As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

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.

Recent Progress in the Synthesis of Porous Carbon Materials

In the present review, aerogels designate dried gels with a very high relative pore volume. These are versatile materials that are synthesized in a first step by low-temperature traditional sol-gel chemistry. However, while in the final step most wet gels are often dried by evaporation to produce so-called xerogels, aerogels are dried by other techniques, essentially supercritical drying. As a result, the dry samples keep the very unusual porous texture which they had in the wet stage. In general these dry solids have very low apparent densities, large specific surface areas, and in most cases they exhibit amorphous structures when examined by X-ray diffraction (XRD) methods. In addition, they are metastable from the point of view of their thermodynamic properties. Consequently, they often undertake a structural evolution by chemical transformation, when aged in a liquid medium and/or heat treated. As aerogels combine the properties of being highly divided solids with their metastable character, they can develop very attractive physical and chemical properties not achievable by other means of low temperature soft chemical synthesis. In other words, they form a new class of solids showing sophisticated potentialities for a range of applications. These applications as well as chemical and physical aspects of these materials were regularly detailed and discussed in a series of symposia on aerogels,1-5 the last of them being held in Albuquerque in 2000.6 Reviews were also regularly published, either on both xerogels and aerogels7 or more focused on the applications of aerogels.8-13 The particularly interesting properties of aerogels arise from the extraordinary flexibility of the solgel processing, coupled with original drying techniques. The wet chemistry is not basically different for making xerogels and aerogels. As this common basis has been extensively detailed in recent books,14 it does not need to be reviewed. Compared to traditional xerogels, the originality of aerogels comes from * To whom all correspondence should be addressed. † Institut de Recherches sur la Catalyse. ‡ Laboratoire d’Application de la Chimie à l’Environnement. 4243 Chem. Rev. 2002, 102, 4243−4265

https://is.muni.cz/el/1431/podzim2006/C7780/um/Read/2711172/aerogel_Pajonk_ChRev02_4243.pdf

Chemistry of Aerogels and Their Applications

The most commonly used electrode materials for electrochemical capacitors are activated carbons, because they are commercially available and cheap, and they can be produced with large specific surface area. However, only the electrochemically available surface area is useful for charging the electrical double layer (EDL). The EDL formation is especially efficient in carbon pores of size below 1 nm because of the lack of space charge and a good attraction of ions along the pore walls. The pore size should ideally match the size of the ions. However, for good dynamic charge propagation, some small mesopores are useful. An asymmetric configuration, where the positive and negative electrodes are constructed from different materials, e.g., activated carbon, transition metal oxide or conducting polymer, is of great interest because of an important extension of the operating voltage. In such a case, the energy as well as power is greatly increased. It appears that nanotubes are a perfect conducting additive and/or support for materials with pseudocapacitance properties, e.g. MnO2, conducting polymers. Substitutional heteroatoms in the carbon network (nitrogen, oxygen) are a promising way to enhance the capacitance. Carbons obtained by one-step pyrolysis of organic precursors rich in heteroatoms (nitrogen and/or oxygen) are very interesting, because they are denser than activated carbons. The application of a novel type of electrolyte with a broad voltage window (ionic liquids) is considered, but the stability of this new generation of electrolyte during long term cycling of capacitors is not yet confirmed.

Carbon materials for supercapacitor application.

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.

Mesoporous Carbon Materials: Synthesis and Modification

New nanoporous carbons with extremely high mesopore volumes and surface areas have been produced using silica nanoparticles as templates. The polymerization of resorcinol and formaldehyde (RF) in the presence of silica sol particles generated RF gel-silica nanocomposites. Carbonization followed by HF etching of silica templates generated nanoporous carbons with pore sizes predominantly in the range of 10−100 nm. These carbons exhibited very high pore volumes of >4 cm3/g and high surface areas of ∼1000 m2/g. These nanoporous carbons exhibited excellent adsorption capacities for bulky dyes. In the best case, the adsorption capacity of the nanoporous carbon is over 10 times higher than that of commercial activated carbon.

Fabrication of New Nanoporous Carbons through Silica Templates and Their Application to the Adsorption of Bulky Dyes

Simple Solid‐Phase Synthesis of Hollow Graphitic Nanoparticles and their Application to Direct Methanol Fuel Cell Electrodes

Simple silica-particle template synthesis of mesoporous carbons

The effect of silica template structure on the pore structure of mesoporous carbons

Disclosed herein is the fabrication method of producing nanoporous carbon materials with pore sizes ranging from 2 nanometer to 20 nanometer which can be used as electrode materials for a supercapacitor and an electric double layer capacitors being a kind of supercapacitor. The invention also relates to electric double layer capacitors utilizing these carbon materials as electrodes. The carbon materials presented in the present invention possess regular pores with dimensions ranging in between 2 nm and 20 mm and exhibit high electrical conductivity. These carbon materials shows low equivalent series resistance (ESR) and thus exhibits high charge storage capacity at high charging/discharging current density.

Sangjin Han

Papers

Fabrication of New Nanoporous Carbons through Silica Templates and Their Application to the Adsorption of Bulky Dyes

Simple Solid‐Phase Synthesis of Hollow Graphitic Nanoparticles and their Application to Direct Methanol Fuel Cell Electrodes

Simple silica-particle template synthesis of mesoporous carbons

The effect of silica template structure on the pore structure of mesoporous carbons

Method for preparing nanoporous carbon materials and electric double-layer capacitors using them