Synthetic carbons activated with phosphoric acid III. Carbons prepared in air

Synthetic activated carbons were prepared by phosphoric acid activation of a styrene-divinylbenzene copolymer in an air atmosphere at various temperatures in the 400-900 °C interval. The carbons were characterized by elemental analysis, cation-exchange capacity measurement, infrared spectroscopy, potentiometric titration, copper adsorption from solution and physical adsorption of N₂ at −196 °C and CO₂ at 0 °C. It was shown that, similarly to synthetic phosphoric acid activated carbons obtained in argon, the synthetic carbons activated with phosphoric acid in air possess an acidic character and show considerable cation-exchange properties. The contribution of oxygen-containing surface groups along with phosphorus-containing groups to CEC is higher for carbons obtained in air. Three types of surface groups were identified on carbons prepared at temperatures up to 600 °C, and four types on carbons prepared at higher temperatures. These groups were assigned to ‘super-acidic’ (pK<0), phosphorus-containing (pK=1.1-1.2), carboxylic (pK=4.7-6.0) and phenolic (pK=8.1-9.4) groups. The cation-exchange capacity was at a maximum for the carbon prepared at 800 °C. Copper adsorption by synthetic phosphoric acid activated carbons obtained in air at temperatures lower than 800 °C is higher than for similar carbons obtained in argon. The increase is due to additional formation of oxygen-containing surface groups. Calculated copper binding constants revealed the importance of phosphorus-containing and carboxylic groups for adsorption of copper from aqueous solution. All carbons show a multimodal pore size distribution including simultaneously micropores and mesopores, but the porous texture is not a prime factor in determining the cation-exchange capacities of these carbons. Synthetic phosphoric acid activated carbons show a greater development of porosity when obtained in air as compared to carbons carbonized in argon.     

Solid-state NMR and ESR studies of activated carbons produced from pecan shells

A large number of solid-state NMR and ESR experiments were explored as potential tools to study chemical structure, mobility, and pore volume of activated carbon. We used a model system where pecan shells were activated with phosphoric acid, and carbonized at 450 °C for 4 h with varying amounts of air flow. Through the use of different NMR experiments (e.g., CP-MAS, SPE-MAS, and DD-MAS) several structural parameters were calculated such as mole fraction of bridgehead aromatic carbons, number of carbons per aromatic ring system, and number of phenolic carbons per aromatic ring system. The relaxation time measurements (T₁, T_CH, and ) were indicative of the relative mobility of different structural units. ESR spectra showed the presence of π-type aromatic free radicals in the carbonized samples with a slight shift in g value with increasing oxidation. The combined NMR and ESR data give a consistent picture of the carbon structure and the carbonization process, which is not easily available otherwise. In addition, the ¹H NMR data on adsorbed water are shown to be consistent with the trends in the amount of pore volumes for different samples of activated carbons.     

磷酸、氯化锌活化亚麻屑制备活性炭过程中的行为对比

以亚麻屑为原料,采用磷酸和氯化锌进行了对比活化实验,探讨了浸渍比、活化温度对活性炭的吸附性能、得率和比表面积的影响。结果表明,在浸渍比为300∶1,500℃下活化60 m in,均能得到吸附性能较好的活性炭,其中碘值是氯化锌法高于磷酸法,亚甲基蓝吸附则是磷酸法高于氯化锌法,说明在活化过程中磷酸和氯化锌对活性炭的影响不尽相同,孔隙结构存在差别。     

Acid properties of phosphoric acid activated carbons and their catalytic behavior in ethyl-tert-butyl ether synthesis

Carbon catalysts were prepared by phosphoric acid activation of styrene-divinylbenzene copolymer followed by liquid phase oxidation with nitric acid. Their surface properties were modified by heat treatment at 300-600 °C in an argon atmosphere, and their acid properties were characterized by quasi-equilibrium temperature desorption of ammonia and by acid-base titration. The pore structure was characterized by nitrogen adsorption at −196 °C. Their catalytic activity in the synthesis of ethyl-tert-butyl ether (ETBE) from isobutene and ethanol was investigated. It has been shown that the carbon catalysts are active and selective in ETBE synthesis. The main factor determining the catalytic activity of carbon catalysts is the total number of acid surface sites. A linear correlation between total amount of surface sites and catalytic activity was found.     

Preparation, characterization and Methylene Blue adsorption of phosphoric acid activated carbons from globe artichoke leaves

Activated carbons were prepared by the pyrolysis of artichoke leaves impregnated with phosphoric acid at 500 °C for different impregnation ratios: 100, 200, 300 wt.%. Materials were characterized for their surface chemistry by elemental analysis, “Boehm titrations”, point of zero charge measurements, infrared spectroscopy, as well as for their porous and morphological structure by Scanning Electron Microscopy and nitrogen adsorption at 77 K. The impregnation ratio was found to govern the porous structure of the prepared activated carbons. Low impregnation ratios (~ 100 wt.%) led to essentially microporous and acidic activated carbons whereas high impregnation ratios (> 100 wt.%) gave essentially microporous-mesoporous carbons with specific surface areas as high as 2038 m²·g^− 1, pore volume as large as 2.47 cm³·g^− 1, and a slightly acidic surface. The prepared activated carbons were studied for their adsorption isotherms of Methylene Blue at pH = 3 and pH = 9. The supermicroporous structure of the material produced at 200 wt.% H₃PO₄ ratio was found to be appropriate for an efficient adsorption of this dye controlled by dispersive and electrostatic interactions depending on the amount of oxygen at the surface.     

The characterization of nitrogen-enriched activated carbons by IR, XPS and LSER methods

The aim of this work is to study the efficiency of the nitrogen enrichment by urea of lignites and the induced changes of the adsorptive properties towards volatile organic compounds (VOCs) of the activated carbons derived from these modified precursors. The study is made using infrared and X-ray photoelectrons spectroscopies and the LSER (linear solvation energy relationship) modeling. Four activated lignites derived from the same raw material, original or enriched with nitrogen, are characterized in this way. The effect of the chemical treatment by urea and of the burn-off amount are investigated in term of evolution of the chemistry of the studied materials. The influence of these parameters on the selective behavior of the activated lignites towards two pairs of VOCs is also discussed in terms of molecular interactions using the LSER approach. The results show that the chemical treatment of the raw material is successful, leading to significant enrichment with nitrogen under pyridinic form at the surface of the activated carbons. Moreover, they reveal some selective properties well explained by the LSER analysis and spectroscopic measurements. The selective character of the studied materials is modulated by the duration of the activation step.     

Small and wide angle X-ray studies of impregnated activated carbons

Small angle X-ray scattering (SAXS) and powder X-ray diffraction (XRD) measurements were made on CuO-impregnated activated carbons, prepared with and without an HNO₃ co-impregnant, in order to determine the effect of impregnant loading and HNO₃ content on impregnant distribution. A comprehensive matrix of 30 CuO-impregnated samples with five HNO₃ concentrations and six impregnant loadings was prepared and studied. As a highlight, in Cu-based samples prepared with no HNO₃, relatively small particle size CuO impregnant (approximately 3 nm) was observed at low impregnant loading and additional CuO appeared in large particles (>10 nm diameter) in meso and macropores as the impregnant loading increased. By contrast, when 4 M HNO₃ was present during the impregnation, the largest impregnant particles found were less than 4 nm. Results from SAXS data were shown to be in good agreement with XRD and data obtained from nitrogen gas adsorption isotherms. The combination of SAXS and XRD is shown to be a powerful combination in elucidating the nanostructure of impregnated activated carbons.     

Activated carbons prepared from rice hull by one-step phosphoric acid activation

Activated carbons were prepared from rice hull by one-step phosphoric acid activation in this work. The evolution of pore structure and surface chemistry in the activation temperature range of 170–450 °C was investigated through various characterization techniques. The results showed that the development of porosity (extent of activation) was negligible at activation temperature below 300 °C, and rapid evolution occurred in 300–400 °C. Porous activated carbon with bimodel pore structure (pore < 1 nm and pore > 1 nm) and BET surface area as high as 1295 m²/g was obtained at 450 °C. The ash contents of samples prepared in this study were in the range of 5–21%. The ash contents of carbons prepared in this study initially decreased from 21.03% to 4.89% with the change of temperature from 170 to 300 °C, then increased to 8.72% at 450 °C. Boehm titration results suggested that low activation temperature (300 °C) benefits the formation of acidic surface groups. With the increase of activation temperature from 300 to 350 °C, the concentrations of strong, intermediate and weak acidic surface groups decreased from 2.23, 1.87, and 2.73 to 1.66, 1.32, and 2.16 mmol H⁺/g, respectively. Over 350 °C, the change of these groups were insignificant. FTIR results revealed the existence of carbonyl-containing, phosphorus-containing groups, and groups containing Si–O bond. The relative concentration of carbonyl-containing groups decreases with an increase in activation temperature, while that of phosphorus-containing groups follows the reverse trend. The content of Si–O decreased first, then slowly increased with the increase of activation temperature. Boehm titration and FTIR (Fourier transform infrared spectroscopy) results indicated that the surfaces of these carbons contain both temperature-sensitive and temperature-insensitive groups. The temperature-sensitive part consists mainly of carbonyl-containing groups, such as carboxylic groups, while the temperature-insensitive part is primarily phosphorus-containing groups and groups containing Si–O bond. This study demonstrated that carbon products with relative low ash content and high activation degree can be prepared from rice hull by H₃PO₄ activation at suitable temperature.     

Synthesis and NMR studies of the polymer membranes based on poly(4-vinylbenzylboronic acid) and phosphoric acid

Proton conduction in novel anhydrous membranes based on host polymer, poly(4-vinylbenzylboronic acid), (P4VBBA) and phosphoric acid, (H₃PO₄) as proton solvent was studied. The materials were prepared by the insertion of the proton solvent into P4VBBA at different stoichiometric ratios to get P4VBBA·xH₃PO₄ composite electrolytes. Homopolymer and the composite materials were characterized by FT-IR, ¹¹B MAS NMR and ³¹P MAS NMR. ¹¹B MAS NMR results suggested that acid doping favors or leads to a four-coordinated boron arrangement. ³¹P MAS NMR results illustrated the immobilization of phosphoric acid to the polymer through condensation with boron functional groups (B-O-P and/or B-O-P-O-B). Thermogravimetric analysis (TGA) showed that the condensation of composite materials starts approximately at 140 °C. An exponential weight loss above this temperature was attributed to intermolecular condensation of acidic units forming cross-linked polymer. The insertion of phosphoric acid into the matrix softened the materials shifting T_g to lower temperatures. The temperature dependence of the proton conductivity was modeled with Arrhenius relation. P4VBBA·2H₃PO₄ has a maximum proton conductivity of 0.0013 S/cm at RT and 0.005 S/cm at 80 °C.     

Influence of electrochemical treatment in phosphoric acid on the wettability of carbons

A technique developed by Studebaker and Snow was used to determine the contact angle of water (cosθ_H2O) on porous carbons which were electrochemically treated in phosphoric acid. Electrochemical oxidation resulted in a decrease in cosθ_H2O whereas, electrochemical reduction resulted in an increase in cosθ_H2O. These observations were correlated to the oxygen content of the porous carbon samples.     

Significance of the carbonization of volatile pyrolytic products on the properties of activated carbons from phosphoric acid activation of lignocellulosic material

Two series of activated carbons derived from China fir (Cunninghamia lanceolata) wood impregnated with phosphoric acid were prepared in a cylindrical container that was kept in a closed state covered with a lid (the covered case) or in an open state. The effects of the carbonization of volatile pyrolytic products of starting materials on the properties of activated carbon were investigated in the process of phosphoric acid activation. Elemental analysis and SEM observation showed that both activating in the covered case and increasing the mass of starting material used favored the carbonization of volatile pyrolytic products. An investigation of N₂ adsorption isotherms revealed that the carbonization of volatile pyrolytic products significantly enhanced mesopore development in the final carbons, especially pores with a size range from 2.5 to 30 nm, with little influence on micropores, and therefore produced a large increase in the adsorption capacity to Vitamin B12 (with a molecular size of 2.09 nm). Activated carbons with highly developed mesopores could be obtained in the covered case. The carbonization mechanism of volatiles was discussed and two different carbonization pathways (in solid and gas phases) were proposed during phosphoric acid activation.     

Studies on the structure of activated carbon fibers activated by phosphoric acid

By solid‐state ¹³C‐ and ³¹P‐NMR, XPS, and FTIR, the chemical structure of activated carbon fiber–P (ACF‐P) and its reaction with phosphoric acid were studied. Even when activated at low temperatures, these fibers developed a graphitelike carbon structure with a certain amount of phenol groups as well as acetal (or methylenedioxy) carbon. As expected, the oxygen‐containing groups were greatly reduced at high activation temperatures. Different from the ACF‐W, metaphosphoric acid (or polyphosphates) and a small amount of phosphorus exist on ACF‐P. The original ACF‐P activated at low temperature contained a lot of phosphoric acid, so it had to be washed with water to expose the large surface area. The washing process can be omitted for ACF‐P activated at high temperature because most phosphorus compounds in fiber have volatilized. The ACF‐P activated at lower temperature possessed a large amount of oxygen‐containing surface groups and had enhanced adsorption ability for polar adsorbates. The remaining of metaphosphoric acid enhanced the adsorption of silver ion. The experimental results showed that the peaks of ³¹P‐NMR, P_2p‐XPS, and FTIR at 1620 cm^?1 shifted with the increase of activated temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2253–2261, 2003     

酸改性活性炭对甲苯、甲醇的吸附性能

分别用1 mol·L^-1硝酸、1 mol·L^-1盐酸、1 mol·L^-1硫酸对商业活性炭进行浸渍改性。采用比表面积及孔径分析仪、Boehm滴定、傅里叶转换红外光谱(FTIR)对活性炭的物化性质进行表征。以甲苯、甲醇为吸附质,在283 K下进行了固定床吸附实验。研究表明:酸改性能去除表面碱性基团,显著增加表面酸性含氧官能团的含量;酸改性活性炭的吸附量与其比表面积、总孔容、微孔孔容、表面总酸性官能团呈现出良好的线性关系;Langmuir方程比Freundlich方程更加适合描述甲苯、甲醇在活性炭上的吸附;甲醇在活性炭上为物理吸附,甲苯在活性炭上以物理吸附为主,与表面官能团之间的化学键作用能增强甲苯吸附量;甲苯、甲醇在活性炭上的微孔有效扩散系数的大小顺序为:AC-N>AC-1>AC-S>AC-C;并且甲醇的微孔有效扩散系数大于甲苯。     

磷酸活化炭气凝胶微球的电化学性能研究

以磷酸为活化剂,对炭气凝胶微球在高温下进行活化改性,并用活化产品制作超级电容器的电极。采用扫描电镜、N2物理吸附-脱附等对炭气凝胶微球的形貌结构进行表征,采用循环伏安、恒流充放电、交流阻抗等测定了材料的电化学性能。结果表明,磷酸活化效果温和,不会破坏炭气凝胶微球典型的圆球状外观和三维纳米孔隙结构。经过磷酸活化,炭气凝胶微球的电化学性能得到有效改善,材料的内阻降低,同时比电容提高将近一倍,最高可达184 F/g。     

Surface chemistry of wood‐based phosphoric acid‐activated carbons and its effects on adsorptivity

The surface oxygen content of selected wood‐based phosphoric acid‐activated carbons was quantified using X‐ray photoelectron spectroscopy (XPS) and correlated with the residual bulk phosphate levels of the carbons and their adsorptivity in solution. The adsorption of Al³⁺, Cu²⁺, and para‐chlorophenol, respectively, from water decreased as a function of increasing surface oxygen content of the carbons. When the carbon of lowest surface oxygen content was oxidized with ozone to impart a surface oxygen content comparable to that of a carbon with a much higher phosphate level, adsorption of Al³⁺, Cu²⁺, and para‐chlorophenol from water decreased proportionally. The increase in polarity of the carbon surface was accompanied by a decrease in pH and appeared to be the dominant factor with respect to the adsorption of the target species from water. Copyright © 2005 Society of Chemical Industry     

HEMP-derived activated carbon fibers by chemical activation with phosphoric acid

Activated carbon fibers were prepared by chemical activation of hemp fibers with phosphoric acid at different carbonization temperatures and impregnation ratios. Surface properties of the activated carbons fibers were significantly influenced by the activation temperature and the impregnation ratio. An increase of either of these parameters produced a high development of the porous structure of the fibers. Activated carbon fibers with apparent surface area of 1350 m²/g and mesopore volume of 1.25 cm³/g were obtained at 550 °C with an impregnation ratio of 3. The activated carbon fibers presented a high oxidation resistance, due to the presence of phosphorus compounds on the carbon surface. The oxidation resistance results suggest that C-O-PO₃ and mainly C-PO₃ and C-P groups act as a physical barrier, blocking the active carbon sites for the oxidation reaction.     

On the nature of surface acid sites of chlorinated activated carbons

Two activated carbons containing different amounts of chlorine were obtained by chlorination of an activated carbon prepared from olive stones. Variations in surface physics and chemistry of the samples were studied by N₂ and CO₂ adsorption, mercury porosimetry, TPD, XPS, pH_PZC measurements, and by testing their behaviour as catalysts in the decomposition reaction of isopropanol. Our results indicate that chlorination of activated carbon increases its Lewis acidity but decreases its Brönsted acidity, which can be explained by the resonance effect introduced into the aromatic rings of graphene layers by the chlorine atoms covalently bound to their edges. This resonance effect could also explain the changes observed in the thermal stability of C-Cl and C-O bonds.