KOH activation of mesoporous carbons obtained by soft-templating

Mesoporous phenolic resin-based carbons were prepared by soft-templating synthesis and activated by KOH. It is shown that the KOH activation of these mesoporous carbons results in a substantial increase of microporosity with simultaneous preservation of mesoporous structure. The resulting micro- and mesoporous carbons possess high surface area and large volume of mesopores.     

KOH activation of ordered mesoporous carbons prepared by a soft-templating method and their enhanced electrochemical properties

Ordered mesoporous carbon (COU-2) was synthesized by a soft-templating method. The COU-2 mesoporous carbon was activated by using KOH to improve its porosity. The mesopore size of COU-2 was 5.5 nm and did not change by the KOH activation. But, the BET surface area of COU-2 largely increased from 694 to 1685 m²/g and total pore volume was increased from 0.54 to 0.94 cm³/g after the KOH activation. The large increase of micropore volume is due to the increase of the surface area. Electrochemical cyclic voltammetry measurements were conducted in aqueous (1 M sulfuric acid) and organic (1 M tetraethyl ammonium tetrafluoroborate/polypropylene carbonate) electrolyte solutions. The KOH-activated COU-2 carbon shows superior capacitances over the COU-2 carbon and a commercial microporous carbon both in aqueous and organic electrolyte solutions. These results suggest that the carbons having regularly-interconnected uniform mesopores and micropores in thin pore walls are desirable for the electrodes in electrochemical double-layer capacitors.     

CO2 adsorption on amine-modified mesoporous silicas

Mesoporous silicas with enhanced pore structures were synthesized and polyethylenimine (PEI) was immobilized in them to produce adsorbents for CO₂. The prepared samples were characterized by N₂ adsorption–desorption isotherms and small angle X-ray diffraction, and their CO₂ adsorption performance were evaluated. CO₂ adsorption capacity increased with operating temperature initially and then decreased. Besides, CO₂ adsorption capacity increased due to the PEI loading with more amine sites. The results showed that the structure of support played an important role in the CO₂ adsorption capacity. High surface area and large pore volume also favored the CO₂ adsorption capacity.     

Electrochemical capacitors based on highly porous carbons prepared by KOH activation

Various coal and pitch-derived carbonaceous materials were activated for 5 h at 800 °C using potassium hydroxide and 1:4 component ratio. Porosity development of the resultant activated carbons (ACs) was assessed by N₂ sorption at 77 K and their capability of the charge accumulation in electric double layer was determined using galvanostatic, voltammetric and impedance spectroscopy techniques. ACs produced from different precursors are all microporous in character but differ in terms of the total pore volume (from 1.05 to 1.61 cm³ g⁻¹), BET surface area (from 1900 to 3200 m² g⁻¹) and pore size distribution. Very promising capacitance values, ranging from 200 to 320 F g⁻¹, have been found for these materials operating in acidic 1 mol l⁻¹ H₂SO₄ electrolytic solution. The variations in the electrochemical behavior (charge propagation, self-discharge, frequency response) are considered in relation to the porous texture characteristics, elemental composition but also possible effect of structural ordering due to various precursor materials used. Cycling investigation of all the capacitors has been also performed to compare ability of the charge accumulation for different carbon materials during subsequent cycles.     

Synthesis of mesoporous carbons for supercapacitors from coal tar pitch by coupling microwave-assisted KOH activation with a MgO template

Mesoporous carbons (MCs) for supercapacitors were prepared from coal tar pitch by a microwave-assisted one-step process coupling the potassium hydroxide (KOH) activation and magnesium oxide (MgO) template. MCs were characterized by scanning electron microscope and X-ray diffraction. The results show that the specific surface area (S_BET), micropore volume and specific capacitance of MCs made by microwave heating as well as the energy density of MC capacitors pass through a maximum with increasing mass of MgO and the relative mass ratio of KOH/pitch. The S_BET of MCs varies from 1003 to 1394 m²/g. The S_BET and total pore volume of MC and microporous carbon made by microwave heating are bigger than that made by conventional heating. Under optimum conditions with the masses of coal tar pitch, MgO, KOH at 9 g, 12 g, 6 g, and the microwave power at 600 W, MC (MC_9-12-6) made at 30 min heating time shows a high specific capacitance of 224 F/g in 6 M KOH aqueous electrolyte after 1000 cycles. The results have shown that microwave-assisted rapid KOH activation coupled with the MgO template is an efficient one-step approach to the preparation of low cost yet high performance MCs for supercapacitors.     

Hierarchically porous phenolic resin-based carbons obtained by block copolymer-colloidal silica templating and post-synthesis activation with carbon dioxide and water vapor

A series of hierarchically porous carbons was synthesized by self-assembly of polymeric carbon precursors and block copolymer template in the presence of tetraethyl orthosilicate (TEOS) and colloidal silica under acidic conditions. Resorcinol and formaldehyde were used as carbon precursors, poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymer was employed as a soft template, and TEOS-generated silica and colloidal silica were used as hard templates. The carbon precursors were polymerized in hydrophilic domains of block copolymer, followed by carbonization and silica dissolution. This resulted in carbons possessing cylindrical (∼12 nm) and spherical (20 or 50 nm) mesopores created by thermal decomposition of the soft template and by the dissolution of colloidal silica, respectively; fine pores were also formed by the dissolution of the TEOS-generated silica (∼2 nm). A further increase in fine porosity was achieved by post-synthesis activation of the carbons with carbon dioxide and/or water vapor, which resulted in hierarchical carbons with a surface area and pore volume approaching 2800 m²/g and 6.0 cm³/g, respectively.     

Rapid adsorption of alcohol biofuels by high surface area mesoporous carbons

Surfactant templated mesoporous carbons were evaluated as biofuel adsorbents through characterization of equilibrium and kinetic behavior for both ethanol and n-butanol. Variations in synthetic conditions enabled facile tuning of specific surface area (500-1300 m²/g) and pore morphology (hexagonally packed cylindrical or BCC spherical pores). n-Butanol was more effectively adsorbed than ethanol for all mesoporous carbons, suggesting a mechanism of hydrophobic adsorption. The adsorbed alcohol capacity increased with elevated specific surface area of the adsorbents, irrespective of pore morphology. While adsorption capacity of these mesoporous carbons is comparable to commercially-available, hydrophobic polymer adsorbents of similar surface area, the pore morphology and structure of mesoporous carbons greatly influenced adsorption rates, enhancing them by up to 1-2 orders of magnitude over commercial polymer adsorbents. Multiple cycles of adsorbent regeneration did not impact the adsorption equilibrium or kinetics. The high chemical and thermal stability of mesoporous carbons provide potential significant advantages over other commonly examined biofuel adsorbents, such as polymers and zeolites.     

Hydrogen adsorption by nanostructured carbons synthesized by chemical activation

In this work several samples of Quercus agrifolia activated carbon, the porous structure of which was nanostructured by chemical activation with NaOH and KOH, were evaluated for hydrogen adsorption at 77 K and atmospheric pressure. Hydrogen adsorption reached values in the order of 2.7 wt.% for KOH activated carbon. The mechanism of formation of the porous nanostructures was found to be the key factor in controlling the hydrogen adsorption capacity of chemically activated carbon.     

Preparation and characterization of porous carbons from PAN-based preoxidized cloth by KOH activation

Porous carbons (PCs) were prepared from PAN-based preoxidized cloth with potassium hydroxide (KOH) as active reagent by the chemical activation method. The PCs have been systematically studied by the adsorptions of nitrogen, benzene and iodine. It has been found that the process parameters such as weight ratio of KOH to the starting material, activation temperature and activation time are crucial for preparing high quality PCs. A series of PCs with high BET surface area and well-developed porous structure in which micropores are dominant were obtained with less KOH and shorter activation time in comparison to the traditional methods. The optimum conditions for preparing PCs with high BET surface area from PAN-based preoxidized cloth were given, and the relationships between pore structure and adsorption property of PCs were explored.     

有机胺功能化介孔固体吸附剂吸附分离CO2性能研究

针对当前固体胺CO₂吸附剂存在吸附容量小、循环稳定性差等问题,采用高比表面积、易嫁接胺的介孔SBA-15作为载体,研究分子筛模板剂脱除方法和有机胺改性方法对制备的固体吸附剂吸附性能的影响,并采用N₂物理吸附、X射线衍射、红外光谱、热失重分析等表征技术并对样品进行表征。实验结果表明,通过嫁接和浸渍能够合成出不同有机胺负载量的胺功能化吸附剂,其中混合胺嫁接法改性的APTES-SBA（U）-T60吸附剂其吸附容量最大,在75℃下的纯CO₂气氛中吸附量达到192.05 mg/g,优于溶剂萃取和煅烧法去除模板剂。此外,混合胺嫁接法制备的样品在多次的吸/脱附操作下,CO₂吸附稳定性良好,表明混合胺修饰的吸附剂具有很好的稳定性和再生性。     

氨改性的介孔二氧化硅的直接合成和CO2吸附

Amine-functionalized mesoporous silica was prepared by using lauric acid and N-stearoyl-l-glutamic acid as structure directing agents via the SN+-I mechanism and applied to CO2 adsorption at room temperature. With γ-aminopropyltriethoxysilane as co-structure directing agent and due to the direct electrostatic interaction with anionic surfactant, most of the amino groups were uniformly distributed at the inner surface of pores and the performance was stable. The amine-functionalized mesoporous silica was characterized by Fourier transform infrared spectrometer, X-ray diffraction, nitrogen physisorption and thermogravimetric analysis. The CO2 adsorption capacity was measured by digital recording balance. At the room temperature and under the atmospheric pres-sure, the adsorption capacity of LAA-AMS-0.2 for CO2 and N2 is 1.40 mmol•g1 and 0.03 mmol•g1, respectively, indicating high separation coefficient of CO2/N2.     

Hydrothermal synthesis of mesoporous carbons for adsorption of two alkaloids

Two mesoporous carbons were synthesized via a hydrothermal treatment approach, characterized and evaluated for adsorption properties of berberine hydrochloride and matrine from water. The mesoporous carbons have BET specific surface areas of 1568.1 and 769.3 m²/g, pore volumes of 1.44 and 0.89 cm³/g, average pore diameters of 3.75 and 8.22 nm, and few O-containing functional groups on the surfaces. Both the mesoporous carbon adsorbents can effectively adsorb berberine hydrochloride and matrine from aqueous solutions, the higher equilibrium adsorption capacities of berberine hydrochloride and matrine at 298 K are 385, and 275 mg/g at 0.10 mg/mL, respectively. Adsorption enthalpy, entropy and free energy of berberine hydrochloride and matrine on the selected mesoporous carbon (with higher BET specific surface area and pore volume) were calculated. The adsorption of berberine hydrochloride and matrine on the selected carbon sample is fast at 298 K, 95% of the adsorption equilibrium could be achieved within 180 and 120 min, respectively. The dynamic adsorption capacities on the selected adsorbent are calculated to be 343.1 and 383.4 mg/g for berberine hydrochloride and matrine, respectively; and 70.8% of the adsorbed berberine hydrochloride and 79.2% of the adsorbed matrine could be desorbed by a 70% alcohol solution. These results provide a reference to the large-scale industrial production and application of mesoporous carbons as potential adsorbents in purification of alkaloids from herbal plant extracts.     

KOH活化丝瓜络制备高比表面积活性炭

为了探讨以丝瓜络为原料制备高比表面积活性炭的最佳条件,通过设计正交实验,研究了碱炭比、活化温度、活化时间和升温速率等因素对KOH活化丝瓜络制备活性炭性能的影响。结果表明：KOH活化丝瓜络制备活性炭的最佳条件为：碱炭比为4、活化温度800 ℃,活化时间30 min,升温速率10 ℃/ min。在此条件下制备的活性炭为多孔、非晶型的无定形碳,具有高的比表面积（3545 m2/g）和强的吸附性能,其碘值和亚甲基蓝值分别达到2926 mg/g和528.58 mg/g;为丝瓜络的高值化利用提供了一条有价值的途径。     

Nitrogen-doped porous carbons through KOH activation with superior performance in supercapacitors

A series of nitrogen-doped porous carbons are prepared through KOH activation of a nonporous nitrogen-enriched carbon which is synthesized by pyrolysis of the polymerized ethylenediamine and carbon tetrachloride. The porosity and nitrogen content of the nitrogen-doped porous carbons depend strongly on the weight ratio of KOH/carbon. As the weight ratio of KOH/carbon increases from 0.5 to 2, the specific surface area increases from 521 to 1913 m² g⁻¹, while the nitrogen content decreases from 10.8 to 1.1 wt.%. The nitrogen-doped porous carbon prepared with a moderate KOH/carbon weight ratio of 1, which possesses a balanced specific surface area (1463 m² g⁻¹) and nitrogen content (3.3 wt.%), exhibits the largest specific capacitance of 363 F g⁻¹ at a current density of 0.1 A g⁻¹ in 1 M H₂SO₄ aqueous electrolyte, attributed to the co-contribution of double-layer capacitance and pseudocapacitance. Moreover, it shows excellent rate capability (182 F g⁻¹ remained at 20 A g⁻¹) and good cycling stability (97% capacitance retention over 5000 cycles), making it a promising electrode material for supercapacitors.     

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.     

Adsorption of congo red on mesoporous activated carbon prepared by CO2 physical activation

This research demonstrates the production of mesoporous activated carbon from sargassum fusiforme via physical activation with carbon dioxide. Central composite design was applied to conduct the experiments at different levels by altering three operating parameters. Activation temperature(766–934 ℃), CO_2 flow rate(0.8–2.8 L·min(~-1)) and activation time(5–55 min) were the variables examined in this study. The effect of parameters on the specific surface area, total pore volume and burn-out rate of activated carbon was studied,and the influential parameters of methylene blue adsorption value were identified employing analysis of variance. The optimum conditions for maximum methylene blue adsorption value were: activation temperature = 900 ℃, activation time = 29.05 min and CO_2 flow rate = 1.8 L·min(~-1). The activated carbon produced under optimum conditions was characterized by BET, FTIR and SEM. The adsorption behavior on congo red was studied. The effect of parameters on the adsorbent dosage, temperature, PH and initial congo red concentration was investigated. The adsorption properties of the activated carbon were investigated by kinetics. The equilibrium removal rate and maximum adsorption capacity reaches up to 94.72%, 234 mg·g-1,respectively when initial congo red concentration is 200 mg·L~(-1) under adsorbent dosage(0.8 g · L~(-1)),temperature(30℃), PH7.     

氨基功能化介孔超分子聚合物的温和构筑及其CO2吸附性能

以3,3'-二硫代双(丙酰肼)和对苯二甲醛为组装基元,通过动态共价键采用界面组装法在常温常压下温和构筑了具有丰富CO₂吸附位点的介孔超分子聚合物PDP。利用动态共价键的动态可逆性,通过合成后修饰法将两种具有丰富氨基位点的化合物（聚乙烯亚胺及四乙烯五胺）组装于PDP结构上,构建了两种氨基功能化超分子聚合物材料PDPP和PDPT。相较于PDP,修饰后超分子聚合物CO₂吸附性能有了极大提升,PDPT在80℃下CO₂吸附量可达27.79cm³/g。动态亚胺组装策略具有制备条件温和、结构功能可控等特性,为开发CO₂高吸附性能材料提供了全新思路。