Bridging mesoporous carbon particles with carbon nanotubes

The enhancement of the electrical conductivity (EC) of a porous carbon is highly desirable in many applications, especially in those associated with storage and conversion of electrochemical energy. In this work, we demonstrated an approach to largely increasing the EC of ordered mesoporous carbon (OMC) by bridging the OMC particles with carbon nanotubes (CNTs). Infiltration of the pores of ordered mesoporous SBA-15 silica with a carbon precursor yielded a carbon/mesoporous silica composite, which was further used as a support for Ni catalyst. Subsequently, catalytic growth of CNTs on the Ni-supported composite surface was carried out using the chemical vapor deposition (CVD) method with benzene as the carbon precursor. Removal of the silica framework and the metal catalyst left behind OMC particles bridged with CNTs. The EC of the OMC was increased from 138 S/m (before bridging) to 645 S/m (after bridging). Because of the significant enhancement of EC and the availability of mesopores, the cyclability of the hybrid carbon materials as a negative electrode used in rechargeable lithium-ion batteries was significantly improved.     

酚醛树脂基高度有序介孔炭材料的合成及其电容性

以碱性条件下制备出的A阶酚醛树脂为炭前驱体,三元嵌段共聚物P123及F127为介孔模板剂,采用乙醇溶剂蒸发诱导自组装与程序升温策略,制备出高度有序、比表面积达550.12 m2/g、孔容为0.385 4 cm3/g、平均孔径为3.97 nm的酚醛树脂基有序介孔炭材料。利用小角X射线衍射、扫描电镜、透射电镜、物理吸附及电化学性能测试等技术,研究了不同合成条件下得到的有序介孔炭材料的结构和电化学性能。结果表明,在6 mol/L KOH电解质溶液的三电极体系中,该优化有序介孔炭材料在1 A/g的电流密度下比电容可达146.5 F/g。     

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.     

Fabrication of new ordered mesoporous carbons from petroleum pitch by triblock copolymer direct templating method

A highly ordered mesoporous carbon nanocage (OMC) direct synthesis method is introduced in this article. Petroleum pitch is chosen as a hydrophobic carbon precursor, tetrahydrofuran (THF) is used as solvent, the triblock copolymer F127 as structure directing agent, while the liquid crystal templating (LCT) is used as the templating mechanism, and the OMC was obtained via a one-step nanocasting method. Experimental results showed that the introduction of proper amounts of petroleum pitch and THF ratio does not hamper the synthetic process of the structure of OMC, thus a uniform carbon composite is finally formed. It was found that the as-prepared nanoporous carbon has a three-dimensional 7.5 nm-sized carbon nanocage network. Such a uniform mesoporous carbon material exhibits a high Brunauer–Emmett–Teller (BET) surface area (446.9 m² g^??1) and a total pore volume (0.6 cm³ g^??1).     

Superior electric double layer capacitors using ordered mesoporous carbons

This paper reports for the first time superior electric double layer capacitive properties of ordered mesoporous carbon (OMCs) with varying ordered pore symmetries and mesopore structure. Compared to commercially used activated carbon electrode, Maxsorb, these OMC carbons have superior capacitive behavior, power output and high-frequency performance in EDLCs due to the unique structure of their mesopore network, which is more favorable for fast ionic transport than the pore networks in disordered microporous carbons. As evidenced by N₂ sorption, cyclic voltammetry and frequency response measurements, OMC carbons with large mesopores, and especially with 2-D pore symmetry, show superior capacitive behaviors (exhibiting a high capacitance of over 180 F/g even at very high sweep rate of 50 mV/s, as compared to much reduced capacitance of 73 F/g for Maxsorb at the same sweep rate). OMC carbons can provide much higher power density while still maintaining good energy density. OMC carbons demonstrate excellent high-frequency performances due to its higher surface area in pores larger than 3 nm. Such ordered mesoporous carbons (OMCs) offer a great potential in EDLC capacitors, particularly for applications where high power output and good high-frequency capacitive performances are required.     

Effects of ferrocene derivative on the physico-chemical and electrocatalytic properties of ordered mesoporous carbon

This work reports effects of ferrocene derivative on the properties of an ordered mesoporous carbon (OMC). A novel method for the incorporation of iron oxide species in the carbon framework of OMC without any decrease in the surface area is also reported. The decomposition of ferrocene derivative yields iron species that facilitate the formation of the carbon framework. The performance of ordered mesoporous carbon containing iron oxide (OMC-Fe) is compared to OMC and the properties of the new material are found to be improved. OMC-Fe combines electrochemical properties of OMC and iron oxide species. Electrocatalytic properties towards H₂O₂ are enhanced because of synergetic effect of ordered mesoporous carbon and iron oxide species. The electrochemical determination of H₂O₂ at the OMC-Fe modified electrode is more sensitive than that at OMC electrode. A sensitive and stable H₂O₂ sensor was developed based on OMC-Fe electrode with a large determination range and a good reproducibility.     

Ordered mesoporous carbon/sulfur nanocomposite of high performances as cathode for lithium–sulfur battery

Ordered mesoporous carbon/sulfur (OMC/S) nanocomposites with hierarchically structured sulfur loading, ranging from 50 to 75 wt%, were synthesized via a simple melt-diffusion strategy. The OMC with a BET surface area of 2102 m² g⁻¹, a pore volume of 2.0 cm³ g⁻¹ and unique bimodal mesoporous (5.6/2.3 nm) structure, was prepared from a triconstituent co-assembly method. The resulting OMC/S nanocomposite material served as cathode of rechargeable lithium–sulfur (Li–S) battery. It has been tested that the novel OMC/S cathode can deliver a superior reversible capacity and cyclability. In particular, the nanocomposite with a loading of 60 wt% sulfur (OMC/S-60) presents the highest sulfur utilization ca. 70%, an excellent high rate capability ca. 6 C and a good cycling stability for up to 400 full charge–discharge cycles. The exceptional electrochemical performances are exclusively attributed to the large internal surface area and high porosity of the ordered mesoporous carbon, which favorites both electron and Li-ion transportations.     

Synthesis of magnetically separable ordered mesoporous carbons from F127/[Ni(H2O)6](NO3)2/resorcinol-formaldehyde composites

An easy method is described for the synthesis of a mesostructured Ni/ordered mesoporous carbon (OMC) composite with a highly ordered cubic structure (space group Im3m). This synthesis was carried out by the carbonization of the F127/[Ni(H₂O)₆](NO₃)₂/RF (resorcinol-formaldehyde) composite self-assembled in an alkaline medium. The effects of nickel loading content and carbonization temperature on the morphologies, pore features, structures and magnetic properties of these Ni/OMC composites were investigated using the thermogravimetric analysis, X-ray diffraction, nitrogen sorption, transmission electron microscopy and vibrating-sample magnetometer measurements. It was found that Ni²⁺ was captured by the network of F127/RF and further reduced into metallic Ni nanoparticles during the carbonization. The nickel nanoparticles were well-dispersed in the ordered mesoporous carbon walls. The Ni/OMC composites exhibit the soft ferromagnetic behavior and the magnetization parameters can be adjusted by the content of nickel and the carbonization temperatures. The excellent acid-resistant property of the magnetic materials makes them useful in magnetic separation.     

Ordered mesoporous carbons: Implication of surface chemistry, pore structure and adsorption of methyl mercaptan

Three ordered mesoporous carbon materials (OMC) were prepared by pyrolysis of sucrose filled in the mesoporous channels of SBA-15 at three different temperatures of 600 °C (OMC-600), 850 °C (OMC-850) and 1100 °C (OMC-1100), and followed by dissolution of the silica matrix in hydrofluoric acid. The pore structures and surface characteristics of the OMC materials were evaluated using XRD, nitrogen adsorption, FTIR spectroscopy, pH of carbon surface, and the amount of acidic surface groups from Boehm titration, respectively. The increase of the pyrolysis temperature resulted in an increase in surface pH, but a decrease in the amount of acidic surface groups. The surface area and micro- and mesopore volumes increased by increasing the pyrolysis temperature from 600 °C to 850 °C, but there were no significant changes in these properties above 850 °C. In this paper, adsorption characteristics of methyl mercaptan on the OMC materials were studied using a dynamic adsorption method in a fixed bed. The results showed that the adsorption of methyl mercaptan was strongly influenced by pore structure and surface chemistry of the OMC.     

Avoiding structure degradation during activation of ordered mesoporous carbons

Hierarchical micro–mesoporous carbons with high porosity development and ordered structure were prepared. The innovative proposal consists in developing microporosity in ordered mesoporous carbon by chemical activation in template presence in order to minimize the structural damage. Thus, we have directly carried out the chemical activation of a mesoporous carbon/silica composite with KOH. The effect on mesoporous ordered structure of both KOH/carbon ratio and activation temperature has been studied. Following chemical activation the specific surface area is increased from 341 to 1757 m²/g and the micropore volume becomes almost six times larger than initial value. Although a slight widening of the mesopore distribution and an increase in the mesopore volume has been observed during activation, TEM and XRD results reveal an excellent conservation of the ordered mesoporous structure during activation even at conditions well above the limits that a CMK-3 type carbon can resist.     

基于预沥青烯的有序结构中孔炭及其电化学性能

以预沥青烯为碳源、SBA-15为模板,采用模板法合成了结构有序的中孔炭材料。用XRD、TEM、N₂吸附和电化学工作站等对中孔炭的微观结构及电化学性能进行了研究。结果表明,以预沥青烯为碳源合成的炭材料具有高度有序的二维六方孔道和一定的石墨化程度,它反转复制了模板SBA-15的结构。中孔炭的比表面积为542 m²·g^-1,孔容为0.479 cm³·g^-1,孔径呈单峰分布,集中在3.5 nm左右。这种预沥青烯基中孔炭作为电化学电容器电极材料,显示出良好的性能,在1 mA的电流强度下其单电极质量比电容高达310 F·g^-1。     

Synthesis of an ordered mesoporous carbon with graphitic characteristics and its application for dye adsorption

An ordered mesoporous carbon (OMC) was prepared by a chemical vapor deposition technique using liquid petroleum gas (LPG) as the carbon source. During synthesis, LPG was effectively adsorbed in the ordered mesopores of SBA-15 silica and converted to a graphitic carbon at 800 °C. X-ray diffraction and nitrogen adsorption/desorption data and high-resolution transmission electron microscopy (HRTEM) of the OMC confirmed its ordered mesoporous structure. The OMC was utilized as an adsorbent in the removal of dyes from aqueous solution. A commercial powder activated carbon (AC) was also investigated to obtain comparative data. The efficiency of the OMC for dye adsorption was tested using acidic dye acid orange 8 (AO8) and basic dyes methylene blue (MB) and rhodamine B (RB). The results show that adsorption was affected by the molecular size of the dye, the textural properties of carbon adsorbent and surface-dye interactions. The adsorption capacities of the OMC for acid orange 8 (AO8), methylene blue (MB) and rhodamine B (RB) were determined to be 222, 833, and 233 mg/g, respectively. The adsorption capacities of the AC for AO8, MB, and RB were determined to be 141, 313, and 185 mg/g, respectively. The OMC demonstrated to be an excellent adsorbent for the removal of MB from wastewater.     

Ordered mesoporous carbons (OMC) as supports of electrocatalysts for direct methanol fuel cells (DMFC): Effect of carbon precursors of OMC on DMFC performances

This paper presents the effect of graphitic character of ordered mesoporous carbons (OMCs) on the performances of OMC supported catalysts for direct methanol fuel cells (DMFC). Two OMC samples with hexagonal mesostructure were prepared from phenanthrene and sucrose by nano-replication method using mesoporous silica as a template. Structural characterizations revealed that both OMCs exhibited large BET surface area and uniform mesopores, while the OMC synthesized from phenanthrene exhibited lower sheet resistance than the OMC derived from sucrose. The Pt nanoparticles were supported on both OMCs with very high dispersion, as the particle size was estimated under 3 nm despite high metal loading of 60 wt.%. In DMFC single cell test, the OMC supported Pt catalysts exhibited much higher performance than the commercial catalyst, which may be attributed to the high surface area and uniform mesopore networks of OMC. In particular, it was found that the performance of OMC supported catalysts can be significantly enhanced by lowering the resistance of OMC.     

Synthesis of polyaniline/mesoporous carbon nanocomposites and their application for CO<Subscript>2</Subscript> sorption

Ordered mesoporous carbons (OMC), were synthesized by nanocasting using ordered mesoporous silica as hard templates. Ordered mesoporous carbons CMK-1 and CMK-3 were prepared from MCM-48 and SBA-15 materials with pore diameters of 3.4 nm and 4.2 nm, respectively. Mesoporous carbons can be effectively modified for CO₂ adsorption with amine functional groups due to their high affinity for CO₂. Polyaniline (PANI)/mesoporous carbon nanocomposites were synthesized from in-situ polymerization by dissolving OMC in aniline monomer. The polymerization of aniline molecules inside the mesochannels of mesoporous carbons has been performed by ammonium persulfate. The nanocomposition, morphology, and structure of the nanocomposite were investigated by nitrogen adsorption-desorption isotherms, Fourier Transform Infrared (FT–IR), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and thermo gravimetric analysis (TGA). CO₂ uptake capacity of the mesoporous carbon materials was obtained by a gravimetric adsorption apparatus for the pressure range from 1 to 5 bar and in the temperature range of 298 to 348 K. CMK-3/PANI exhibited higher CO₂ capture capacity than CMK-1/PANI owing to its larger pore size that accommodates more amine groups inside the pore structure, and the mesoporosity also can facilitate dispersion of PANI molecules inside the pore channels. Moreover, the mechanism of CO₂ adsorption involving amine groups is investigated. The results show that at elevated temperature, PANI/mesoporous carbon nanocomposites have a negligible CO₂ adsorption capacity due to weak chemical interactions with the carbon nanocomposite surface.     

一步法合成载铁有序介孔碳材料的形成机理

采用软模板路线以三嵌段共聚物F127为模板剂,间苯二酚-甲醛缩聚所形成酚醛树脂(RF)为碳源,与酚羟基有络合作用的无机铁盐为金属前体,在无外加酸碱催化剂的条件下,利用铁盐的水解反应形成酚醛缩聚所需酸性环境,多组分共组装一步合成了载铁有序介孔碳材料(Fe/OMC)。对Fe/OMC合成各阶段过程进行了分析,利用X射线衍射、透射电子显微镜等手段对材料进行表征,比较了不同老化时间、硝酸铁投加量及酚醛比例等合成条件对材料结构的影响规律。结果表明,在较长的老化时间(≥60 h)、适宜的n(Fe)/n(R)比(0.05～0.2)和n(R)/n(F)比[(1/1.5)～(1/2)]条件下,均可形成有序的介孔结构。在此基础上,提出了载铁有序介孔碳材料的形成机理。     

有序介孔碳和活性炭对阿莫西林的吸附研究

阿莫西林是废水中一类典型的药品与个人护理品类新型有机污染物,会对周围环境和人体健康造成潜在威胁。以蔗糖为碳源、以SBA-15为模板制备有序介孔碳（OMC）。采用动态吸附法研究其对阿莫西林的吸附行为,并与常规吸附材料商用活性炭（GAC）作对比。探讨了废水中阿莫西林的初始浓度、温度及流速对动态吸附的影响。结果表明：在同等条件下,OMC的吸附能力远强于GAC,以OMC为吸附剂可有效去除废水中的阿莫西林类新型有机污染物。     

Enhanced liquid phase catalytic hydrodechlorination of 2,4-dichlorophenol over mesoporous carbon supported Pd catalysts

Supported Pd catalysts on ordered mesoporous carbon (OMC) and activated carbon (AC) were prepared and their catalytic behavior for the liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol was investigated. In comparison with Pd/AC, Pd particles of Pd/OMC were effectively confined in the mesopores of OMC, resulting in high Pd dispersion and Pd²⁺ content. Accordingly, Pd/OMC exhibited higher catalytic activity than Pd/AC. Moreover, increasing catalyst reduction temperature lowered the catalytic activities and favored stepwise HDC of 2,4-dichlorophenol.     

Mesoporous carbons as low temperature fuel cell platinum catalyst supports

Platinum catalysts supported on ordered mesoporous carbons (OMC) are described. The mesoporous carbon support, CMK3 type, was synthesised as an inverse replica of a SBA-15 silica template. The platinum catalysts (i.e. Pt 20 wt% and Pt 10 wt%, respectively), obtained through a conventional wet impregnation method, have been investigated to determine their structural characteristics and electrochemical behaviour. The electro-catalytic performance towards the oxygen reduction reaction (ORR) was compared to those of commercial Pt/C-Vulcan XTC72R (E-Tek) catalysts with the same Pt wt%, under the same experimental conditions. The two catalyst samples have allowed the effect of the variation of both the Pt to Nafion and Pt to the supporting carbon ratios to be studied. Electrochemical tests have been carried out in three different systems: a catalyst ink deposited on a glassy carbon rotating disk electrode (RDE), a gas diffusion electrode (GDE) in a three-electrode cell with H₂SO₄ as the electrolyte and a complete PEM single fuel cell. The first results indicate that the OMC performs slightly less well than commercial carbon supports, mainly in the complete fuel cell system. The data from the cell tests indicate a less effective distribution of Nafion on the OMC surface which, probably, decreases the platinum utilisation and the proton conductivity.     

介孔碳的研究进展及应用

介孔碳是一类新型的具有巨大比表面积和孔体积的介孔材料,可以通过不同的方法合成并对其孔结构和形貌进行调节。本文主要综述了介孔碳及介孔碳基复合材料的合成方法,对比阐述了不同方法制备的介孔碳材料所具备的孔道结构和形貌。介绍了将不同非金属和金属元素及其氧化物掺杂在介孔碳中合成复合材料,发现制备的复合材料具有更优的性能且掺杂元素不同复合材料的形貌和孔道结构不同。此外,简要说明了介孔碳及碳基复合材料在环境、催化、储能、电化学和生物医学等方面的应用,指出其在各个领域的应用仍存在不足。调整介孔碳的孔结构和表面性能、采用更简便易控制的合成方法将成为制备介孔碳及碳基材料的主要研究方向。     

Direct synthesis of ordered mesoporous carbon applied in hydrogen storage

In this work, we present a direct, novel and low cost method for the preparation of an ordered mesoporous carbon (OMC). OMC was successfully synthesized by the carbonization of the silica/triblock copolymer/sucrose composite in the presence of sulfuric acid. The resulting material was characterized by XRD, N₂ sorption analysis and TEM techniques. The novel synthesis technique improved significantly the H₂ storage properties (3.78 wt%) compared with that of CMK-3 synthesized using the nanocasting strategy (2.2 wt%) at 77 K and 10 bar.