Fabrication and nano-structure control of carbon aerogels via a microemulsion-templated sol-gel polymerization method

Carbon aerogels were successfully fabricated by a microemulsion-templated sol-gel polymerization method. When a suitable molar ratio of surfactant to resorcinol (S/R) and an appropriate resorcinol-formaldehyde concentration were selected, the organic gels thus obtained could be dried with little shrinkage by heating at ambient pressure. The size of carbon nano-particles and the pore size of carbon aerogels thus produced decrease with an increase of S/R. The highest specific surface area and specific mesopore volume of the carbon aerogels prepared by our method were 620 m² g⁻¹ and 1.14 cm³/g, respectively.     

Catalytic combustion of toluene on platinum-containing monolithic carbon aerogels

Monolithic organic aerogels were prepared by the sol–gel procedure from the polymerisation reaction of resorcinol and formaldehyde in water. The organic aerogels were heat treated in inert atmosphere at either 500 or 1000 °C to obtain the carbon aerogels. The catalysts were prepared by impregnation with an aqueous solution of [Pt(NH₃)₄]Cl₂ or by dissolving this salt in the initial aerogel mixture. Supported catalysts were pretreated in He at 400 °C or H₂ at 300 °C before their characterization by H₂ chemisorption, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy or before testing their catalytic activity. Catalyst activities in toluene combustion were evaluated by conversion versus temperature (light-off curves) and conversion versus time catalytic tests. In the case of catalysts prepared by impregnation, the light-off curves for the total combustion of toluene were shifted to lower temperatures with increasing Pt particle size. This suggests that the reaction was sensitive to the Pt structure within the dispersion range of these catalysts. However, the reverse occurred with catalysts prepared by mixing the precursor in the initial aerogel mixture. Results found could be due to the different surface Pt content of these catalysts as revealed by X-ray photoelectron spectroscopy. This difference was related to the growth of large three-dimensional Pt particles on the surface of the less dispersed catalyst. This means that there is a critical Pt particle size above which the toluene combustion activity decreases with increasing Pt particle size, due to the reduction in active surface sites available for the combustion reaction. Other effect that might influence the activity of these last catalysts is the encapsulation of some Pt particles by the carbon matrix.     

Organic and carbon aerogels derived from poly(vinyl chloride)

Organic aerogels were derived from dimethylformamide solution of poly(vinyl chloride) (PVC) via dehydrochlorination using a strong base, 1,8-diazabicyclo[5,4,0]undec-7-ene, and supercritical drying using carbon dioxide. From these organic aerogels, carbon aerogels were yielded via stabilization and carbonization. Changes in the porous structure of the aerogels during the preparation process and influences of the preparation conditions on the porous structure were investigated. The framework of the aerogels composed the walls of the meso- and macropores. The volume and the size of these pores were reduced during stabilization and carbonization due to the shrinkage of the framework caused by the release of decomposition gases and densification of the material. Simultaneously, the release of decomposition gases produced additional micropores. The extent of dehydrochlorination, the concentration of PVC in the starting solution and the molecular weight of PVC were the factors with which the porous structure of the aerogels could be controlled over a wide range. In addition, the stabilization conditions notably influenced the carbonization behavior of the organic aerogels and the porous structure of the carbon aerogels. The optimum stabilization conditions that minimized the loss of mass and maximized the pore volume of the carbon aerogels were determined.     

Structural changes in carbon aerogels with high temperature treatment

The structural change of carbon aerogels at high temperatures up to 2800°C has been investigated. Change in microtexture of fine particles, which constitute carbon aerogels derived from phenolic resin, was of a typical non-graphitized carbon. The microporosity decreased with an increase of heat-treatment temperature, and disappeared at 2000°C. The mesoporosity still remained even after heat-treatment up to 2800°C, though 50% of mesopore volume was lost because of the fusion of the particles with the change of carbon microtexture.     

硼酸催化炭气凝胶的制备

以苯酚、间甲酚和糠醛为原料,正丙醇作为溶剂,硼酸作为催化剂,通过溶胶-凝胶反应、超临界正己烷干燥以及高温炭化得到了炭气凝胶,并利用扫描电镜、N2吸附、傅立叶变换红外光谱和热重分析等表征手段对所制备的有机气凝胶及其炭气凝胶进行了表征,考察总反应物浓度对有机气凝胶及其炭气凝胶结构的影响.实验结果表明:所制备的炭气凝胶主要是...     

Carbon aerogels derived from cresol–resorcinol–formaldehyde for supercapacitors

The objective of the present paper is to demonstrate the possibility to synthesize mixed carbon aerogels (denoted C_mRF) from cresol (C_m), resorcinol (R) and formaldehyde (F), as an alternative economic route to the classical RF synthesis. These porous carbon aerogels can be used as electrode materials for supercapacitors with a high volume-specific capacitance. Organic precursor gels were synthesized via polycondensation of a mixture of resorcinol and cresol with formaldehyde in an aqueous alkaline (NaOH) solution. After gelation and aging the solvent was removed via drying at ambient pressure to produce organic aerogels. Upon pyrolysis of the organic aerogels at 1173 K, monolithic carbon aerogels can be obtained. By controlling the catalyst (Cat) molar ratio (C_m+R/Cat) in the range 200–500, up to 70% of the resorcinol can be replaced with the cheap cresol. The resulting homogeneous organic aerogels exhibit a drying shrinkage below 15% (linear). The shrinkage and mass loss upon pyrolysis of the mixed aerogels increase with increasing cresol content. Nitrogen adsorption at 77 K was employed to characterize the microstructure of the carbon aerogels. The data show that the porous structure of mixed carbon aerogels is similar to that of RF carbon aerogels. Cyclic voltammetry measurements show that the as-prepared C_mRF carbon aerogels exhibit a high volume-specific capacitance of up to 77 F/cm³.     

Morphology of heat-treated tunsgten doped monolithic carbon aerogels

The morphology of a tungsten-doped monolithic organic aerogel, prepared by the sol-gel method from the polymerisation of a resorcinol, formaldehyde and ammonium tungstate mixture, and of its carbonized derivatives at 500 and 1000 °C was studied by scanning and high-resolution electron microscopy. Tungsten influenced the surface morphology of the carbon aerogels. The tungsten-containing phase was homogeneously distributed in the organic aerogel and its heat treatment produced changes in the metal phase distribution throughout the pellets. Tungsten oxide particles of needle-like structure similar to hollow tubules were detected after heat treatments at different temperatures. In addition, particles of dendritic appearance, formed by tungsten carbide and an intermediate Magnelli phase, appeared when the heat treatment was carried out at 1000 °C.     

Preparation of mesoporous carbon by freeze drying

Resorcinol–formaldehyde (RF) cryogels were synthesized by sol-gel polycondensation of resorcinol with formaldehyde and freeze drying with t-butanol. The cryogels were characterized by nitrogen adsorption and density measurements. Their porous properties were compared with those of RF aerogels prepared by supercritical drying with carbon dioxide. RF cryogels were mesoporous materials with large mesopore volumes >0.58 cm³/g. Although surface areas and mesopore volumes of the cryogels were smaller than those of the aerogels, the cryogels were useful precursors of mesoporous carbons. Carbon cryogels were obtained by pyrolyzing RF cryogels in an inert atmosphere. Carbon cryogels were mesoporous materials with high surface areas >800 m²/g and large mesopore volumes >0.55 cm³/g. When pyrolyzed, micropores are formed inside the cryogels more easily than inside the aerogels.     

Requirements of organic gels for a successful ambient pressure drying preparation of carbon aerogels

In this paper, we investigated the requirements of organic gels for a successful ambient pressure drying by analyzing the role of the strength, the pore size and the surfactant of organic gels in decreasing the drying shrinkage of organic aerogels. Experimental results showed the effect of the decrease of the surface tension, resulting from the surfactant, on the drying shrinkage was very small and negligible. The drying shrinkage depended strongly on the strength and the pore size. Subsequently, the respective role of the strength and the pore size was evaluated. It can be found that the strength plays a greater role than the pore size.     

Characterization of single wall carbon nanotubes by nonane preadsorption

The preferential blocking of the interior adsorption sites of single walled carbon nanotubes (SWNTs) by n-nonane is demonstrated. Following adsorption of n-nonane and evacuation for 24 h at 323 K, it was found that interior sites with diameters less than ∼14 Å remained filled with n-nonane, blocking the physical adsorption of N₂ on these sites at 77.3 K. We demonstrate that “nonane blocking” is a very useful technique for nanotube porosity characterization.     

Surface characteristics and electrochemical capacitances of carbon aerogels obtained from resorcinol and pyrocatechol using boric and oxalic acids as polymerization catalysts

Carbon aerogels were prepared by carbonizing (at 500–1500 °C) organic aerogels obtained from the polymerization reaction of resorcinol and/or pyrocatechol with formaldehyde using boric and oxalic acids as polymerization catalysts. Prepared samples were characterized by different techniques to ascertain their composition, surface chemistry, morphology, and surface physics, determining their electrochemical capacitances in acidic medium. The use of pyrocatechol yielded carbon aerogels that were micro–mesoporous, showing Type IV N₂ adsorption isotherms with Type H2 hysteresis cycles. The volume and size of mesopores depended on the acid catalyst used and the temperature at which the carbon aerogel was obtained. Conversely, the sample prepared with resorcinol and boric acid as catalyst was micro–macroporous and that obtained with a resorcinol–pyrocatechol mixture was micro–mesoporous but with large mesopores. Most of the boric acid used was lost during the exchange of water with acetone in the organic hydrogels before their supercritical CO₂ drying. Carbon aerogels obtained at 900 °C and using boric acid as polymerization catalyst showed a capacitance between 17 and 24 μF/cm². Boron influenced the capacitance because it increased the oxygen content. Sample synthesized using pyrocatechol, formaldehyde, and oxalic acid and heat-treated at 900 °C had the highest capacitance, 34 μF/cm².     

Adsorption and electrothermal desorption of organic vapors using activated carbon adsorbents with novel morphologies

Novel morphologies of activated carbons such as monolith, beads and fiber cloth can effectively capture organic vapors from industrial sources. These adsorbent materials are also unique because they can undergo direct electrothermal regeneration to recover the adsorbed organic vapors for potential re-use. This investigation compares and contrasts the properties of these adsorbents when using electrothermal-swing adsorption. The adsorption systems consisted of an organic vapor generation system, an electrothermal-swing adsorption vessel, a gas detection unit, and a data acquisition and control system. The activated carbon monolith (ACM) had the lowest pressure drop, highest permeability, highest electrical resistivity and lowest cost as compared to the activated carbon beads (ACB) and the activated carbon fiber cloth (ACFC). ACB had the largest throughput ratio and lowest length of unused bed as compared to the other adsorbents. However, ACFC had the largest adsorption capacity for toluene when compared to ACM and ACB. ACFC was also faster to regenerate and had a larger concentration factor than ACM and ACB. These results describe relevant physical, electrical, adsorption and cost properties for specific morphologies of the adsorbents to more effectively capture and recover organic vapors from gas streams.     

Improved performance of PEM fuel cell using carbon paper electrode prepared with CNT coated carbon fibers

Porous conducting carbon paper has been identified as the most suitable material to be used as a backing material for the fuel cell electrode. The surface of carbon fiber, the major constituent of the carbon paper was modified by: (1) removing the functional groups by heat cleaning process and (2) coating the non-functionalized carbon fiber with multi-walled carbon nanotubes (MWCNTs). This has a marked influence on the fiber–matrix interactions during later stages of processing of carbon paper that helped in controlling its various characteristic properties. Using the carbon paper formed with CNT coated carbon fiber as electrode, the maximum power density achieved from a unit fuel cell was found to be 783 mW/cm² as compared to 630 mW/cm² when the paper was formed with normal fiber.     

Control of mesoporous properties of carbon cryogels prepared from wattle tannin and furfural

Wattle tannin–furfural (TFu) carbon cryogels are synthesized by sol–gel polycondensation of wattle tannin with furfural by using sodium hydroxide (NaOH) as a catalyst, dried by freeze-drying technique and then pyrolyzed under inert atmosphere, respectively. The amounts of wattle tannin (T), furfural (Fu), NaOH (C) and distilled water (W) are changed for preparing the mesoporous TFu carbon cryogels. The mole ratio of tannin to catalyst T/C plays a crucial role for the synthesis of TFu organic and carbon cryogels. The results suggest that the T/C ratio should be above 0.25 but <1.0 to prepare the mesoporous and homogeneous cryogels. Although TFu carbon cryogels have the broad mesopore size distribution, the mesoporous structure is controllable by the synthesis conditions. The carbon cryogels possess the mesopore volume less than 0.56 cm³/g and the BET surface area less than 600 m²/g. Moreover, the ratio of catalyst to water C/W can be used to prepare the homogeneous and mesoporous carbon cryogels, and to control the mesopore radius of carbon cryogels in the range of 1.6–9.6 nm.     

Preparation and characterization of antibacterial silver-dispersed activated carbon aerogels

Silver-dispersed carbon aerogels (CAs) were obtained by direct immersion of organic aerogels prepared by ambient pressure drying technique in AgNO₃ aqueous solution and then carbonization. The effect of preparation conditions such as the resorcinol/catalyst ratio, the feed AgNO₃ concentration, the ratio of aerogel mass/solution volume, immersion time and carbonization temperature on the bulk density and silver content as well as the BET surface area of the dispersed CAs was studied. The dispersion and structure of silver nanoparticles in obtained materials were investigated by means of scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The Ag-dispersed CAs prepared exhibit strong and long-term antibacterial activity.