Carbon-coated mesoporous silica with hydrophobicity and electrical conductivity

The pore surface of mesoporous silica SBA-15 was coated with 2,3-dihydroxynaphthalene (DN) through a dehydration reaction between the surface silanol groups in SBA-15 and the hydroxyl groups of the DN molecules. By the carbonization of DN in the SBA-15 pores, the pore surface was uniformly covered with an extremely thin carbon layer, which comprised only 1-2 graphene sheets. The resulting carbon-coated SBA-15 still possessed the characteristics of the original SBA-15—large surface area and pore volume, long-range ordered structure, and sharp mesopore size distribution. In addition, the carbon-coated SBA-15 showed marked hydrophobicity and high electrical conductivity, both of which are not intrinsic properties of SBA-15. The appearance of these features can be explained from the almost perfect carbon coating on the pore surface. Newly developed graphene coating technique can donate characteristic carbon properties to mesoporous silica.     

Monodispersed nanoporous starburst carbon spheres and their three-dimensionally ordered arrays

Controlled syntheses of highly monodispersed nanoporous carbon spheres via a nanocasting route are described. Previously reported monodispersed super-microporous or mesoporous silica spheres with hexagonally ordered pore channels were used as sacrificial templates, and the effect of pore sizes of the templates on the porous properties of the nanocast carbon spheres was comprehensively studied. The resultant carbon spheres exhibited a unique starburst structure derived from radially-aligned pore channels in the silica template, and had a BET surface area of over 1000 m²g^?1. It was found out that the radial alignment and sufficiently large pore size of hexagonally ordered pore channels in the silica spheres were effective to enhance the degree of order of the starburst structure in the nanocast carbon spheres and that ordered nanoporous carbon spheres could be obtained even from the MCM-41-type mesoporous silica. The diameters of the nanoporous carbon spheres were controlled in the sub-micrometer range by changing the sizes of silica templates. Furthermore, three-dimensionally ordered arrays consisting of nanoporous carbon spheres were successfully fabricated via the self-assembly of mesoporous silica/carbon composite spheres and the subsequent dissolution of the silica templates.     

共聚法制备疏水性SiO2气凝胶

以正硅酸乙酯为原料,应用溶胶-凝胶两步催化,甲基丙烯酸基丙基三甲氧基硅烷作为改性剂,无水乙醇为溶剂,共聚法常压下制备疏水性SiO₂气凝胶。运用原位红外在线监测反应历程,确定制备工艺步骤。运用N₂吸附仪、扫描电镜、红外光谱、TG-DSC对SiO₂气凝胶孔径分布、形貌、表面官能团及热稳定性进行分析。结果表明,经甲基丙烯酸基丙基三甲氧基硅烷改性的SiO₂气凝胶疏水性能良好,疏水的耐温性可达到407℃,比表面积为877.17 m²·g^-1, 由球形纳米颗粒堆积而成,颗粒尺寸范围在10～50 nm,孔径集中分布在1.9相似文献   

Synthesis of mesoporous carbon spheres with a hierarchical pore structure for the electrochemical double-layer capacitor

Mesoporous carbon spheres with hierarchical foam-like pore structures have been synthesized by a dual-templating strategy using phenolic resol as a carbon source, Pluronic F127 and spherical silica mesocellular foams (Si-MCFs) as the soft and hard template, respectively. The results show that the morphology and mesostructure of the silica template are faithfully replicated. The obtained mesoporous carbon material with spherical diameter size of ca. 3–5 μm exhibits hierarchical pore sizes (from ca. 3.5 to 60 nm), high specific surface area (1320 m²/g) and large pore volume (3.5 cm³/g). The carbon surface contains plenty of oxygen-containing groups, resulting in hydrophilic property for an electrode material. In addition, Pluronic F127 plays an important role in the synthesis for maintaining the foam-like mesostructure of the silica templates and faithful replication of the spherical morphology. The electrochemical measurements show that the hierarchically mesoporous carbon spheres as an electrochemical double-layer capacitor (EDLC) electrode present a long cyclic life, excellent rate capability, and high specific capacitance as ca. 208 F/g at 0.5 A/g in (2.0 M) H₂SO₄ aqueous solution. Its specific capacitance can still remain ca. 146 F/g at a high loading current density of 30 A/g with the retention of ca. 70%. Furthermore, this material also exhibits excellent capacitive performance in (C₂H₅)₄NBF₄/propylene carbonate electrolyte, and its specific capacitance is 97 F/g at loading current density of 0.5 A/g.     

Direct fabrication of mesoporous carbons using in-situ polymerized silica gel networks as a template

Mesoporous carbons were synthesized by in-situ polymerized silica gel networks as a template. The co-condensation of carbon precursor (sucrose) and silica precursor (sodium silicate) followed by heat treatment generated a carbon/silica nanocomposite. After etching the silica template, mesoporous carbons were obtained. Under optimum synthesis conditions a mesoporous carbon with a high surface area of >800 m²/g and a narrow pore size distribution centered at 3 nm was produced. The three-dimensionally interconnected silica structures effectively functioned as the template for the porous carbon materials.     

Simple synthesis of mesoporous carbon with magnetic nanoparticles embedded in carbon rods

Magnetically separable ordered mesoporous carbon containing magnetic nanoparticles embedded in the carbon walls was synthesized using a simple synthetic procedure. The resulting magnetically separable mesoporous carbon was denoted as M-OMC (magnetically separable ordered mesoporous carbon) poly(pyrrole) with residual Fe²⁺ ions in the mesoporous channel was converted to carbon material containing superparamagnetic nanoparticles. The size of the magnetic nanoparticles obtained was restricted by the channel size of the SBA-15 silica template, which resulted in the generation of superparamagnetic nanoparticles embedded in the carbon rods. The blocking temperature of M-OMC is 110 K. Pore size and textural property of M-OMC is similar to that of hexagonally ordered mesoporous carbon fabricated using SBA-15 silica as a template. The saturation magnetization of M-OMC is ca. 30.0 emu/g at 300 K, high enough for magnetic separation.     

Simple synthesis of highly ordered mesoporous carbon by self-assembly of phenol–formaldehyde and block copolymers under designed aqueous basic/acidic conditions

In view of the low reactivity of phenol with formaldehyde under acidic condition in the synthesis of ordered mesoporous carbons, a strategy to accelerate the polymerization of phenol and formaldehyde by using designed aqueous basic/acidic conditions (first weakly basic condition then highly acidic condition) is developed. The first weakly basic condition benefits the formation of hydroxymethyl phenols at 313 K. The latter highly acidic condition mainly induces the condensation reaction between the formed hydroxymethyl phenols, as well as the self-assembly of phenol–formaldehyde and block copolymer template. After removal of the template, the obtained carbon exhibits highly ordered hexagonal mesostructure with a surface area of 760 m² g⁻¹, large pore volume (0.64 cm³ g⁻¹) and uniform pore size (3.32 nm). This developed strategy affords a simple and highly reproducible approach for the synthesis of ordered mesoporous carbon from the less expensive phenol under strong acidic condition, which also provides a wide and easily accessed synthesis condition for the further functionalization, such as the in situ introducing of metal ions.     

Facile preparation and unique H2 adsorption behavior of three-dimensional novel Pt–Ru hollow sphere assemblies

Three-dimensional long range ordered hollow Pt–Ru sphere assemblies were prepared using a sacrificial three-dimensionally ordered macroporous (3DOM) carbon template. Metallic salts, such as a mixture of RuCl₃ with H₂PtCl₆ were infiltrated into the carbon template, and a reduced Pt–Ru phase was produced on the surface of the 3DOM carbon template by a borohydride reduction reaction. The sacrificial template was then burnt off in air at 650 °C. The diameter of the hollow Pt–Ru spheres could be tailored using a different pore size 3DOM carbon template. Assemblies with an outer diameter of 550 nm showed high BET surface area of 584.3 m²/g. In addition, a high hydrogen adsorption stoichiometry (>0.5 H/M) was obtained on the Pt–Ru sphere assemblies, which indicated that most of the metal atoms on the surface were exposed.     

Hollow micro-mesoporous carbon polyhedra produced by selective removal of skeletal scaffolds

An approach has been demonstrated for fabricating hollow micro-mesoporous carbon polyhedra by selective removal of the skeletal scaffolds of polyurethane (PU) foam in monolithic mesostructured resin/PU composites. Hollow micro-mesoporous carbon polyhedra with an irregular shape molded from the cellular cavities of PU foam were synthesized by using phenolic resol as a precursor, triblock copolymer Pluronic F127 as a template, PU foam as a skeletal scaffold and triethyl phosphate as a reaction agent. By a reaction with triethyl phosphate, the PU foam in resin/PU composites can be degraded, simultaneously leading to the disassembly of the monolithic structure into separated polyhedral particles. The method can also be used for synthesizing hollow micro-mesoporous carbon–silica polyhedra, using tetraethyl orthosilicate as a silica source. Moreover, after etching the silica away, hollow micro-mesoporous carbon polyhedra with an ordered hexagonal mesostructure (space group p6mm), large particle sizes of 65–500 μm, a large surface area of 1384 m² g^?1, a uniform pore size of 3.2 nm and a high pore volume of 1.15 cm³ g^?1 as well as a high mesoporosity of 81% can be obtained, which exhibits excellent adsorption performance toward methylene blue compared with the active carbon having a similar surface area.     

Synthesis and characterization of mesoporous carbon through inexpensive mesoporous silica as template

Mesoporous silica materials have been synthesized through sol–gel reaction using inexpensive sodium silicate as source of silica and low cost hydroxy carboxylic acid compounds as templates/pore forming agents. The material measured surface area of 1014 m²/g, pore diameter of 65 Å and pore volume of 1.4 cc/g when parameters like time and temperature of synthesis along with mole ratio of TA/SiO₂ were optimized. Here TA stands for tartaric acid. Carbonization of sucrose inside the pores of above silica material at 900 °C followed by removal of silica framework using aqueous ethanoic solution of NaOH gave rise to mesoporous carbon material. The resulting materials were characterized by N₂-sorption, FTIR spectroscopy, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, thermal analysis and cyclic voltammetry. Three dimensional interconnecting wormhole channel arrangement of mesoporous silica template leads to mesoporous carbon replica with surface area of 1200 m²/g. X-ray photoelectron spectroscopic study (XPS) of the mesoporous carbon material shows the concentration of carbon atom in the range of 97–98% with 1–2% oxygen and negligible amount of silica. The electrochemical double layer capacitance behavior of carbon material with the specific capacitance value of 88.0 F/g at the scan rate of 1 mV/s appears to be promising.     

Morphology control of ordered supermicroporous silicas

A feasible method has been developed for the morphology control of ordered supermicroporous silicas by adopting a kind of rosin-based surfactant as the templating agent. By adjusting the molar ratio of sodium silicate (SS) and ethyl acetate (EA), the morphologies of the materials can be changed from hollow sphere to hollow tube, and solid rod, while the degree of ordering of the samples showed a trend of firstly increasing and then decreasing. When the molar ratio of SS/EA was 0.38, an ordered supermicroporous silica with a hollow tubular morphology was obtained. The material had a surface area of 645.5 m²/g, a pore volume of 0.3 cm³/g, and a pore size distribution centered at 1.8 nm. When the molar ratio of SS/EA was increased to 0.46, the resulting sample exhibited a solid-rod morphology with a highly ordered hexagonal supermicroporous structure. This material had a large surface area of 1478.1 m²/g, a high pore volume of 0.7 cm³/g, and a uniform pore size distribution centered at 2.0 nm.     

Preparation of hollow submicrocapsules with a mesoporous carbon shell

The preparation of carbon submicrocapsules with size up to 800 nm and a mesoporous shell by hard silica templating is reported. Washing and template synthesis conditions were varied to promote porosity and avoid deformation of the microcapsules. The silica template synthesis conditions analyzed were: silica nucleus formation time (0.25–6 h), octadecyltrimethoxysilane/tetraethylorthosilicate volume ratio for silica shell formation (0.2–0.6) and silica shell formation time (1–24 h). The samples were characterized by 77 K nitrogen adsorption/desorption, mercury porosimetry and electron microscopy. Under all the washing conditions tested the carbon submicrocapsules were deformed due to the large size of the hollow core and the thickness of the shell. Changes in the silica template synthesis conditions did not result in substantial improvement of the strength of the microcapsules. The synthesis of a silica template with a double shell allowed us to obtain thick shell carbon submicrocapsules without significant deflation and with higher porosity. The characterization of these microcapsules showed that they have a BET surface area of 1541 m²/g and a pore size distribution with peaks centered at 0.75, 0.86, 1.0 nm in the micropore range and 3.5 nm in the mesopore range. The pore volume in the 2–80 nm range was 1.7 cm³/g.     

Worm-hole structured mesoporous carbon monoliths synthesized with amphiphilic triblock copolymer

In the present work, mesoporous carbon monoliths with worm-hole structure had been synthesized through hydrothermal reaction by using amphiphilic triblock copolymer F127 and P123 as templates and resole as carbon precursor. Synthesis conditions, carbonization temperature and pore structure were studied by Fourier transform infrared, thermogravimetric analysis, transmission electron microscopy and N₂ adsorption–desorption. The results indicated that the ideal pyrolysis temperature of the template is 450 °C. The organic ingredients were almost removed after further carbonized at 600 °C and the mesoporous carbon monoliths with worm-hole structure were obtained. The mesoporous carbon synthesized with P123 as single template exhibited larger pore size (6.6 nm), higher specific surface area (747 m² g^?1), lower pore ratio (45.9 %) in comparison with the mesoporous carbon synthesized with F127 as single template (with the corresponding value of 4.9 nm, 681 m² g^?1, 49.6 %, respectively), and also exhibited wider pore size distribution and lower structure regularity. Moreover, the higher mass ratio of template P123/resole induced similar pore size, larger specific surface area and lower pore ratio at the same synthesizing condition. It was also found that the textural structure of mesoporous carbon was affect by calcination atmosphere.     

A wormhole-structured mesoporous carbon with superior adsorption for dyes

A series of large-pore mesoporous carbon materials with a three-dimensional wormhole framework structure were synthesized by nanocasting using mesoporous silica as a hard template. Samples of hard-template mesoporous silica with pore diameters from 3.08 to 6.43 nm, pore volumes from 0.59 to 1.02 cm³ g⁻¹ and surface areas from 832 to 579 m² g⁻¹ were prepared from tetraethyl orthosilicate as the silica source and ionic liquid 1-butyl-3-methylimidazolium bromide as structure-directing agent through hydrothermal treatment at different temperatures (110–150 °C) followed by calcining at 550 °C. Subsequently, carbon materials with large pore diameters (2.76–6.70 nm), pore volumes (0.74–2.10 cm³ g⁻¹) and high surface areas (1074–1276 m² g⁻¹) were synthesized using the various mesoporous silicas synthesized at the different hydrothermal temperatures as a hard-template. The carbon material obtained at a hydrothermal temperature of 150 °C possesses outstanding adsorbility for amaranth and methylene blue dyes.     

A simplified synthesis of N-doped zeolite-templated carbons, the control of the level of zeolite-like ordering and its effect on hydrogen storage properties

Nitrogen-doped, microporous carbon materials have been prepared using zeolite EMC-2 as a hard template and acetonitrile as the carbon source via chemical vapour deposition (CVD) in the temperature range 700–950 °C. The carbon products exhibited high surface areas (up to 3360 m²/g), high pore volumes (up to 1.71 cm³/g) and had zeolite-like structural ordering derived from the template. The carbons had XRD patterns that exhibited two well resolved peaks and TEM images that showed well ordered pore channels. A high proportion of porosity (up to 85% of surface area and 73% of pore volume) for the best ordered carbon arose from micropores that exhibited narrow size distribution in the range 5–15 Å. The carbons generally retained the morphology of the template with solid-core particles at CVD temperatures up to 900 °C and hollow shells at 950 °C. The carbons had total hydrogen storage capacities up to 6.0 wt.% at −196 °C and 20 bar. The hydrogen uptake was found to be dependent on the level of zeolite-like ordering and the resulting textural properties. Particularly, high levels of zeolite-like ordering favoured micropores of size <15 Å which are favourable for higher hydrogen uptake capacities.     

Functionalization of Tailored Porous Carbon Monolith for Decontamination of Radioactive Substances

As the control over radioactive species becomes critical for the contemporary human life, the development of functional materials for decontamination of radioactive substances has also become important. In this work, a three-dimensional (3D) porous carbon monolith functionalized with Prussian blue particles was prepared through removal of colloidal silica particles from exfoliated graphene/silica composite precursors. The colloidal silica particles with a narrow size distribution were used to act a role of hard template and provide a sufficient surface area that could accommodate potentially hazardous radioactive substances by adsorption. The unique surface and pore structure of the functionalized porous carbon monolith was examined using electron microscopy and energy-dispersive X-ray analysis (EDS). The effective incorporation of PB nanoparticles was confirmed using diverse instrumentations such as X-ray diffraction (XRD), Fourier-transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS). A nitrogen adsorption/desorption study showed that surface area and pore volume increased significantly compared with the starting precursor. Adsorption tests were performed with ¹³³Cs ions to examine adsorption isotherms using both Langmuir and Freundlich isotherms. In addition, adsorption kinetics were also investigated and parameters were calculated. The functionalized porous carbon monolith showed a relatively higher adsorption capacity than that of pristine porous carbon monolith and the bulk PB to most radioactive ions such as ¹³³Cs, ⁸⁵Rb, ¹³⁸Ba, ⁸⁸Sr, ¹⁴⁰Ce, and ²⁰⁵Tl. This material can be used for decontamination in expanded application fields.     

Soft-template synthesis of ordered mesoporous carbon/nanoparticle nickel composites with a high surface area

Ordered mesoporous carbon/nanoparticle nickel composites have been synthesized via multi-component co-assembly strategy associated with a direct carbonization process from resol, tetraethyl orthosilicate, Ni(NO₃)₂·6H₂O and triblock copolymer F127 and subsequent silicates removal with NaOH solution. The incorporation of rigid silicates in the pore walls can reduce framework shrinkage significantly during the pyrolysis process, creating large mesopores. Moreover, plenty of complementary small pores caused by silica removal are observed in the carbon pore walls, which contribute to the large surface area. The mesoporous carbon/nanoparticle nickel composites with a low Ni content (1.7 wt%) possess ordered two-dimensional hexagonal structure, large mesopores (6.8 nm), high surface area (1580 m² g⁻¹) and large pore volume (1.42 cm³ g⁻¹). Magnetic Ni nanocrystals with particle size of ∼16.0 nm are confined in the matrix of carbon frameworks. With increase of Ni content, the surface area and pore volume of the composites decrease. The particle size of metallic Ni nanocrystals increases up to 20.3 nm, when its content increases to 10 wt%. These carbon/nanoparticle nickel composites with high surface area, large pore size and superparamagnetic property show excellent adsorption properties for bulky dye fuchsin base and an easy separation procedure.     

Hierarchically porous monoliths of carbon and metal oxides with ordered mesopores

Hierarchically porous carbon and metal oxide materials offer great benefits in separations, catalysis and renewable energy. We have here used hierarchically porous silica monoliths with ordered mesopores as hard templates to produce nanocast carbon, Co₃O₄, and NiO monoliths with similar structures. Besides providing the materials with more well-defined physicochemical properties, the ordered mesopore structure also offers an excellent model system for investigating the nanocasting process in detail. The mesopores of the silica monoliths were first infiltrated with furfuryl alcohol or metal nitrate precursor solutions, which subsequently could be thermally converted to carbon or the corresponding metal oxides. After the silica scaffolds have been removed by etching in base solutions, the resulting replica monoliths display macroscopic morphology and macropore structure similar to the original silica template. However, while the carbon and Co₃O₄ materials both display a well-organized nanowire structure, giving rise to high surface area and narrow pore size distribution, the NiO monoliths exhibit a significantly lower surface area and less well-defined mesopore structure implying that only part of the silica mesopores has been replicated. We believe this apparent difference between the two metal oxides is a consequence of differences in mass transport.     

Preparation of phenolic resin derived 3-D ordered macroporous carbon

Three-dimensionally ordered long-range macroporous carbon structures were prepared using commercially available phenolic resin by utilizing sacrificial colloidal silica crystalline arrays as templates that were subsequently removed by HF etching after pyrolysis in an argon atmosphere. SEM, TEM, and BET were employed to characterize the morphology and the surface area of the porous carbon structures. The pore size (150–1000 nm) and BET surface area, which reflect pore volume (298.6 m²/g (1.32 cm³/g) ∼ 93.7 m²/g (0.12 cm³/g)), of the macroporous carbon structures produced were approximately proportional to the size (150–1000 nm) of the sacrificial silica sphere templates used (annealing temp. 550°C). The achieved 550 nm porous carbon structures were examined to function as potential catalyst carriers and were successfully impregnated with Ag or Pt-Ru on their inner walls after borohydride reduction at room temperature. In addition, porous carbon patterns were fabricated using the ‘micromolding in capillary’ technique, which has potential applications in the microreaction technology.     

Controlling the textural parameters of mesoporous carbon materials

The mesoporous carbon materials prepared by inorganic templating technique using mesoporous silica, SBA-15 as a template and sucrose as a carbon source, have been systematically investigated as a function of sucrose to mesoporous silica composition, with a special focus on controlling the mesoporous structure, surface morphology and the textural parameters such as specific surface area, specific pore volume and pore size distribution. All the materials have been unambiguously characterized by XRD, N₂ adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron microscopy, and Raman spectroscopy. It has been found that the porous structure, morphology and the textural parameters of the mesoporous carbons materials, CMK-3-x where x represent the sucrose to silica weight ratio, can be easily controlled by the simple adjustment of concentration of sucrose molecules. It has also been found that the specific surface area of the mesoporous carbon materials systematically increases with decreasing the sucrose to silica weight ratio. Moreover, the specific pore volume of the materials increases from 0.57 to 1.31 cm³/g with decreasing the sucrose to silica weight ratio from 5 to 1.25 and then decreases to 1.23 cm³/g for CMK-3-0.8. HRTEM and HR-FESEM also show a highly ordered pore structure and better surface morphology for CMK-3-1.25 as compared to other materials prepared in this study. Thus, it can be concluded that the sucrose to silica weight ratio of 1.25 is the best condition to prepare well ordered mesoporous carbon materials with good textural parameters, pore structure and narrow pore size distribution.