Unified mechanistic interpretation of amine-assisted silica synthesis methods to enable design of more complex materials
The design of porous sol–gel silica materials is a thriving research field, owing to silica's diversity of properties and potential applications. Using a variety of additives, most commonly amine-based organic molecules, several families of silica materials have been developed including silica nanospheres, zeolites, mesoporous silicas, and bioinspired silicas with controlled particle and pore morphology on multiple length scales. Despite the wide range of study into these materials, and similarity in terms of reagents and additive compounds, none can recreate the features and complexity present within naturally occurring biosilica materials. This is due in part to a lack of ‘joined-up’ thinking during research into silica synthesis strategies and methodology. Specifically, mechanistic insights gained for one set of conditions or additive structures (i.e. material types) are not translated to other material types. In order to improve the structural complexity available in synthetic silica materials, as well as to improve both understanding and synthesis methods for all silica types, a unified approach to mechanistic understanding of formation in amine-assisted silica synthesis is required. Accordingly, in this review we analyse contemporary investigations into silica synthesis mechanism as a function of (amine) additive structure, analysing how they imprint varying levels of order into the eventual silica structure. We identify four fundamental driving forces through which additives control silica structure during synthesis: (i) controlling rates of silica precursor hydrolysis and condensation; (ii) forming charge-matched adducts with silicate ions in solution; (iii) self-assembling into mesophases to physically template pores; and (iv) confining the location of synthesis into specifically shaped vesicles. We analyse how each of these effects can be controlled as a function of additive structure, and highlight recent developments where multiple effects have been harnessed to form synthetic silica materials with further structural complexity than what was previously possible. Finally, we suggest further avenues of research which will lead to greater understanding of the structure–function relationship between amine additives and final materials, hence leading to more complex and high-value silica and other materials.
- This article is part of the themed collection: Nature-inspired solutions for engineering