Studies on pore structures and surface functional groups of pitch-based activated carbon fibers

The present study concerns the physical activation and chemical oxidation of pitch-based activated carbon fibers (ACFs) as ways to improve the adsorption properties. The surface oxides of the ACFs studied were determined by Boehm's titration and the pore structures were studied by the BET method with N(2)/77 K adsorption. Also, the adsorption properties of the ACFs were investigated with chromium ion adsorption by different adsorption models. As a result, it was observed that carboxyl groups were largely created after nitric acid treatment on ACFs. The affinity for chromium ions increases with increasing specific surface area, micropore volume, and surface functionalities of ACFs as the activation time increases.     

Influence of anodic treatment on heavy metal ion removal by activated carbon fibers

In this work, the effect of electrochemical oxidation treatment on activated carbon fibers (ACFs) was studied in the context of Cr(VI), Cu(II), and Ni(II) adsorption behavior. Ten weight percent phosphoric acid (A-ACFs) and ammonia (B-ACFs) were used for acidic and basic electrolytes, respectively. Surface properties of ACFs were determined by X-ray photoelectron spectroscopy (XPS). The specific surface area and the pore structure were evaluated from nitrogen adsorption data at 77 K. As a result, the electrochemical oxidation treatment led to an increase in the amount of oxygen-containing functional groups. Also, the adsorption capacity of the electrochemically oxidized ACFs was improved in the order B-ACFs > A-ACFs > untreated-ACFs, in spite of a decrease in specific surface area which resulted from pore blocking by functional groups and pore destruction by acidic electrolyte. It was clearly found that the heavy metal ions were largely influenced by the functional groups on the ACF surfaces.     

Ammonia removal of activated carbon fibers produced by oxyfluorination

In this study, activated carbon fibers (ACFs) were produced by an oxyfluorination treatment to enhance the capacity of ammonia gas removal. The introduction of polar groups, such as CF, CO, and COOH, on the ACFs was confirmed by a XPS analysis, and N2/77 K adsorption isotherm characteristics including specific surface area and total and micropore volumes were studied by the BET and t-plot methods. The ammonia-removal efficiency was confirmed by a gas-detecting tube technique. As a result, the specific surface area and micropore volume of ACFs were slightly destroyed as the surface treatment time was increased. However, the oxyfluorinated ACFs led to an increase of fluorine and oxygen-containing polar functional groups in ACF surfaces, resulting in an increase in the ammonia-removal efficiency of the ACFs produced.     

Adsorption behavior of propylamine on activated carbon fiber surfaces as induced by oxygen functional complexes

In this study, the surfaces of activated carbon fibers (ACFs) were modified by nitric acid to introduce surface oxygen complexes and to observe the influence of those complexes on the propylamine adsorption of the ACFs. It was found that the oxygen complexes including carboxylic and phenolic groups were predominantly increased, resulting in the increase of total surface acidity. However, the specific surface areas and the total pore volumes of the modified ACFs were decreased by 5-8% due to the increased blocking (or demolition) of micropores in the presence of newly introduced complexes. Despite the decrease of textural properties, it was found that the amount of propylamine adsorbed by the modified ACFs was increased by approximately 17%. From the XPS results, it was observed that propylamine reacted with strong or weak acidic groups, such as COOH or OH, on the ACF surfaces, resulting in the formation of pyrrolic-, pyridonic-, or pyridine-like structures.     

Influence of oxygen plasma treatment on hydrogen chloride removal of activated carbon fibers

The oxygen plasma treatment of activated carbon fibers (ACFs) was carried out to introduce oxygen-containing groups onto carbon surfaces. Surface properties of the ACFs were determined by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). N2/77 K adsorption isotherms were investigated by BET and D-R plot methods to characterize specific surface area, pore volume, and pore size distribution. The efficiency of hydrochloride removal was confirmed by two kinds of methods; one is detecting tubes (range: 1-40 ppm), and the other is a gas chromatography technique. As experimental results, the hydrochloride removal efficiency of the ACFs was increased with the number of plasma treatment times up to around 300%, resulting from newly formed oxygen-containing functional groups (especially phenolic and carboxylic) on carbon surfaces, in the decreased specific surface areas or pore volumes. These results indicate that the plasma treatment leads to the increase of hydrochloride removal due to the improvement of surface functional groups containing oxygen on the carbon surfaces.     

Adsorption of ammonia and water on functionalized edge-rich carbon nanofibers

The preparation, characterization and ammonia and water adsorption properties of edge-rich carbon nanofibers (CNFs) were studied, including platelet CNFs (PCNFs) and cup-stacked CNFs (CSCNFs). Since PCNFs and CSCNFs have many chemically active exposed edges, functionalization by oxidizing the edges was carried out by ozone stream and by nitric acid. Transmission electron microscopy, N₂ adsorption isotherms and temperature-programmed desorption analysis showed that the nitric acid treatment partly destroyed the graphite structure of the PCNFs and created acid functional groups and micropores, whereas the ozone treatment created functional groups without damaging the structure. Ammonia adsorption isotherms clarified that NH₃ adsorption on PCNFs and CSCNFs occurred mainly on oxygen-containing groups, whereas the adsorption on activated carbon fibers (ACFs) occurred on both oxygen-containing groups and the carbon surface without the functional groups, and the CSCNFs showed larger amounts of adsorbed ammonia compared to the PCNFs. Especially at a relatively low pressure range (<0.2 atm), the PCNFs/CSCNFs/ACFs showed the same ammonia adsorption mechanism; that is, the one-to-one interaction between oxygen atoms in the functional groups and hydrogen atoms in ammonia molecules. In addition, the adsorption on the ACFs appeared to occur mainly by interaction with the carbon surface at relatively high pressure (0.3–1.0 atm). Our experimental results and previous findings suggest that NH₃ adsorption on PCNFs is due mainly to NH…O hydrogen bonding between oxygen-containing groups and ammonia rather than to chemical bonding.     

Pore structure and surface properties of chemically modified activated carbons for adsorption mechanism and rate of Cr(VI)

Effects of hydrochloric acid and sodium hydroxide treatments of activated carbons (ACs) on chromium(VI) reduction were studied. The surface properties were determined by pH, acid-base values, FT-IR, and X-ray photoelectron spectrometer (XPS). And the porous structure of the activated carbons was characterized by adsorption of N(2)/77 K. The Cr(VI) adsorption experiments were carried out to analyze the influence of porous texture and surface properties changed by the chemical surface treatments of ACs on adsorption rate with carbon-solution contact time. From the experimental results, it was observed that the extent of adsorption and reduction processes depends on both microporous structure and functional groups. And the adsorption of Cr(VI) ion was more effective in the case of acidic treatment on activated carbons, resulting from the increases of acid value (or acidic functional group) of activated carbon surfaces. However, basic treatment on activated carbons was not significantly effective on the adsorption of Cr(VI) ion, probably due to the effects of the decrease of specific surface area and basic Cr(VI) in nature.     

Influence of copper content on NO removal of the activated carbon fibers produced by electroplating

In this study, the activated carbon fibers (ACFs) on which copper metal was deposited by electroplating were used to remove nitric oxide (NO). N(2)/77 K adsorption isotherm characteristics, including the specific surface area and micropore volume, were investigated by BET and T-plot methods. NO removal efficiency was confirmed by gas chromatographic technique. From the experimental results, the copper content supported on ACFs led to an increase in the NO conversion, in spite of the decrease of the specific surface area or the micropore volume of ACFs. Consequently, the presence of Cu on ACFs played an important role in improving the NO reduction into O(2) and N(2), which was mainly attributed to the catalytic reactions of Cz-NO-Cu.     

Formaldehyde removal by Rayon-based activated carbon fibers modified by <Emphasis Type="Italic">P</Emphasis>-aminobenzoic acid

We impregnated Rayon-based activated carbon fibers (ACFs) by p-aminobenzoic acid (PABA) and systematically investigated their porous structure, surface chemistry, and formaldehyde removal behavior. Using standard nitrogen adsorption analysis, we found that the specific surface area, the micropore volume, and the total pore volume decreased with increasing concentration of PABA. Through elemental analysis and X-ray photoelectron spectroscopy, it was found that some nitrogen-containing functional groups presented on the surface of modified Rayon ACFs. The modified Rayon-based ACFs showed much higher adsorption capacity and longer breakthrough time for formaldehyde than did as-prepared Rayon-based ACF. We proposed that the improvement of formaldehyde removal by modified ACFs was attributed to the combined effects of physisorption contributed by pore structures and chemisorption contributed by the N-containing functional groups, whereas there was only physisorption between the as-prepared ACF and formaldehyde molecules.     

乙炔法合成醋酸乙烯催化剂载体表面羧基与羰基作用机理的研究

比较了硝酸、硫酸、过氧乙酸改性对载体比表面积、孔结构、pH值以及载体表面基团的影响. 研究了过氧乙酸(PAA)改性条件对催化剂活性的影响. 改性提高了活性炭表面羧基和羰基的含量, 由在最佳PAA改性条件下制备的乙炔法合成醋酸乙烯催化剂生产能力比未经过氧乙酸改性活性炭制备的催化剂提高了14.58%. 得到了过氧乙酸改性后活性炭表面羧基和羰基总量(m)和合成醋酸乙烯催化剂生产能力(P)之间的关系为P＝1.83＋2.26×10－3×e3.17m, 并讨论了催化剂表面羧基与羰基提高催化剂活性的机理.     

Highly active catalyst for vinyl acetate synthesis by modified activated carbon

A new zinc acetate catalyst which was prepared from modified activated carbon exhibited extreme activity towards the synthesis of vinyl acetate.The activated carbon was modified by nitric acid,vitriol and peroxyacetic acid(PAA).The effect on specific area, structure,pH and surface acidity groups of carriers by modification was discussed.Amount of carbonyl and carboxyl groups in activated carbon was increased by peroxyacetic acid treatment.The productivity of the new catalyst was 14.58%higher than that of...     

Characterization and metal sorptive properties of oxidized active carbon

A commercial activated carbon Chemviron F 400 has been oxidized using nitric acid in order to introduce a variety of acidic surface functional groups. Both unoxidized and oxidized carbon samples were characterized using nitrogen porosimetry, elemental analysis, pH titration, Boehm's titration, and electrophoretic mobility measurements. Results show that oxidation treatment reduced surface area and pore volume. However, the carbon surface acquires an acidic character with carboxylic groups being the dominant surface functional groups. The modified sample displays cation-exchange properties over a wide range of pH values and exhibits polyfunctional nature. Both carbon samples were challenged for the removal of transition metals such as copper(II), nickel(II), cobalt(II), zinc(II), and manganese(II). The affinity series Mn2+Zn2+ has been found to coincide with the general stability sequence of metal complexes (the Irving-Williams series). The higher preference displayed by carbons toward copper(II) is a consequence of the fact that copper(II) often forms distorted and more stable octahedral complexes.     

介孔炭表面性质对吸附去除低浓度氨性能的影响

室内环境中低浓度氨污染普遍存在,影响人的身体健康,而消除这些低浓度的氨相对困难。本文报道了一种适用于低浓度氨吸附去除的介孔炭材料,其性能明显优于经硝酸处理的活性炭材料。该介孔炭采用磷酸铝为硬模板制备,炭表面存在大量含氧官能团,研究显示炭表面羧基和内酯基在吸附氨过程中发挥着重要作用,它们作为酸性中心与氨发生化学作用,可以有效地捕获空气中低浓度的氨污染物。     

Adsorption of organic matter at mineral/water interfaces. IV. Adsorption of humic substances at boehmite/water interfaces and impact on boehmite dissolution

The adsorption of Suwannee River fulvic acid (SRFA) and Pahokee peat humic acid (PPHA) at the boehmite (gamma-AlOOH)/water interface and the impact of SRFA on boehmite dissolution have been examined over a wide range of solution pH conditions (pH 2-12), SRFA surface coverages (Gamma(SRFA), total SRFA binding site concentration normalized by the boehmite surface area) of 0.0-5.33 micromol m(-2), and PPHA surface coverages (Gamma(PPHA), PPHA binding site concentration normalized by boehmite surface area) of 0.0-4.0 micromol m(-2), using macroscopic adsorption and in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. At relatively high SRFA surface coverages (Gamma(SRFA) = 5.33 micromol m(-2)), in situ ATR-FTIR spectral features of adsorbed SRFA are very similar to those measured for SRFA in solution at approximately 1-3 pH units higher. At sub-monolayer surface coverages (Gamma(SRFA) = 1.20 and 2.20 micromol m(-2)), several new peaks and enhancements of the intensities of a number of existing peaks are observed. The latter spectral changes arise from several nonorganic extrinsic species (i.e., adsorbed carbonate and water, for alkaline solution conditions), partially protonated SRFA carboxyl functional groups (near-neutral pH conditions), and small quantities of inner-spherically adsorbed SRFA carboxyl groups and/or Al(III)-SRFA complexes (for acidic conditions). The spectra of PPHA adsorbed at boehmite/water interfaces also showed changes generally consistent with our observations for SRFA sorbed on boehmite. These observations confirm that SRFA and PPHA are predominantly adsorbed at the boehmite/water interface in an outer-sphere fashion, with minor inner-sphere adsorption complexes being formed only under quite acidic conditions. They also suggest that the positively charged boehmite/water interface stabilizes SRFA and PPHA carboxyl functional groups against protonation at lower pH. Measurements of the concentration of dissolved Al(III) ions in the absence and presence of SRFA showed that the boehmite dissolution process is clearly inhibited by the adsorption of SRFA, which is consistent with previous observations that outer-spherically adsorbed organic anions inhibit Al-(oxyhydr)oxide dissolution.     

Adsorption of Basic Dyes Using Walnut Shell-based Biochar Produced by Hydrothermal Carbonization

Hydrothermal carbon(HC) was prepared from walnut shells, which are abundant in Northeastern China. The prepared HC was used as a precursor to produce nitric acid modified carbon(MC). The hydrothermal carbonization included dehydration and decarboxylation processes wherein the hemicellulose was completely decomposed and the cellulose was partly decomposed, with some oxygen-containing functional groups being produced. The aromati-city, specific surface area and pore content of the HC increased, but its polarity decreased. With 6 mol/L nitric acid and a modification time of 15 min, the specific surface area and pore content decreased, but the proportion of oxygen-containing functional groups on the surface increased significantly, thereby improving the dye adsorption performance. The adsorption of methylene blue and malachite green was best described by the pseudo-second-order kinetic and Langmuir isotherm models. The adsorption capacity of MC was determined to be much larger than that of HC.     

Synthesis of activated carbon foams with high specific surface area using polyurethane elastomer templates for effective removal of methylene blue

Carbon foams have gained significant attention due to their tuneable properties that enable a wide range of applications including catalysis, energy storage and wastewater treatment. Novel synthesis pathways enable novel applications via yielding complex, hierarchical material structure. In this work, activated carbon foams (ACFs) were produced from waste polyurethane elastomer templates using different synthesis pathways, including a novel one-step method. Uniquely, the produced foams exhibited complex structure and contained carbon microspheres. The ACFs were synthesized by impregnating the elastomers in an acidified sucrose solution followed by direct activation using CO₂ at 1000 ℃. Different pyrolysis and activation conditions were investigated. The ACFs were characterized by a high specific surface area (S_BET) of 2172 m²/g and an enhanced pore volume of 1.08 cm³/g. Computer tomography and morphological studies revealed an inhomogeneous porous structure and the presence of numerous carbon spheres of varying sizes embedded in the porous network of the three-dimensional carbon foam. X-ray diffraction (XRD) and Raman spectroscopy indicated that the obtained carbon foam was amorphous and of turbostratic structure. Moreover, the activation process enhanced the surface of the carbon foam, making it more hydrophilic via altering pore size distribution and introducing oxygen functional groups. In equilibrium, the adsorption of methylene blue on ACF followed the Langmuir isotherm model with a maximum adsorption capacity of 592 mg/g. Based on these results, the produced ACFs have potential applications as adsorbents, catalyst support and electrode material in energy storage systems.     

活性炭的表面化学改性及其对有机硫化物的吸附性能的研究

活性炭； 表面化学改性； 有机硫化物； 吸附性     

Acid/Base-treated activated carbons: characterization of functional groups and metal adsorptive properties

Surface modification of activated carbons by various physicochemical methods directs an attractive approach for improvement of heavy metal uptake from aqueous solutions. Activated carbons were modified with HCl and HNO3 optionally followed by NaOH. The effects of surface modifications on the properties of the carbons were studied by the specific surface area, carbon pH, and total acidity capacity as well as by scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The modifications bring about substantial variation in the chemical properties whereas the physical properties remain nearly unchanged. NaOH causes an increase in the content of hydroxyl groups, while the HCl treatment results in an increase in the amount of single-bonded oxygen functional groups such as phenols, ethers, and lactones. The HNO3 modification generates a large number of surface functional groups such as carbonyl, carboxyl, and nitrate groups. The HNO3 modification significantly increases the copper adsorption, while the HCl treatment slightly reduces the copper uptake. Most of the copper ions are adsorbed rapidly in the first 2 h; the adsorption equilibrium is established in around 8 h. An intraparticle diffusion model successfully describes the kinetics of copper adsorption onto the carbons.     

NO removal of Ni-electroplated activated carbon fibers

In this study, activated carbon fibers (ACFs) were treated by a Ni-electroplating technique in order to remove nitric oxide (NO). The surface properties of the ACFs were investigated by XPS measurement. N2/77 K adsorption isotherm characteristics were determined by the BET equation. Also, NO-removal efficiency was confirmed by gas chromatography. For experimental results, Ni2p was introduced on ACFs during the Ni-electroplating technique. The nickel deposited on ACFs appeared to increase the NO removal despite the decrease in the BET specific surface areas and micropore volumes compared to nontreated ACFs. Consequently, it was found that NO conversion of ACFs was significantly improved due to the catalytic reaction of nickel deposited on ACFs.     

Application of modified multiwall carbon nanotubes as a sorbent for zirconium (IV) adsorption from aqueous solution

Modified multiwall carbon nanotubes (MWCNTs) by nitric acid solution were used to investigate the adsorption behavior of zirconium from aqueous solution. Pristine and oxidized MWCNTs were characterized using nitrogen adsorption/desorption isotherm, Boehm’s titration method, thermogravimetry analysis, transmission electron microscopy and Fourier transform infrared spectroscopy. The results showed that the surface properties of MWCNTs such as specific surface area, total pore volume, functional groups and the total number of acidic and basic sites were improved after oxidation. These improvements are responsible for their hydrophobic properties and consequently an easy dispersion in water and suitable active sites for more adsorption of zirconium. The adsorption of Zr(IV) as a function of initial concentration of zirconium, contact time, MWCNTs dosage, HCl and HNO₃ concentration and also ionic strength was investigated using a batch technique under ambient conditions. The experimental results indicated that sorption of Zr(IV) was strongly influenced by zirconium concentrations, oxidized MWCNTs content and acid pH values. The calculated correlation coefficient of the linear regressions values showed that Langmuir model fits the adsorption equilibrium data better than the Freundlich model. Kinetic data of sorption indicated that equilibrium was achieved within 60 min and the adsorption process can be described by the pseudo second-order reaction rate model. Based on the experimental results, surface complexation is the major mechanism for adsorption of Zr(IV) onto MWCNTs. Also, Study on the desorption process of zirconium showed that the complete recovery can be obtained using nitric or hydrochloric acids of 4 M.