•Polyhedral oligosilsesquioxanes are assembled into hierarchically porous carbons.•The carbons contain uniform micropores interconnected with highly ordered mesopores.•Nitrogen functionalities can spontaneously be incorporated into the carbon materials.•The porous carbons have desired structural characteristics towards supercapacitors.Polyhedral oligosilsesquioxanes (POSS), regarded as the smallest possible particles of silica, are used as carbon source and assembled into hierarchically porous carbon structures by a block copolymer-assisted method. The obtained carbon materials with high specific surface area of over 2000 m2 g−1 and large pore volume of over 1.19 cm3 g−1 possess both quite uniform micropores with the size of ~1 nm and highly ordered mesopores with the size of ~4 nm, owing to the molecular-scale templating effect of POSS siloxane cages as well as the good assembly compatibility between the block copolymers and the aminophenyl-functionalized POSS used. The mesopore arrangement can be two-dimensionally hexagonal (p6m) or body-centered cubic (Im  3¯m) by simply adjusting different block copolymers. Nitrogen functionalities with a relatively high content (~4 wt%) can spontaneously be incorporated into those carbon materials. Benifiting from the uniform microporosity and the nitrogen doping, the specific capacitance of the POSS-derived hierarchically porous carbons can reach ~160 F g−1 in ionic liquid electrolyte and ~210 F g−1 in 1 M H2SO4 aqueous electrolyte, when measured at a current density of 0.25 A g−1 in a symmetrical two-electrode cell. More importantly, the highly ordered mesopores can facilitate ions fast transportion to the fine micropores to achieve the excellent power performance. The hierarchial carbon sample with a hexagonal mesostructure and a high mesoporosity displays the best rate capability with 94% and 97% of capacitance retention in ionic liquid and 1 M H2SO4, respectively, with the current density range from 0.25 to 10 A g−1. By combining self-assembly strategy with rich POSS chemistry, we believe that many other hierarchical hybrid materials or carbon materials with unique electrochemical properties can be synthesized.

A strongly acidic aqueous cooperative assembly route has been developed to synthesize ordered mesoporous carbons (OMCs) through using the triblock copolymer P123 (EO20PO70EO20) as a template and resorcinol/hexamine as a precursor pair. By replacing commonly used formaldehyde with hexamine as a cross-linking monomer, the self-assembly kinetics of resorcinol/formaldehyde resin and P123 can be well controlled, leading to high-quality carbon materials with 2-D hexagonal mesostructure and fiberlike morphology. The sizes and structural properties of the fiberlike carbons can be tailored easily through varying reaction parameters, such as P123 concentration and reaction temperature. A coulombic interaction between resorcinolic species and P123 is proposed to be the driving force that induces the organic–organic cooperative assembly. The additional KOH activation of the fiberlike carbons can increase significantly the surface area due to the generation of microporosity in mesopore walls while the ordered mesostructure remains intact. The structural characteristics of these fiberlike OMCs also endow them with excellent electrochemical capacitive performance. Hierarchically ordered mesostructures with microporosity can further improve the capacitive performance.

We proposed here a one-pot route to prepare resorcinol/formaldehyde (RF) resin-based carbon materials with highly ordered mesostructures in an aqueous media. Compared with other techniques, the synthesis is a single-step process; neither prepolymerization nor thermal solidification is needed. The crucial difference to the previous methods is that the commonly used formaldehyde is replaced with hexamine. Hexamine can serve as a release source of formaldehyde to control the kinetics of RF polymerization reaction. The combined use of resorcinol and hexamine allows the accelerated synthesis without disturbing the cooperative self-assembly of RF resin and amphiphilic triblock copolymer. A mesophase transformation from body-centered cubic (Im3¯m) to 2-D hexagonal (p6m) structure can be achieved by simply adding 1,3,5-trimethylbenzene to the synthesis. Especially, this synthesis can be performed not only under weakly basic conditions but also under highly acidic conditions, despite that the acid-catalyzed synthesis will result in the formation of the product with a relatively low thermal stability.

Hexamine has been used as a release source of formaldehyde towards the self-assembly synthesis of resorcinol/formaldehyde (RF) resin-based mesoporous carbons under hydrothermal conditions. The obtained mesoporous carbons exhibit the micrometer-sized, sphere-like morphology and a high surface area. The use of hexamine instead of formaldehyde efficiently harnesses the organic–organic self-assembly of RF resin and block copolymer. Ordered mesostructures can be obtained over a wide range of hydrothermal temperature without the extra addition of inorganic bases or acids as catalysts. The method described here has the advantage of being a one-pot procedure and only involves the use of several organic precursors in an aqueous system.

We demonstrate a simple and reproducible method to prepare thermally stable, crystalline mesoporous Ti oxide/carbon composites. The composites were obtained using titania nanoparticles as inorganic precursors, phenolic resols as carbon sources, and triblock copolymer F127 as a template based on the solvent evaporation-induced self-assembly process. The use of stable titania nanoparticles favored the reproducible preparation of mesoporous Ti–C composites over a wide range of Ti oxide/carbon ratios without the control of atmospheric humidity. Various analysis techniques have been used to investigate the pore structure and crystallinity as a function of synthesis conditions. The resultant composites have an ordered 2D hexagonal mesostructure with high surface areas (200–800 m2 g−1). In addition to the calcination temperature, the carbon content also has significant effect on the crystalline transformation of titanium species.Graphical abstractAs-made mesostructrued titania/resin composite.Research highlights► Crystalline ordered mesoporous titanium oxide/carbon composites are prepared by a nanoparticle assembly method. ► Ti species/carbon ratios in the composites can be tuned freely. ► The carbon content has significant effect on the crystalline transformation of titanium species. ► Anatase, rutile or TiO nanocrystals are formed in the pore walls of ordered mesoporous composites.

A strongly acidic aqueous cooperative assembly route has been developed to synthesize ordered mesoporous carbons (OMCs) through using the triblock copolymer P123 (EO20PO70EO20) as a template and resorcinol/hexamine as a precursor pair. By replacing commonly used formaldehyde with hexamine as a cross-linking monomer, the self-assembly kinetics of resorcinol/formaldehyde resin and P123 can be well controlled, leading to high-quality carbon materials with 2-D hexagonal mesostructure and fiberlike morphology. The sizes and structural properties of the fiberlike carbons can be tailored easily through varying reaction parameters, such as P123 concentration and reaction temperature. A coulombic interaction between resorcinolic species and P123 is proposed to be the driving force that induces the organic–organic cooperative assembly. The additional KOH activation of the fiberlike carbons can increase significantly the surface area due to the generation of microporosity in mesopore walls while the ordered mesostructure remains intact. The structural characteristics of these fiberlike OMCs also endow them with excellent electrochemical capacitive performance. Hierarchically ordered mesostructures with microporosity can further improve the capacitive performance.