The syntheses of a family of highly ordered mesoporous polymers and carbon frameworks from organic−organic assembly of triblock copolymers with soluble, low-molecular-weight phenolic resin precursors (resols) by an evaporation induced self-assembly strategy have been reported in detail. The family members include two-dimensional hexagonal (space group, p6m), three-dimensional bicontinuous (Ia3̄d), body-centered cubic (Im3̄m), and lamellar mesostructures, which are controlled by simply adjusting the ratio of phenol/template or poly(ethylene oxide)/poly(propylene oxide) in the templates. A five-step mechanism from organic−organic assembly has been demonstrated. Cubic FDU-14 with a gyroidal mesostructure of polymer resin or carbon has been synthesized for the first time by using the copolymer Pluronic P123 as a template in a relatively narrow range. Upon calcination at 350 °C, the templates should be removed to obtain mesoporous polymers, and further heating at above a critical temperature of 600 °C transforms the mesoporous polymers to the homologous carbon frameworks. The mesoporous polymer resin and carbon product materials exhibit ordered structures, high surface areas, (670−1490 m2/g), large pore volumes (0.65−0.85 cm3/g), and uniform, large pore sizes (7.0−3.9 nm), as well as very thick pore walls (6−8 nm). The carbon open frameworks with covalently bonded constructions and thick pore walls exhibit high thermal stability (>1400 °C). Our results show that the feed gas used during the calcination has a great influence on the porosity of the products. The presence of a small amount of oxygen facilitates the large pore sizes and high surface areas of mesoporous materials with different mesostructures. An extraction method employing sulfuric acid can also decompose the template from hexagonal mesostructured polymers with little framework shrinkage. Preliminary studies of the mechanical and electrochemical properties of mesoporous carbon molecular sieves are also presented.
Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized.
is still hindered by some main fundamental obstacles, including the insulating nature of sulfur and lithium sulfides (Li 2 S), and the notorious shuttle effect of lithium polysulfides (LiPSs) intermediates during cycling process. The shuttle effect brings about not only the loss of the active materials but also the anode corrosion, leading to rapid capacity degradation and low Coulombic efficiency. [4,5] Carbon nanomaterials with high electrical conductivity, desirable porous structure, and controlled dimensions have been devoted to the design of sulfur hosts [6][7][8][9][10][11][12][13] or interlayers [14][15][16] to physically restrain LiPSs in the cathode area, however, the weak interactions between nonpolar carbon and polar LiPSs discount the effectiveness during the long-term cycling. Chemical trapping of LiPSs with polar transition metal compounds such as TiO 2 , MnO 2 , etc., via polar-polar interactions is an available approach to mitigate the LiPSs shuttling. [17][18][19][20][21] Nonetheless, when the sulfur content and electrode mass loading are high, the massive generated LiPSs are difficult to be immobilized due to the adsorption saturation by these compounds. The detrimental shuttle effect in lithium-sulfur batteries mainly results from the mobility of soluble polysulfide intermediates and their sluggish conversion kinetics. Herein, presented is a multifunctional catalyst with the merits of strong polysulfides adsorption ability, superior polysulfides conversion activity, high specific surface area, and electron conductivity by in situ crafting of the TiO 2 -MXene (Ti 3 C 2 T x ) heterostructures. The uniformly distributed TiO 2 on MXene sheets act as capturing centers to immobilize polysulfides, the hetero-interface ensures rapid diffusion of anchored polysulfides from TiO 2 to MXene, and the oxygen-terminated MXene surfaceis endowed with high catalytic activity toward polysulfide conversion. The improved lithium-sulfur batteries deliver 800 mAh g −1 at 2 C and an ultralow capacity decay of 0.028% per cycle over 1000 cycles at 2 C. Even with a high sulfur loading of 5.1 mg cm −2 , the capacity retention of 93% after 200 cycles is still maintained. This work sheds new insights into the design of highperformance catalysts with manipulated chemical components and tailored surface chemistry to regulate polysulfides in Li-S batteries.
We demonstrate, for the first time, the application of ordered mesoporous carbons with large pore sizes prepared from the surfactant-templating approach in efficient disposal of wastewater containing bulky dye molecules. The adsorption amount for the bulky dye (methylthionine chloride, fuchsin basic, rhodamine B, brilliant yellow, methyl orange, or Sudan G) is almost twice that of the activated carbon in which mesopores contribute almost 100% to the total surface area and volume. The ordered mesoporous carbon adsorbent has a high adsorption rate (>99.9%) for low-concentration dyes, good performance in decoloration regardless of the dye nature, including basic, acidic, or azo dyes, and high stability after dye elution. To establish the relationship between the pore texture and adsorption properties, three kinds of ordered mesoporous carbons with different pore sizes, surface areas, and pore volumes have been synthesized by using phenolic resins as carbon sources and triblock copolymer as a structure-directing agent. The XRD, TEM, and N 2 sorption measurements reveal that all mesoporous carbonaceous materials have the highly ordered 2D hexagonal mesostructure, high surface areas (398-2580 m 2 /g), large pore volumes (0.51-2.16 cm 3 /g), and uniform pore sizes ranging from 4.5 to 6.4 nm. The adsorption capacities are compared and the pore occupation is estimated to understand the adsorption behaviors in the ordered mesopores with different diameters and models. The spatial effect of dye molecules is the determinative factor for the adsorption in ordered mesoporous carbons with various pore textural properties. The mesoporous carbon with an extremely high surface area (2580 m 2 /g), a large pore volume (2.16 cm 3 /g), and bimodal pores (6.4 and 1.7 nm) prepared from the silica-carbon composite shows the highest adsorption capacities for bulky basic dyes among the three ordered mesoporous carbons.
Supramolecular aggregate's self-assembling approach has derived diverse mesostructured inorganic solids. Recent progresses involve ordered mesoporous carbonaceous frameworks. This review paper summarizes the synthesis of ordered mesoporous polymers and carbons based on the supramolecular aggregates as templates. Block copolymers are mainly introduced here. Both the aggregates of block copolymers themselves and the assembling with thermosetting resins have the abilities to organize ordered mesostructures. The understanding of the synthesis is on the formation of supramolecular arrangement of molecules, templating, cross-linking, removal of templates, and carbonization. In addition, the morphological control and the functionalization of ordered mesoporous carbonaceous materials are briefly summarized. The attractive mesoporous carbonaceous materials offer great opportunities in catalysis, water purification, electrodes, adsorbents, gas storage, aero-space, etc.
Ordered mesoporous inorganic non-oxide materials attract increasing interest due to their plenty of unique properties and functionalities and potential applications. Lots of achievements have been made on their synthesis and structural characterization, especially in the last five years. In this critical review, the ordered mesoporous non-oxide materials are categorized by compositions, including non-oxide ceramics, metal chalcogenides, metal nitrides, carbides and fluorides, and systematically summarized on the basis of their synthesis approaches and mechanisms, as well as properties. Two synthesis routes such as hard-templating (nanocasting) and soft-templating (surfactant assembly) routes are demonstrated. The principal issues in the nanocasting synthesis including the template composition and mesostructure, pore surface chemistry, precursor selection, processing and template removal are emphatically described. A great number of successful cases from the soft-templating method are focused on the surfactant liquid-crystal mesophases to synthesize mesostructured metal chalcogenide composites and the inorganic-block-organic copolymer self-assembly to obtain non-oxide ceramics (296 references).
The continual needs for improved performances in applications derived by diversified compositions and mesostructures have pushed forward the development of mesoporous solids. The nonionic-surfactant-templating approach has been a critical route in this advancement. A large number of nonionic surfactants widely used in industries and featured with low cost, low toxicity, bio-degradation and ordered microdomains can be utilized as effective templates to the design and synthesis of abundant mesoporous solids. This feature article provides recent reports on the use of nonionic surfactant self-assembly as examples to fabricate high-quality ordered mesoporous solids which illustrates advances in synthesis and understanding of formation mechanisms. It includes the selection of surfactants, a summary of the effects of synthetic parameters, the current understanding of the synthetic pathways and related mechanisms with some emphasis on evaporation induced self-assembly (EISA), as well as the design and synthesis on the microscale (atomic and molecular compositions) and mesoscale (mesostructures). Preliminary applications of mesoporous solids particularly in optical devices, electrodes and biomaterials are also presented.
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