Ordered Mesoporous Polymers and Homologous Carbon Frameworks: Amphiphilic Surfactant Templating and Direct Transformation
TL;DR: Organic porous materials—a class of advanced materials— possess enormous potential for many high-tech applications, such as bioreactors, dielectrics, sensors, microelectrophoresis, thermal insulation, and catalysts, but large porosity has rarely been reported.
Abstract: Organic porous materials—a class of advanced materials— possess enormous potential for many high-tech applications, such as bioreactors, dielectrics, sensors, microelectrophoresis, thermal insulation, and catalysts. In general, they can be prepared by phase separation, and a hard templating approach, such as those employing colloidal particles. Phase separation can be derived from organic– organic phases, while the pore structures can be formed after etching, or by dissolving one block (A) from the assembled block copolymer (A–B). However, most of the resulting porous polymer structures are disordered with wide pore size distributions because of the contraction and swelling from changes in volume, as well as the structured defects formed during template removal. Large porosities have rarely been reported. Furthermore, the resistance of the pore structure to heat and solvents is rather low because the materials are formed by weak van der Waals forces and physical twists between polymer chains, which means that the framework is not connected by covalent bonds. Recently, a procedure for cross-linking lyotropic liquid crystals (LLC) in water was introduced to prepare periodic porous organic mesostructures. Unfortunately, polymerization only occurs between nearest neighboring head groups, and the mesostructured channels are fully occupied with solution. Therefore, it is not surprising that porosity has yet to be reported. Carbon materials, including nanotubes and fullerenes, have attracted considerable attention because of their remarkable properties. The traditional carbonization process for active carbon and related materials can only generate
Citations
More filters
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: A review of the progress made in the last ten years concerning the synthesis of porous carbon materials is summarized in this paper, where several different routes have been used to synthesize mesoporous carbon materials.
Abstract: In this review, the progress made in the last ten years concerning the synthesis of porous carbon materials is summarized. Porous carbon materials with various pore sizes and pore structures have been synthesized using several different routes. Microporous activated carbons have been synthesized through the activation process. Ordered microporous carbon materials have been synthesized using zeolites as templates. Mesoporous carbons with a disordered pore structure have been synthesized using various methods, including catalytic activation using metal species, carbonization of polymer/polymer blends, carbonization of organic aerogels, and template synthesis using silica nanoparticles. Ordered mesoporous carbons with various pore structures have been synthesized using mesoporous silica materials such as MCM-48, HMS, SBA-15, MCF, and MSU-X as templates. Ordered mesoporous carbons with graphitic pore walls have been synthesized using soft-carbon sources that can be converted to highly ordered graphite at high temperature. Hierarchically ordered mesoporous carbon materials have been synthesized using various designed silica templates. Some of these mesoporous carbon materials have successfully been used as adsorbents for bulky pollutants, as electrodes for supercapacitors and fuel cells, and as hosts for enzyme immobilization. Ordered macroporous carbon materials have been synthesized using colloidal crystals as templates. One-dimensional carbon nanostructured materials have been fabricated using anodic aluminum oxide (AAO) as a template.
1,904 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
TL;DR: In this article, a route for the controlled synthesis of mesoporous polymer nanospheres, which can be further converted into carbon nanosphere through carbonization, is presented.
Abstract: The controlled synthesis of monodisperse nanospheres faces a number of difficulties, such as extensive crosslinking during hydrothermal processes. Here, the authors show a route for the controlled synthesis of mesoporous polymer nanospheres, which can be further converted into carbon nanospheres through carbonization.
1,542 citations
References
More filters
TL;DR: In this paper, the synthesis of mesoporous inorganic solids from calcination of aluminosilicate gels in the presence of surfactants is described, in which the silicate material forms inorganic walls between ordered surfactant micelles.
Abstract: MICROPOROUS and mesoporous inorganic solids (with pore diameters of ≤20 A and ∼20–500 A respectively)1 have found great utility as catalysts and sorption media because of their large internal surface area. Typical microporous materials are the crystalline framework solids, such as zeolites2, but the largest pore dimensions found so far are ∼10–12 A for some metallophosphates3–5 and ∼14 A for the mineral cacoxenite6. Examples of mesoporous solids include silicas7 and modified layered materials8–11, but these are invariably amorphous or paracrystalline, with pores that are irregularly spaced and broadly distributed in size8,12. Pore size can be controlled by intercalation of layered silicates with a surfactant species9,13, but the final product retains, in part, the layered nature of the precursor material. Here we report the synthesis of mesoporous solids from the calcination of aluminosilicate gels in the presence of surfactants. The material14,15 possesses regular arrays of uniform channels, the dimensions of which can be tailored (in the range 16 A to 100 A or more) through the choice of surfactant, auxiliary chemicals and reaction conditions. We propose that the formation of these materials takes place by means of a liquid-crystal 'templating' mechanism, in which the silicate material forms inorganic walls between ordered surfactant micelles.
15,125 citations
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: Many potential applications have been proposed for carbon nanotubes, including conductive and high-strength composites; energy storage and energy conversion devices; sensors; field emission displays and radiation sources; hydrogen storage media; and nanometer-sized semiconductor devices, probes, and interconnects.
Abstract: Many potential applications have been proposed for carbon nanotubes, including conductive and high-strength composites; energy storage and energy conversion devices; sensors; field emission displays and radiation sources; hydrogen storage media; and nanometer-sized semiconductor devices, probes, and interconnects. Some of these applications are now realized in products. Others are demonstrated in early to advanced devices, and one, hydrogen storage, is clouded by controversy. Nanotube cost, polydispersity in nanotube type, and limitations in processing and assembly methods are important barriers for some applications of single-walled nanotubes.
9,693 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: Ordered carbon molecular sieves exhibiting Bragg diffraction of X-ray lines have been synthesized for the first time, using mesoporous silica sieves as the template.
Abstract: Ordered carbon molecular sieves exhibiting Bragg diffraction of X-ray lines have been synthesized for the first time, using mesoporous silica molecular sieves as the template. Sucrose was converted to carbon inside the mesopores of the silica molecular sieves through a mild carbonization process using a sulfuric acid catalyst. The carbon molecular sieves were obtained after the removal of the silica framework using an aqueous solution of sodium hydroxide. The X-ray diffraction, transmission electron microscopy, and pore size analysis showed that the structure of the carbon molecular sieves consisted of a three-dimensional regular array of uniform mesopores 3 nm in diameter. The structure was not simply a negative replica of the used silica template, but the synthesis mechanism involved the unique transformation into a new ordered array that was triggered by the removal of the silica frameworks. The highly ordered mesoporous texture suggested its scientific and technological importance as a new shape-selec...
2,298 citations