© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1 www.advmat.de www.MaterialsViews.com wileyonlinelibrary.com REVIEW Wei Li, Qin Yue, Yonghui Deng,* and Dongyuan Zhao Ordered Mesoporous Materials Based on Interfacial Assembly and Engineering W. Li, Q. Yue, Prof. Y. H. Deng, Prof. D. Y. Zhao Department of Chemistry and Shanghai Key Lab of Molecular Catalysis and Innovative Materials State key Laboratory of Molecular Engineering of Polymers Laboratory of Advanced Materials Fudan University Shanghai 200433, P. R. China E-mail: yhdeng@fudan.edu.cn DOI: 10.1002/adma.201302184 1. Introduction With recent progresses made in modern nanoscience and nanotechnology, ordered mesoporous materials have been one of the hottest research topics in scientific communities spanned chemistry, materials science, physics and biology. [1–3] That is because ordered mesoporous materials possess fas- cinating properties including regular, uniform and interpen- etrating mesopores, tunable pore sizes, high surface areas as well as abundant framework compositions. Compared with their bulk counterparts, they can interact with atoms, ions, mol- ecules or even larger guest species not only at the external sur- face, but also through the whole internal pore system. [4] As a result, ordered mesoporous materials exhibit substantial perfor- mance boosts in numerous applications such as adsorption, [5–7] separation, [8] catalysis, [9–11] sensors, [12] drug delivery, [13,14] energy conversion and storage, [15–19] and so on. Since the exciting dis- covery of this new kind of materials based on the supramolec- ular assembly chemistry in the early nineties, [20–22] considerable work has been done to synthesize ordered mesoporous materials with diverse com- positions, morphologies and pore symme- tries; meanwhile, tremendous effort has been devoted to elucidate the mechanism of mesostructure formation and explore their applications. The construction of mesoporous mate- rials is mainly concerned with building monodispersed mesosized (2-50 nm) pore voids and arranging them in a long- range ordered array. [23–25] Generally, two kinds of templates are used to produce the mesopores: supramolecular aggregates such as surfactant micelle arrays, and rigid preformed mesoporous solids such as ordered mesoporous silica, carbon, and colloidal crystals. [26,27] The corresponding synthesis pathways are commonly described in literatures as soft- and hard-templating (nano- casting) methods, respectively. Noticeably, besides the template, the interface also plays a central role in the processing, because it provides a rich and crucial space for the assembly and con- struction of mesostructures. Generally, there are two types of interfaces involved in the synthetic system. The first one is at between surfactant templates and guest species, which has been extensively investigated by several research groups. [28–32] It suggests that the effective interaction of surfactants-guest species is critical to govern the soft-templating route for syn- thesis of ordered mesoporous materials. [24] Although excel- lent progresses have been made on the cooperative assembly of mesostructures in an aqueous phase system, it has several inherent drawbacks: i) the resultant products are typically pow- ders with ill-defined morphology, precluding their general use in thin films or other shape-based technologies; ii) the prepa- ration of non-siliceous mesoporous materials is more chal- lenging because the hydrolysis and condensation of non-sili- ceous precursors (e.g., metal alkoxides) are generally difficult to control; iii) the arranged patterns and sizes of mesopores are often limited; iv) it is a great challenge to obtain multifunc- tional mesoporous materials through such one-pot cooperative assembly. Another important interface is the two-phase (solid, liquid and gas) one in the synthetic system, including liquid-solid, gas- liquid, liquid-liquid, gas-solid, and solid-solid interface, which has been well developed for synthesis of mesoporous mate- rials ( Figure 1). Compared with one-phase synthesis referring to homogeneous nucleation and growth, the introduction of a Ordered mesoporous materials have inspired prominent research interest due to their unique properties and functionalities and potential applications in adsorption, separation, catalysis, sensors, drug delivery, energy conver- sion and storage, and so on. Thanks to continuous efforts over the past two decades, great achievements have been made in the synthesis and structural characterization of mesoporous materials. In this review, we summarize recent progresses in preparing ordered mesoporous materials from the viewpoint of interfacial assembly and engineering. Five interfacial assembly and synthesis are comprehensively highlighted, including liquid-solid interfacial assembly, gas-liquid interfacial assembly, liquid-liquid interfacial assembly, gas-solid interfacial synthesis, and solid-solid interfacial synthesis, basics about their synthesis pathways, princples and interface engineering strategies. Adv. Mater. 2013, DOI: 10.1002/adma.201302184