Recent Progress in the Synthesis of Porous Carbon Materials

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.     

Ordered Mesoporous Carbons

Ordered mesoporous carbons have recently been synthesized using ordered mesoporous silica templates. The synthesis procedure involves infiltration of the pores of the template with appropriate carbon precursor, its carbonization, and subsequent template removal. The template needs to exhibit three‐dimensional pore structure in order to be suitable for the ordered mesoporous carbon synthesis, otherwise disordered microporous carbon is formed. MCM‐48, SBA‐1, and SBA‐15 silicas were successfully used to synthesize carbons with cubic or hexagonal frameworks, narrow mesopore size distributions, high nitrogen Brunauer–Emmett–Teller (BET) specific surface areas (up to 1800 m² g^–1), and large pore volumes. Ordered mesoporous carbons are promising in many applications, including adsorption of large molecules, chromatography, and manufacturing of electrochemical double‐layer capacitors.     

Direct template synthesis of mesoporous carbon and its application to supercapacitor electrodes

A direct templating method which is facile, inexpensive and suitable for the large scale production of mesoporous carbon is reported herein. A meso-structure surfactant/silicate template was made in a solution phase and resorcinol-formaldehyde as a carbon precursor was incorporated into the template solution. After aging, carbonization and hydrofluoric acid (HF) etching, mesoporous carbon was obtained. Using X-ray diffraction, scanning and transmission electron microscopy and nitrogen sorption, the synthesis mechanism of the mesoporous carbon was elucidated. According to the small angle X-ray scattering measurements, the surface became smoother after the removal of the silica, indicating that the silica was mostly located at the pore surface of the carbon. Also, the calculation of the pore volume demonstrated that the silica was transferred into the pores of the carbon without structural collapse during HF etching. When the prepared mesoporous carbon was applied to a supercapacitor electrode, the rectangular shape of the cyclic voltammogram was less collapsed, even at a high scan rate, which is indicative of its high rate capability. This was due to the low resistance of the electrolyte in the pores (3.8 Ω cm²), which was smaller than that of conventional activated carbon electrodes and even comparable to that of ordered mesoporous carbon electrodes. This improved performance was probably due to the well developed mesoporosity and high pore connectivity of the prepared mesoporous carbon.     

Nanoparticles of Mesoporous SO3H‐Functionalized Si‐MCM‐41 with Superior Proton Conductivity

Nanometer‐sized mesoporous silica particles of around 100‐nm diameter functionalized with a large amount of sulfonic acid groups are prepared using a simple and fast in situ co‐condensation procedure. A highly ordered hexagonal pore structure is established by applying a pre‐hydrolysis step in a high‐dilution synthesis approach, followed by adding the functionalization agent to the reaction mixture. The high‐dilution approach is advantageous for the in situ functionalization since no secondary reagents for an effective particle and framework formation are needed. Structural data are determined via electron microscopy, nitrogen adsorption, and X‐ray diffraction, proton conductivity values of the functionalized samples are measured via impedance spectroscopy. The obtained mesoporous SO₃H‐MCM‐41 nanoparticles demonstrate superior proton conductivity than their equally loaded micrometer‐sized counterparts, up to 5 × 10^?2 S cm^?1. The mesoporosity of the particles turns out to be very important for effective proton transport since non‐porous silica nanoparticles exhibit worse efficient proton transport, and the obtained particle size dependence might open up a new route in rational design of highly proton conductive materials.     

Synthesis and characterization of surface-modified and organic-functionalized MCM-41 type ordered mesoporous materials

A new and efficient method for the preparation of MCM-41 type ordered mesoporous phases using phosphate as promoter under reflux conditions is reported. The various mesoporous materials studied were: silica (Si-MCM-41), alumino-silicate (Al-MCM-41), and titanium-silicate (Ti-MCM-41). Our concept of promoter-assisted synthesis of zeolites and related microporous materials was found to be applicable in the synthesis of ordered mesoporous materials as well. The addition of small catalytic quantity of phosphate ions (PO ₄ ³⁻ ), used as promoters, significantly reduced the synthesis time (by a factor of 3–4) of all these mesoporous materials. The synthesis of new MCM-41 type organic-inorganic composite materials with unique properties is also reported.     

Defect-sealing synthesis of vertically oriented ordered mesoporous silica membranes

Vertically oriented ordered mesoporous silica membranes have been successfully synthesized in our laboratory in the form of silica plugs filling the macron-sized straight pores of hydrophobic track-etched polycarbonate membrane support. However, these membranes have shown gaps between the plugs and support pore wall which make the membranes unfeasible for use. This paper reports on techniques of synthesis of defect-free ordered mesoporous silica membranes by filling the gaps with microporous silica. Here, the elimination of defects is achieved by filling the membrane gaps with an alkoxysilane followed by exposure to humid air to allow controlled hydrolysis and condensation resulting in the formation of microporous silica within the gaps. Molecular probing gas permeation and helium/nitrogen (or oxygen) binary separation tests, coupled with surface characterization methods, show that the final membranes contain ordered mesopores of about 2.7 nm pore diameter, running through the membrane, with gaps sealed by microporous silica having a pore size <0.55 nm.     

General Construction of 2D Ordered Mesoporous Iron‐Based Metal–Organic Nanomeshes

Nanomeshes with highly regular, permeable pores in plane, combining the exceptional porous architectures with intrinsic properties of 2D materials, have attracted increasing attention in recent years. Herein, a series of 2D ultrathin metal–organic nanomeshes with ordered mesopores is obtained by a self‐assembly method, including metal phosphate and metal phosphonate. The resultant mesoporous ferric phytate nanomeshes feature unique 2D ultrathin monolayer morphologies ( ≈ 9 nm thickness), hexagonally ordered, permeable mesopores of ≈ 16 nm, as well as improved surface area and pore volume. Notably, the obtained ferric phytate nanomeshes can directly in situ convert into mesoporous sulfur‐doped metal phosphonate nanomeshes by serving as an unprecedented reactive self‐template. Furthermore, as advanced anode materials for Li‐ion batteries, they deliver excellent capacity, good rate capability, and cycling performance, greatly exceeding the similar metal phosphate‐based materials reported previously, resulting from their unique 2D ultrathin mesoporous structure. Therefore, the work will pave an avenue for constructing the other 2D ordered mesoporous materials, and thus offer new opportunities for them in diverse areas.     

Solvent‐Induced Self‐Assembly Strategy to Synthesize Well‐Defined Hierarchically Porous Polymers

Porous polymers with well‐orchestrated nanomorphologies are useful in many fields, but high surface area, hierarchical structure, and ordered pores are difficult to be satisfied in one polymer simultaneously. Herein, a solvent‐induced self‐assembly strategy to synthesize hierarchical porous polymers with tunable morphology, mesoporous structure, and microporous pore wall is reported. The poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer micelles are cross‐linked via Friedel–Crafts reaction, which is a new way to anchor micelles into porous polymers with well‐defined structure. Varying the polarity of the solvent has a dramatic effect upon the oleophobic/oleophylic interaction, and the self‐assembly structure of PEO‐b‐PS can be tailored from aggregated nanoparticles to hollow spheres even mesoporous bulk. A morphological phase diagram is accomplished to systematically evaluate the influence of the composition of PEO‐b‐PS and the mixed solvent component on the pore structure and morphology of products. The hypercrosslinked hollow polymer spheres provide a confined microenvironment for the in situ reduction of K₂PdCl₄ to ultrasmall Pd nanoparticles, which exhibit excellent catalytic performance in solvent‐free catalytic oxidation of hydrocarbons and alcohols.     

利用线性酚醛树脂制备有序介孔碳

三嵌段共聚物F127为模板剂,线性酚醛树脂为碳前驱体,采用溶剂挥发诱导有机-有机自组装法(EI-SA)制备了具有二维六方结构的有序介孔碳。利用FT-IR、XRD、TEM、N2吸附/脱附等方法对有序介孔碳的结构进行了表征,研究了不同焙烧温度和模板剂用量对有序介孔碳结构的影响。结果表明,当模板剂的用量一定时,有序介孔碳的孔径、孔容和孔壁厚度都随着焙烧温度的升高而降低,但比表面积却随着微孔含量的增加而增大。随着模板剂用量的增加,介孔碳的有序性降低。有序介孔碳PF-2-500的比表面积、孔径、孔容、孔壁厚度和微孔比表面积比分别为583.82m2/g、3.05nm、0.31cm3/g、3.40nm和361.18m2/g,而有序介孔碳PF-1-500的比表面积、孔径和孔容相对于PF-2-500有所提高,分别为647.79m2/g、3.44nm和0.41cm3/g,但微孔比表面积和孔壁厚度分别降低为309.46m2/g和3.35nm。     

有序介孔二氧化钛粉体研究进展

主要综述了高度有序六方相和立方相孔道结构介孔二氧化钛以及具有低有序蠕虫状孔道结构介孔二氧化钛的制备方法及其结构特征。总结了后处理法、模板剂脱除法在制备稳定、具有有序介孔和锐钛矿相孔壁的介孔二氧化钛粉体中的应用,指出采用直接合成法制备孔壁结晶的介孔二氧化钛原粉,之后用萃取法脱除模板剂并用钛酸异丙酯蒸气增强骨架,将是得到高稳定性有序介孔二氧化钛材料的良好途径。     

New Triblock Copolymer Templates,PEO‐PB‐PEO,for the Synthesis of Titania Films with Controlled Mesopore Size,Wall Thickness,and Bimodal Porosity

The synthesis and properties of a series of new structure‐directing triblock copolymers with PEO‐PB‐PEO structure (PEO = poly(ethylene oxide) and PB = polybutadiene) and their application as superior pore‐templates for the preparation of mesoporous titania coatings are reported. Starting from either TiCl₄ or from preformed TiO₂ nanocrystalline building blocks, mesoporous crystalline titanium oxide films with a significant degree of mesoscopic ordered pores are derived, and the pore size can be controlled by the molecular mass of the template polymer. Moreover, the triblock copolymers form stable micelles already at very low concentration, i.e., prior to solvent evaporation during the evaporation‐induced self‐assembly process (EISA). Consequently, the thickness of pore walls can be controlled independently of pore size by changing the polymer‐to‐precursor ratio. Thus, unprecedented control of wall thickness in the structure of mesoporous oxide coatings is achieved. In addition, the micelle formation of the new template polymers is sufficiently distinct from that of typical commercial PPO‐PEO‐PPO polymers (Pluronics; PPO = poly(propylene oxide)), so that a combination of both polymers facilitates bimodal porosity via dual micelle templating.     

Silica‐Templated Synthesis of Ordered Mesoporous Tungsten Carbide/Graphitic Carbon Composites with Nanocrystalline Walls and High Surface Areas via a Temperature‐Programmed Carburization Route

Ordered mesostructured tungsten carbide and graphitic carbon composites (WC/C) with nanocrystalline walls are fabricated for the first time by a temperature‐programmed carburization approach with phosphotungstic acid (PTA) as a precursor and mesoporous silica materials as hard templates. The mesostructure, crystal phase, and amount of deposited graphitic carbon can be conveniently tuned by controlling the silica template (SBA‐15 or KIT‐6), carburizing temperature (700–1000 °C), the PTA‐loading amount, and the carburizing atmosphere (CH₄ or a CH₄/H₂ mixture). A high level of deposited carbon is favorable for connecting and stabilizing the WC nanocrystallites to achieve high mesostructural regularity, as well as promoting the carburization reaction. Meanwhile, large pore sizes and high mesoporosity of the silica templates can promote WC‐phase formation. These novel, ordered, mesoporous WC/C nanocomposites with high surface areas (74–169 m² g^?1), large pore volumes (0.14–0.17 cm³ g^?1), narrow pore‐size distributions (centered at about 3 nm), and very good oxidation resistance (up to 750°C) have potential applications in fuel‐cell catalysts and nanodevices.     

Fabrication and Optical Properties of Periodic Ag Nano‐Pore and Nano‐Particle Arrays with Controlled Shape and Size over Macroscopic Length Scales

A facile and economical route to preparation of highly ordered sliver pore or particle arrays with controlled pore‐shape and size extended over cm² areas is described. The substrates are prepared at planar and curved surfaces via sphere‐imprinted polymer (PDMS) templating using polystyrene spheres with diameters of 820, 600, or 430 nm. Nano‐pore arrays are created by sputtering 80 nm of Ag directly onto the templates and nano‐particle arrays are prepared by electrode‐less deposition of Ag from Tollen's reagent. The shape of the nano‐pore or particles in the array conformed to that of the imprint of the sphere on the template. Stretching the flexible template enable creation of cuboid shaped nano‐voids and nano‐particles following Ag deposition. Diffuse reflectance from the spherical Ag nano‐cavity arrays showed absorbance maxima at wavelengths comparable similar to the diameter of the templating sphere, whereas reflectance from the cuboid arrays, showed little correlation with the sphere diameter. The cuboid nano‐particle arrays showed the most intense visible absorption which is red‐shifted compared to the spherical arrays. White light diffraction from the arrays, observed by rotating 1 cm² substrates relative to a fixed light source, reflected exactly the symmetry axes of the periodic nano‐features in the arrays demonstrating the remarkable macroscopic order of the periodic structures. Raman spectra of 1‐benzenethiol adsorbed at the arrays indicated SERS enhancements from the substrates are attributed mainly to surface nano‐roughness with only moderate contributions from the periodically corrugated structures. Despite excitation at the major resonance dip in the reflectance spectrum, a weak, localized rim dipole mode is found to elicit a small increase in the SERS enhancement factor for the 430 nm diameter spherical arrays. FDTD studies of nano‐void arrays provided insights into v arious factors affecting the SERS experiment and confirmed the array's plasmonic spectra are dominated by propagating plasmon modes under microscope excitation/collection angles.     

Extension of the Stöber Method to Construct Mesoporous SiO2 and TiO2 Shells for Uniform Multifunctional Core–Shell Structures

Core–shell nanoparticles (CSNs) have attracted considerable attention because of their promising applications in a wide range of fields. Recently, substantial efforts have been focused on the development of facile and versatile methods for preparing CSNs with mesoporous SiO₂ or TiO₂ shells because of their fascinating properties, such as high surface area, large pore channels and high pore volume. This Research News reviews the recent progress in facile, versatile and reproducible approaches which are simply extended from the well‐known Stöber method to construct mesoporous SiO₂ and TiO₂ shells for uniform multifunctional core–shell nanostructures. Several strategies, including the surfactant‐templating process, the long‐chain organosilane‐assisted approach, the phase transfer assisted surfactant‐templating process, and the kinetics‐controlled coating approach, are discussed. In addition, new trends in this field for the creation of multifunctional CSNs and novel nanostructures are highlighted.     

A Nanoporous Cytochrome c Film with Highly Ordered Porous Structure for Sensing of Toxic Vapors

Creating well‐ordered nanoporosity in biomolecules promises stability and activity, offering access to an even wider range of application possibilities. Here, the preparation of nanoporous protein films containing cytochrome c protein molecules is reported through a soft‐templating strategy using polystyrene (PS) spheres of different sizes as templates. The stability of the cytochrome c film is demonstrated through electrochemistry studies to show a reusable nature of these films over a long period of time. The size of the PS spheres is varied to tune the pore diameter and the thickness of the cytochrome c films, which are quite stable and highly selective for sensing toxic acidic vapors. The fusion of the templating strategy and the self‐assembly of biomolecules may offer various possibilities by generating a new series of porous biomolecules including enzymes with different molecular weights and diameters, peptides, antibodies, and DNA with interesting catalytic, adsorption, sensing, and electronic properties.     

Conditions and features of matrix and bulk carbonization of the organic precursors

Comparative research of matrix and bulk carbonization of some organic precursors (sucrose, acetonitrile) in silica mesoporous materials SBA-15 and KIT-6 was conducted. X-ray diffraction, nitrogen adsorption analysis, Raman spectroscopy were used for determination of the structural-sorption characteristics of the obtained materials. It was shown that the carbon mesoporous materials CMK-8 obtained in the mesopores of KIT-6 had higher adsorption characteristics because of features of three-dimensional cubic structure, larger pore volume and framework’s wall thickness. It was established that partially graphitized spatially well-organized carbon materials were formed as a result of pyrolysis of acetonitrile in the silica matrices SBA-15 and KIT-6. It was conditioned by the absence of considerable spatial limitations for growth of graphite structures on the initial stage of the synthesis when the pores of the matrix were not filled up with the organic precursor. Product of bulk carbonization of sucrose is compact carbon microporous framework with low sorption characteristics (micropore volume is 0.09 cm³/g).     

Ultrathin Amorphous Nickel Doped Cobalt Phosphates with Highly Ordered Mesoporous Structures as Efficient Electrocatalyst for Oxygen Evolution Reaction

Herein, the facile preparation of ultrathin (≈3.8 nm in thickness) 2D cobalt phosphate (CoPi) nanoflakes through an oil‐phase method is reported. The obtained nanoflakes are composed of highly ordered mesoporous (≈3.74 nm in diameter) structure and exhibit an amorphous nature. Attractively, when doped with nickel, such 2D mesoporous Ni‐doped CoPi nanoflakes display decent electrocatalytic performances in terms of intrinsic activity, and low kinetic barrier toward the oxygen evolution reaction (OER). Particularly, the optimized 10 at% Ni‐doped CoPi nanoflakes (denoted as Ni10‐CoPi) deliver a low overpotential at 10 mA cm^?2 (320 mV), small Tafel slope (44.5 mV dec^?1), and high stability for OER in 1.0 m KOH solution, which is comparable to the state‐of‐the‐art RuO₂ tested in the same condition (overpotential: 327 mV at 10 mA cm^?2, Tafel slope: 73.7 mV dec^?1). The robust framework coupled with good OER performance enables the 2D mesoporous Ni10‐CoPi nanoflakes to be a promising material for energy conversion applications.     

Chiral mesoporous materials based on the self-assembly

Ordered mesoporous materials with various structures are synthesized based on the self-assembly of surfactant and inorganic precursors and covered by several excellent reviews. However, less work has been directed to chiral structured mesoporous materials, although these could have wide-ranging applications on the manufacturing of enantio-pure chemicals and pharmaceuticals as catalysts and separation media with both shape selectivity and enantioselectivity. This short review will address the synthesis of chiral mesoporous materials by chiral organic compounds templating route, covering single and 2-dimensional ordered chiral channel mesoporous materials. Non-porous helical fiber, atomic-scale enantio-morphism and zeolite-like materials with three-dimensional helical pores are beyond the scope of this paper.     

Hierarchical micro- and mesoporous carbide-derived carbon as a high-performance electrode material in supercapacitors

Ordered mesoporous carbide-derived carbon (OM-CDC) materials produced by nanocasting of ordered mesoporous silica templates are characterized by a bimodal pore size distribution with a high ratio of micropores. The micropores result in outstanding adsorption capacities and the well-defined mesopores facilitate enhanced kinetics in adsorption processes. Here, for the first time, a systematic study is presented, in which the effects of synthesis temperature on the electrochemical performance of these materials in supercapacitors based on a 1 M aqueous solution of sulfuric acid and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid are reported. Cyclic voltammetry shows the specific capacitance of the OM-CDC materials exceeds 200 F g(-1) in the aqueous electrolyte and 185 F g(-1) in the ionic liquid, when measured in a symmetric configuration in voltage ranges of up to 0.6 and 2 V, respectively. The ordered mesoporous channels in the produced OM-CDC materials serve as ion-highways and allow for very fast ionic transport into the bulk of the OM-CDC particles. At room temperature the enhanced ion transport leads to 75% and 90% of the capacitance retention at current densities in excess of ～10 A g(-1) in ionic liquid and aqueous electrolytes, respectively. The supercapacitors based on 250-300 μm OM-CDC electrodes demonstrate an operating frequency of up to 7 Hz in aqueous electrolyte. The combination of high specific capacitance and outstanding rate capabilities of the OM-CDC materials is unmatched by state-of-the art activated carbons and strictly microporous CDC materials.     

Fabrication of a magnetic helical mesostructured silica rod

We report a one-step synthesis of magnetic helical mesostructured silica (MHMS) by self-assembly of an achiral surfactant, magnetic nanocrystals with stearic acid ligands and silicate. This core-shell structured material consists of an Fe(3)O(4) superparamagnetic nanocrystal core and a highly ordered periodic helical mesoporous silica shell. We propose that the formation of the helical structure is induced by the interaction between the surfactant and dissociated stearic acid ligands. The MHMS obtained possesses superparamagnetism, uniform mesostructure, narrow pore size distribution, high surface area, and large pore volume. Furthermore, the drug release process is demonstrated using aspirin as a drug model and MHMS as a drug carrier in a sodium phosphate buffer solution.