny-Le Follotec, A, Metlas-Komunjer, L, Pezron, I, Blin, J. L
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Chemistry; Colloidal state and disperse state; Exact sciences and technology; General and physical chemistry; Liquid Crystals - chemistry; Micelles; Particle Size; Polymers - chemistry; Porosity; Porous materials; Silicon Dioxide - chemical synthesis; Silicon Dioxide - chemistry; Siloxanes - chemistry; Surface Properties; Surface-Active Agents - chemistry
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la304315v

Ordered mesoporous silica materials with a spherical morphology have been prepared for the first time through the cooperative templating mechanism (CTM) by using a silicone triblock copolymer as template. The behavior of the pure siloxane copolymer amphiphile in water was first investigated. A direct micellar phase (L1) and a hexagonal (H1) liquid crystal were found. The determination of the structural parameters by SAXS measurements leads us to conclude that in the hexagonal liquid crystal phase a part of the ethylene oxide group is not hydrated as observed for the micelles. Mesoporous materials were then synthesized from the cooperative templating mechanism. The recovered materials were characterized by SAXS measurements, nitrogen adsorption–desorption analysis, and transmission and scanning electron microscopy. The results clearly evidence that one can control the morphology and the nanostructuring of the resulting material by modifying the synthesis parameters. Actually, highly ordered mesoporous materials with a spherical morphology have been obtained with a siloxane copolymer/tetramethoxysilane molar ratio of 0.10 after hydrothermal treatment at 100 °C. Our study also supports the fact that the interactions between micelles and the hydrolyzed precursor are one of the key parameters governing the formation of ordered mesostructures through the cooperative templating mechanism. Indeed, we have demonstrated that when the interactions between micelles are important, only wormhole-like structures are recovered.