Synthesis of mesoporous carbons using ordered and disordered mesoporous silica templates and polyacrylonitrile as carbon precursor

Mesoporous carbons were synthesized from polyacrylonitrile (PAN) using ordered and disordered mesoporous silica templates and were characterized using transmission electron microscopy (TEM), powder X-ray diffraction, nitrogen adsorption, and thermogravimetry. The pores of the silica templates were infiltrated with carbon precursor (PAN) via polymerization of acrylonitrile from initiation sites chemically bonded to the silica surface. This polymerization method is expected to allow for a uniform filling of the template with PAN and to minimize the introduction of nontemplated PAN, thus mitigating the formation of nontemplated carbon. PAN was stabilized by heating to 573 K under air and carbonized under N2 at 1073 K. The resulting carbons exhibited high total pore volumes (1.5-1.8 cm3 g(-1)), with a primary contribution of the mesopore volume and with relatively low microporosity. The carbons synthesized using mesoporous templates with a 2-dimensional hexagonal structure (SBA-15 silica) and a face-centered cubic structure (FDU-1 silica) exhibited narrow pore size distributions (PSDs), whereas the carbon synthesized using disordered silica gel template had broader PSD. TEM showed that the SBA-15-templated carbon was composed of arrays of long, straight, or curved nanorods aligned in 2-D hexagonal arrays. The carbon replica of FDU-1 silica appeared to be composed of ordered arrays of spheres. XRD provided evidence of some degree of ordering of graphene sheets in the carbon frameworks. Elemental analysis showed that the carbons contain an appreciable amount of nitrogen. The use of our novel infiltration method and PAN as a carbon precursor allowed us to obtain ordered mesoporous carbons (OMCs) with (i) very high mesopore volume, (ii) low microporosity, (iii) low secondary mesoporosity, (iv) large pore diameter (8-12 nm), and (v) semi-graphitic framework, which represent a desirable combination of features that has not been realized before for OMCs.     

有序介孔炭的合成及液相有机大分子吸附性能研究

分别采用有序介孔氧化硅SBA-15和NaY分子筛为硬模板合成了系列有序介孔炭OMC和微孔炭CFY. N₂静态吸附测试表明, 所合成的介孔炭具有丰富的介孔结构和集中的介孔分布. 以亚甲基蓝为探针分子, 研究其在有序介孔炭OMC和微孔炭CFY上的吸附行为. 研究结果表明, 有序介孔炭中大于3.5 nm的大介孔孔容是决定亚甲基蓝吸附容量和吸附速率的关键因素. 吸附动力学理论研究表明, 准二级动力学方程可以很好地描述亚甲基蓝分子在介孔炭上吸附动力学行为.     

The characteristics of highly ordered mesoporous carbons as electrode material for electrochemical sensing as compared with carbon nanotubes

In this paper, the unique properties of highly ordered mesoporous carbons modified glassy carbon electrode (OMCs/GE) are illustrated from comparison with carbon nanotubes modified glassy carbon electrode (CNTs/GE) for the electrochemical sensing applications. Electrochemical behaviors of eight kinds of inorganic and organic electroactive compounds were studied at OMCs/GE, which shows more favorable electron transfer kinetics than that at CNTs/GE. Especially, OMCs/GE exhibits remarkably strong and stable electrocatalytic response toward NADH compared with CNTs/GE. The ability of OMCs to promote electron transfer not only provides a new platform for the development of dehydrogenase-based bioelectrochemical devices, but also indicates a potential of OMCs in a wide range of sensing applications. OMCs prepared are the novel carbon electrode materials, exhibiting more favorable electrochemical reactivity than CNTs for the wide electrochemical sensing applications without pretreatments, while purification or end-opening processing was usually required in case of CNTs.     

Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-pore mesoporous carbons with high surface areas

Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized.     

Electrical double-layer capacitor performance of nitrogen-doped ordered mesoporous carbon prepared by nanotemplating method

In this work, the electrical double-layer capacitive properties of nitrogen-doped ordered mesoporous carbons (N-OMCs) were investigated. Ordered mesoporous carbons (OMCs) with 3D body-centered Ia3d structure has been prepared by KIT-6 mesoporous silica as a hard template with aniline for N-OMC and sucrose for Su-OMC as a carbon precursor. Using the different carbon precursor, moderate amounts of nitrogen atoms could be doped to the OMC structures. The obtained materials were characterized by powder X-ray diffraction (XRD), nitrogen adsorption isotherms at 77 K, elemental analysis, and X-ray photoelectron spectroscopy (XPS). Prepared OMCs had mesopore properties such as a high surface area with narrow pore-size distribution. From cyclic voltammograms (CVs) test, N-OMC compared to Su-OMC exhibit higher capacitance and fast charge/discharge characteristics, which results from their pseudo-capacitive effect of incorporated nitrogen atoms. It was thought that N-OMC prepared by the nanotemplating method with KIT-6 and aniline were suitable electrode materials for electrical double-layer capacitors.     

Templated Synthesis of Ordered Mesoporous Carbons with Tailored Structures and Morphologies

Due to the excellent biocompatibility and the capability to load and release drugs, ordered mesoporous carbons (OMCs) have been highly prospective and valuable in drug delivery system. In this contribution, synthesis of OMCs with tailored pore sizes from 4.1 to 3.4 nm was achieved by employing SBA‐15 as template and furfuryl alcohol (FA) as carbon precursors. An array of OMCs with controlled structures and morphologies by incipient wetness with FA was analyzed by powder X‐ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), and Raman spectroscopy. The resulting carbon replicas retained the hexagonal symmetry of the silica templates SBA‐15 with p6mm space group, although the framework suffered shrinkage in the replicated process. The pore size distribution, uniformity and pore volume of the mesopores in the OMCs were affected by structural properties of the SBA‐15 templates as shown by N₂ sorption and XRD pattern analysis. The process had the advantage that the textural parameters of the obtained OMCs were tunable simply by varying aging temperature of the silica template and the ratio of carbon precursor.     

有序介孔碳负载Fe、Co、Ni纳米晶的软模板合成及其表征

报道了在有序介孔碳基体中一步合成负载Fe、Co、Ni纳米晶的方法. 以间二苯酚和甲醛为碳源, F127为模板剂, Fe、Co、Ni的硝酸盐为前驱体, 通过软模板组装路线在酸性条件下合成了负载型有序介孔碳复合材料. 采用X射线衍射(XRD)、透射电镜(TEM)和氮气吸附等手段对所合成材料进行了表征. 结果表明: 合成的材料具有类似于SBA-15的有序介孔结构, 有序介孔碳负载Fe、Co、Ni纳米晶复合材料的比表面积分别为586、626和698 m²·g^-1. XRD和TEM表征结果证实了金属物种以高分散纳米晶的形式分布在介孔碳基体中.     

A family of ordered mesoporous carbons derived from mesophase pitch using ordered mesoporous silicas as templates

A variety of ordered mesoporous carbons (OMCs) were synthesized using ordered mesoporous silicas (OMSs) as hard templates and the mesophase pitch (MP) as a carbon precursor. The synthesis included the mixing of OMS with MP, the infiltration of OMS with MP at 450–550?°C and the carbonization of MP in OMS/MP composite followed by the dissolution of the OMS template. OMCs with structures of two-dimensional hexagonal arrays of nanorods and three-dimensional arrays of nanospheres were obtained through the replication of silica templates, including large-pore SBA-15, KIT-6, large-pore FDU-12 and SBA-16. In particular, 2-D hexagonal array of carbon nanorods (CMK-3 carbon) with (100) interplanar spacing of ～13 nm as well as an array of carbon nanospheres arranged in the face-centered cubic structure with the unit-cell parameter of 33 nm were successfully prepared. The specific surface areas of the resulting carbons were up to 400 m²/g, and the total pore volumes were up to 0.43 cm³/g, with the highest values achieved when the MP infiltration temperature was 500?°C. The OMCs exhibited narrow mesopore size distributions. As inferred from XRD, the frameworks of OMCs featured semi-graphitic structures even though moderate carbonization temperature (850?°C) was employed.     

Soft-templating synthesis and adsorption properties of mesoporous carbons with embedded silver nanoparticles

Mesoporous carbons containing silver nanoparticles have been successfully synthesized under acidic conditions by employing resorcinol and formaldehyde as carbon precursors and triblock copolymer EO₁₀₁PO₅₆EO₁₀₁ (Lutrol F127) as a soft template. Silver nanoparticles of ∼90 nm were added to the synthesis mixture to achieve 10 wt% and 20 wt% of Ag loading in the carbon. Also, tetraethyl orthosilicate (TEOS) was introduced to the system in order to improve adsorption properties of the silver-carbon composites and to reinforce its structure. The resulting carbons with incorporated silver nanoparticles featured high surface areas, large total pore volumes and primary mesopores in the range between ∼6–7 nm.     

Efficient synthesis and sulfonation of ordered mesoporous carbon materials

Ordered mesoporous carbons (OMCs) with hexagonal structure were efficiently synthesized via cooperative self-assembly of phenol/formaldehyde resol and surfactant F127 under acidic aqueous conditions. Induced by HCl, a gel phase mainly containing phenol/formaldehyde resol and F127 was obtained within several hours. X-ray diffraction (XRD), transmission electron microscope (TEM) and nitrogen adsorption isotherms indicated that the synthesized samples possess 2-D hexagonal mesostructure. The influence of the synthesis conditions, including acid concentration and mass ratio of resol to F127, was investigated. When the acid concentration was fixed in the range of 0.6-2.0 M and the mass ratio of resol to F127 in the range of 3.5-4.0, highly ordered mesoporous carbon could be synthesized. The synthesized OMCs could be easily sulfonated in concentrated sulfuric acid at elevated temperature. The results indicate that the mesostructural stability and the content of the surface sulfonic acid (SO(3)H) groups depend mainly on the pyrolysis temperature of the OMCs and the sulfonation temperature, suggesting that the combination of pyrolysis and sulfonation temperature is essential for developing OMCs with high densities of SO(3)H groups.     

孔径渐变的有序介孔炭的合成及电化学应用

以SBA-15为模板,硼酸为孔道扩张剂,蔗糖为碳源制备了一系列孔径渐变的有序硼杂介孔炭材料,并研究了其电化学电容性能。氮气静态吸附测试表明,当硼酸物质的量分数从0%增大到75%时,介孔炭的孔径从3.3nm增大至8.1nm,并保持有序的介孔结构。电化学测试表明,在KOH电解液中,硼杂介孔炭比电容明显高于未掺杂硼有序介孔炭,孔道有序性和孔径大小共同影响了炭材料的电容性能。当硼酸物质的量分数为50%时,炭材料的比电容性能最优。     

Preparation and drug release behavior of temperature-responsive mesoporous carbons

A temperature-responsive composite based on poly (N-isopropylacrylamide) (PNIPAAm) and ordered mesoporous carbons (OMCs) has been successfully prepared by a simple wetness impregnation technique. The structures and properties of the composite were characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ sorption, thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). The results showed that the inclusion of PNIPAAm had not greatly changed the basic ordered pore structure of the OMCs. Ibuprofen (IBU) was selected as model drug, and in vitro test of IBU release exhibited a temperature-responsive controlled release delivery.     

Self-catalyzed synthesis of mesoporous carbons with tunable pore size and structure by soft-templating method

A series of mesoporous carbons (MCs) have been obtained through organic–organic self-assembly method by using phloroglucinol–formaldehyde as carbon precursor and a reverse amphiphilic triblock copolymer as a template. Because of its acidity, the phloroglucinol was used as a catalyst itself. Results show that the pore size and structure of MCs were tailored by simply tuning the weight content of formaldehyde while keeping other reactants constant. A cylindrical mesostructure was obtained when the weight content was 1.0, 1.2 and 1.4. Further increasing the weight content to 1.6 or 2.0, a three-dimensional cage-like mesostructure was obtained. Specific surface area and pore volume up to 485 m²/g and 0.78 cm³/g can be reached, respectively. In addition, the pore size can be tuned in the range of 4.9–14.8 nm by changing the content of formaldehyde.     

Surface functionalization of ordered mesoporous carbons--a comparative study

Hexagonally structured mesoporous carbons C15 and CMK-5 and cubically structured carbon C48 were synthesized using ordered silica SBA-15 and MCM-48 as templates and carbon precursors of different structures. The surfaces of these ordered carbons were chemically functionalized by employing an approach, in which the selected diazonium compounds were in situ generated and reacted with the carbon frameworks of the mesoporous carbons. The aromatic organic molecules containing chlorine, ester, and alkyl groups were covalently attached to the surface of these ordered mesoporous carbons. The presence of functional groups on the modified carbons was confirmed with Fourier transform infrared spectroscopy, thermogravimetric analysis, and nitrogen adsorption. The BET-specific surface area and the pore width of ordered carbons were significantly reduced, whereas the primary structure of these ordered carbons and their unit cells were intact. Basically, the density of grafted functional groups is related to the specific surface area of the sample, particularly the surface area of mesopores. The surface functionalization reaction takes place only on the external surface of carbon C15, while it occurs on both of the internal and external surface of CMK-5 carbon with the nanopipe structure. The presence of the micropores in CMK-5 carbon should be responsible for its lower grafting density because the small micropores are inaccessible in the reaction. It was also proposed that the preferred adsorption/reaction in C48 may be related to the observed unsymmetrical degradation of the XRD patterns for the functionalized C48 samples. The chemical modification process considerably reduced the primary mesopores in these ordered carbons by approximately 1-1.5 nm, affording carbons with micropores in the cases of C15 and C48, and mixed micropores and small mesopores in the case of CMK-5. A grafting density of approximately 0.9-1.5 micromol/m(2) was achieved under current research.     

Partially graphitized ordered mesoporous carbons for high-rate supercapacitors

Partially graphitized ordered mesoporous carbons have been prepared with a soft template method using low-molecular-weight phenolic resol as a carbon source, triblock copolymer F127 as a template, and ferric citrate as a graphitization catalyst. N₂ sorption and transmission electron microscopy analysis show that the ordered mesoporous carbons have been partially graphitized when the carbonization temperature is above 700 °C. The graphitic ordered mesoporous carbons exhibit better rate performance than amorphous ordered mesoporous carbons. The specific capacitance of the graphitic ordered mesoporous carbons (GOMCs) prepared at 700 °C reaches to 112 F g^?1 at a scan rate of up to 1,000 mV s^?1. Its capacitance retention ratio is 64 %, which is much higher than that of the amorphous ordered mesoporous carbons prepared at 600 °C (33 %). High electronic conductivity and ordered mesoporous structure lead to the high electrochemical performance of the partially graphitized ordered mesoporous carbons.     

Nitrogen-doped cobalt nanoparticles/nitrogen-doped plate-like ordered mesoporous carbons composites as noble-metal free electrocatalysts for oxygen reduction reaction

In this work, nitrogen-doped cobalt nanoparticles/nitrogen-doped plate-like ordered mesoporous carbons(N/Co/OMCs) were used as noble-metal free electrocatalysts with high catalytic efficiency. Compared with OMCs with long channel length, due to more entrances for catalytic target accessibility and a short pathway for rapid diffusion, the utilization efficiency of cobalt nanoparticles inside the plate-like OMCs with short pore length is well improved, which can take full advantage of porous structure in electrocatalysis and increase the utilization of catalysts. The active sites in N/Co/OMCs for oxygen reduction reaction(ORR) are highly exposed to oxygen molecule, which results in a high activity for ORR. By combination of the catalytic properties of nitrogen dopant, incorporation of Co nanoparticles, and structural properties of OMCs, the N/Co/plate-like OMCs are highly active noble-metal free catalysts for ORR in alkaline solution.     

Adsorption of bulky molecules of nonylphenol ethoxylate on ordered mesoporous carbons

Ordered mesoporous carbons (OMCs) with varying pore sizes were prepared using ordered mesoporous silica SBA-15 as hard templates. The OMCs possess abundant mesopores with narrow pore size distribution, on which the adsorption behavior of bulky molecules of nonylphenol ethoxylate (NPE) were investigated. The isotherms of NPE on OMCs can be fitted by Langmuir adsorption model, evidenced by the adsorption data. The surface area of the pores larger than 1.5 nm is a crucial factor to the adsorption capacity of NPE, whereas the most probable pore diameter of OMCs is crucial to the adsorption rate of NPE. The adsorption temperature has more significant effects on adsorption rate than the adsorption capacity. Theoretical studies show that the adsorption kinetics of NPE on OMCs can be depicted with the pseudo-second-order kinetic model. In addition, thermodynamic parameters of adsorption were evaluated based on the equilibrium constants related to the equilibrium of adsorption at different temperatures.     

HCl对有序介孔氧化硅结构与形貌的影响

以三嵌段共聚物P123为有机模板导向剂、正硅酸乙酯TEOS为无机硅源, 在HCl存在的强酸性环境下, 采用水热法合成了有序介孔分子筛SBA-15. 采用XRD、SEM、TEM、N2吸附-脱附等手段对产物的结构与形貌进行了分析, 考察了HCl用量对有序介孔材料结构及形貌的影响. 结果表明, 在合成有序介孔氧化硅时, HCl发挥了催化和中间离子的双重作用, 促使棒状胶束形成六方有序排列, 降低SBA-15中微孔的数量, 而且对合成有序介孔氧化硅SBA-15的形貌有显著影响. 适宜的HCl用量对形成“珍珠链状”形貌的、热稳定性优良的SBA-15介孔材料具有重要作用.     

Solution-phase synthesis of ordered mesoporous carbon as resonant-gravimetric sensing material for room-temperature H_2S detection

H_2S can cause multiple diseases and poses a great threat to human health.However,the precise detection of extremely toxic H_2S at room temperature is still a great challenge.Here,a facile solvent evaporation induced aggregating assembly(EIAA) method has been applied for the production of ordered mesoporous carbon(OMCs) in an acidic THF/H_2 O solution with high-molecular-weight poly(ethylene oxide)-b-polystyrene(PEO-b-PS) copolymers as the structure-directing agent,formaldehyde and resorcinol as carbon precursors.Along with the continuous evaporation of THF from the mixed solution,cylindrical micelles are formed in the solution and further assemble into highly ordered mesostructure.The obtained OMCs possesses a two-dimensional(2 D) hexagonal mesostructure with uniform and large pore diameter(～19.2 nm),high surface area(599 m~2/g),and large pore volume(0.92 cm~3/g).When being used as the resonant cantilever gas sensor for room-temperature H_2S detection,the OMCs has delivered not only a superior gas sensing performance with ultrafast re s ponse(14 s) and recovery(21 s) even at low concentration(2 ppm) but also an excellent selectivity toward H_2S among various common interfering gases.Moreover,the limit of detection is better than 0.2 ppm,indicating its potential application in environmental monitoring and health protection.     

Nitric acid oxidation of ordered mesoporous carbons for use in electrochemical supercapacitors

Ordered mesoporous carbon materials with high microporosity were synthesized by a low temperature autoclaving of citric acid-catalyzed polymerized resorcinol/formaldehyde in the presence of the triblock copolymer F127 and were activated by nitric acid oxidation. The materials were used as electrode materials in electrochemical supercapacitors. A bimodal pore size distribution of 2.1–2.3 and 5.3 nm with a surface area of 465–578 m² g^?1 and pore volume of 0.44–0.54 cm³ g^?1 was obtained with the retention of an ordered mesoporous structure after nitric acid (2 M) treatment. The introduced functional groups produced a pseudocapacitance, which resulted in an increase in the specific capacitance. The electrochemical capacitance of the resulting mesoporous carbons showed a marked increase after 3 h of nitric acid activation, exhibiting a high value of 295 F g^?1 at the scan rate of 10 mV s^?1 in 6 M KOH aqueous solution and good cycling stability with specific capacitance retention over 500 cycles.