A Family of Highly Ordered Mesoporous Polymer Resin and Carbon Structures from Organic−Organic Self-Assembly
TL;DR: In this paper, the synthesis of 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 has been reported.
Abstract: 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 (Ia3d), body-centered cubic (Im3m), 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 transfor...
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TL;DR: The "polymer chemistry" of g-C(3)N(4) is described, how band positions and bandgap can be varied by doping and copolymerization, and how the organic solid can be textured to make it an effective heterogenous catalyst.
Abstract: Polymeric graphitic carbon nitride materials (for simplicity: g-C(3)N(4)) have attracted much attention in recent years because of their similarity to graphene. They are composed of C, N, and some minor H content only. In contrast to graphenes, g-C(3)N(4) is a medium-bandgap semiconductor and in that role an effective photocatalyst and chemical catalyst for a broad variety of reactions. In this Review, we describe the "polymer chemistry" of this structure, how band positions and bandgap can be varied by doping and copolymerization, and how the organic solid can be textured to make it an effective heterogenous catalyst. g-C(3)N(4) and its modifications have a high thermal and chemical stability and can catalyze a number of "dream reactions", such as photochemical splitting of water, mild and selective oxidation reactions, and--as a coactive catalytic support--superactive hydrogenation reactions. As carbon nitride is metal-free as such, it also tolerates functional groups and is therefore suited for multipurpose applications in biomass conversion and sustainable chemistry.
2,735 citations
TL;DR: In order to further improve the power and energy densities of the capacitors, carbon-based composites combining electrical double layer capacitors (EDLC)-capacitance and pseudo-Capacitance have been explored and show not only enhanced capacitance, but as well good cyclability.
Abstract: Carbon materials have attracted intense interests as electrode materials for electrochemical capacitors, because of their high surface area, electrical conductivity, chemical stability and low cost. Activated carbons produced by different activation processes from various precursors are the most widely used electrodes. Recently, with the rapid growth of nanotechnology, nanostructured electrode materials, such as carbon nanotubes and template-synthesized porous carbons have been developed. Their unique electrical properties and well controlled pore sizes and structures facilitate fast ion and electron transportation. In order to further improve the power and energy densities of the capacitors, carbon-based composites combining electrical double layer capacitors (EDLC)-capacitance and pseudo-capacitance have been explored. They show not only enhanced capacitance, but as well good cyclability. In this review, recent progresses on carbon-based electrode materials are summarized, including activated carbons, carbon nanotubes, and template-synthesized porous carbons, in particular mesoporous carbons. Their advantages and disadvantages as electrochemical capacitors are discussed. At the end of this review, the future trends of electrochemical capacitors with high energy and power are proposed.
2,497 citations
2,090 citations
TL;DR: In this paper, the authors reviewed several key issues for improving the energy densities of supercapacitors and some mutual relationships among various effecting parameters, and challenges and perspectives in this exciting field are discussed.
Abstract: In recent years, tremendous research effort has been aimed at increasing the energy density of supercapacitors without sacrificing high power capability so that they reach the levels achieved in batteries and at lowering fabrication costs For this purpose, two important problems have to be solved: first, it is critical to develop ways to design high performance electrode materials for supercapacitors; second, it is necessary to achieve controllably assembled supercapacitor types (such as symmetric capacitors including double-layer and pseudo-capacitors, asymmetric capacitors, and Li-ion capacitors) The explosive growth of research in this field makes this review timely Recent progress in the research and development of high performance electrode materials and high-energy supercapacitors is summarized Several key issues for improving the energy densities of supercapacitors and some mutual relationships among various effecting parameters are reviewed, and challenges and perspectives in this exciting field are also discussed This provides fundamental insight into supercapacitors and offers an important guideline for future design of advanced next-generation supercapacitors for industrial and consumer applications
1,761 citations
TL;DR: Methods for the preparation of mesoporous carbon materials with extremely high surface areas and ordered mesostructures, with potential applications as catalysts, separation media, and advanced electronic materials in many scientific disciplines are developed.
Abstract: Porous carbon materials are of interest in many applications because of their high surface area and physicochemical properties. Conventional syntheses can only produce randomly porous materials, with little control over the pore-size distributions, let alone mesostructures. Recent breakthroughs in the preparation of other porous materials have resulted in the development of methods for the preparation of mesoporous carbon materials with extremely high surface areas and ordered mesostructures, with potential applications as catalysts, separation media, and advanced electronic materials in many scientific disciplines. Current syntheses can be categorized as either hard-template or soft-template methods. Both are examined in this Review along with procedures for surface functionalization of the carbon materials obtained.
1,716 citations
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TL;DR: Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms.
Abstract: Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms. The SBA-15 materials are synthesized in acidic media to produce highly ordered, two-dimensional hexagonal (space group p6mm) silica-block copolymer mesophases. Calcination at 500°C gives porous structures with unusually large interlattice d spacings of 74.5 to 320 angstroms between the (100) planes, pore sizes from 46 to 300 angstroms, pore volume fractions up to 0.85, and silica wall thicknesses of 31 to 64 angstroms. SBA-15 can be readily prepared over a wide range of uniform pore sizes and pore wall thicknesses at low temperature (35° to 80°C), using a variety of poly(alkylene oxide) triblock copolymers and by the addition of cosolvent organic molecules. The block copolymer species can be recovered for reuse by solvent extraction with ethanol or removed by heating at 140°C for 3 hours, in both cases, yielding a product that is thermally stable in boiling water.
10,807 citations
TL;DR: In this paper, the synthesis, characterization, and proposed mechanism of formation of a new family of silicatelaluminosilicate mesoporous molecular sieves designated as M41S is described.
Abstract: The synthesis, characterization, and proposed mechanism of formation of a new family of silicatelaluminosilicate mesoporous molecular sieves designated as M41S is described. MCM-41, one member of this family, exhibits a hexagonal arrangement of uniform mesopores whose dimensions may be engineered in the range of - 15 A to greater than 100 A. Other members of this family, including a material exhibiting cubic symmetry, have ken synthesized. The larger pore M41S materials typically have surface areas above 700 m2/g and hydrocarbon sorption capacities of 0.7 cc/g and greater. A templating mechanism (liquid crystal templating-LCT) in which surfactant liquid crystal structures serve as organic templates is proposed for the formation of these materials. In support of this templating mechanism, it was demonstrated that the structure and pore dimensions of MCM-41 materials are intimately linked to the properties of the surfactant, including surfactant chain length and solution chemistry. The presence of variable pore size MCM-41, cubic material, and other phases indicates that M41S is an extensive family of materials.
10,349 citations
TL;DR: In this paper, a family of highly ordered mesoporous (20−300 A) structures have been synthesized by the use of commercially available nonionic alkyl poly(ethylene oxide) (PEO) oligomeric surfactants and poly(alkylene oxide) block copolymers in acid media.
Abstract: A family of highly ordered mesoporous (20−300 A) silica structures have been synthesized by the use of commercially available nonionic alkyl poly(ethylene oxide) (PEO) oligomeric surfactants and poly(alkylene oxide) block copolymers in acid media. Periodic arrangements of mescoscopically ordered pores with cubic Im3m, cubic Pm3m (or others), 3-d hexagonal (P63/mmc), 2-d hexagonal (p6mm), and lamellar (Lα) symmetries have been prepared. Under acidic conditions at room temperature, the nonionic oligomeric surfactants frequently form cubic or 3-d hexagonal mesoporous silica structures, while the nonionic triblock copolymers tend to form hexagonal (p6mm) mesoporous silica structures. A cubic mesoporous silica structure (SBA-11) with Pm3m diffraction symmetry has been synthesized in the presence of C16H33(OCH2CH2)10OH (C16EO10) surfactant species, while a 3-d hexagonal (P63/mmc) mesoporous silica structure (SBA-12) results when C18EO10 is used. Surfactants with short EO segments tend to form lamellar mesost...
6,274 citations
TL;DR: In this article, a gas can condense to high density inside narrow, single-walled nanotubes (SWNTs) under conditions that do not induce adsorption within a standard mesoporous activated carbon.
Abstract: Pores of molecular dimensions can adsorb large quantities of gases owing to the enhanced density of the adsorbed material inside the pores1, a consequence of the attractive potential of the pore walls. Pederson and Broughton have suggested2 that carbon nanotubes, which have diameters of typically a few nanometres, should be able to draw up liquids by capillarity, and this effect has been seen for low-surface-tension liquids in large-diameter, multi-walled nanotubes3. Here we show that a gas can condense to high density inside narrow, single-walled nanotubes (SWNTs). Temperature-programmed desorption spectrosocopy shows that hydrogen will condense inside SWNTs under conditions that do not induce adsorption within a standard mesoporous activated carbon. The very high hydrogen uptake in these materials suggests that they might be effective as a hydrogen-storage material for fuel-cell electric vehicles.
3,558 citations
TL;DR: In this article, the authors proposed a self-assembly approach for the generation of a well-defined supramolecular architecture by self-assembling from their components under a given set of conditions.
Abstract: The selective binding of a substrate by a molecular receptor to form a supramolecular species involves molecular recognition which rests on the molecular information stored in the interacting species. The functions of supermolecules cover recognition, as well as catalysis and transport. In combination with polymolecular organization, they open ways towards molecular and supramolecular devices for information processing and signal generation. The development of such devices requires the design of molecular components performing a given function (e.g., photoactive, electroactive, ionoactive, thermoactive, or chemoactive) and suitable for assembly into an organized array. Light-conversion devices and charge-separation centers have been realized with photoactive cryptates formed by receptors containing photosensitive groups. Eleclroactive and ionoactive devices are required for carrying information via electronic and ionic signals. Redox-active polyolefinic chains, like the “caroviologens”, represent molecular wires for electron transfer through membranes. Push-pull polyolefins possess marked nonlinear optical properties. Tubular mesophases, formed by organized stacking of suitable macro-cyclic components, as well as “chundle”-type structures, based on bundles of chains grafted onto a macrocyclic support, represent approaches to ion channels. Lipophilic macrocyclic units form Langmuir-Blodgett films that may display molecular recognition at the air-water interface. Supramolecular chemistry has relied on more or less preorganized molecular receptors for effecting molecular recognition, catalysis, and transport processes. A step beyond preorganization consists in the design of systems undergoing self-organization, that is, systems capable of spontaneously generating a well-defined supramolecular architecture by self-assembling from their components under a given set of conditions. Several approaches to self-assembling systems have been pursued: the formation of helical metal complexes, the double-stranded helicates, which result from the spontaneous organization of two linear polybipyridine ligands into a double helix by binding of specific metal ions; the generation of mesophases and liquid crystalline polymers of supramolecular nature from complementary components, amounting to macroscopic expression of molecular recognition; the molecular-recognition-directed formation of ordered solid-state structures. Endowing photo-, electro-, and ionoactive components with recognition elements opens perspectives towards the design of programmed molecular and supramolecular systems capable of self-assembly into organized and functional supramolecular devices. Such systems may be able to perform highly selective operations of recognition, reaction, transfer, and structure generation for signal and information processing at the molecular and supramolecular levels.
2,650 citations