Effect of activated carbons modification on porosity, surface structure and phenol adsorption

The primary objective of this work was the examination of modified activated carbons with tailored adsorption capacity properties. Production of activated carbons with desired properties was accomplished by modification of surface functional groups and introduction of acidic/basic properties. Modification of an activated carbon was performed using partial oxygen gasification, nitric acid treatment, urea impregnation followed by pyrolysis and pyrolysis in a urea saturated stream. The surface properties of the produced samples were estimated by the multibasic titration method of Boehm and by the CO/CO2 gas evolution profiles, while pore structure development was measured by the N2 and CO2 gas adsorption isotherms. Oxygen gasification resulted in samples with surface area slightly lower that the raw activated carbon; the introduction of surface functional groups depended upon the severity of the treatment: carbonylic and phenolic type groups were introduced in all partially gasified samples, while low temperatures and short reaction times enhanced the basic character of the carbon. However, nitric acid treatment resulted in the introduction of high nitrogen amounts in the samples, the reduction of surface area and the development of a surface containing carboxylic, lactonic, phenolic and carbonylic groups with negligible HCl neutralization capacity. Treatment of activated carbon by urea supported the formation of basic groups and carbonyls. The presence of surface functional groups affected the adsorption capacity of the produced samples for the removal of specific pollutants such as phenols. Urea treated samples with a basic character and high nitrogen content presented the highest phenol uptake capacity; nitric acid treated carbons and oxygen gasified samples presented an acidic surface functionality and a low phenol adsorption capacity. The beneficial role of nitrogen on phenol adsorption was attributed to adsorbate-adsorbent interactions.     

Effect of the surface chemical groups of activated carbons on their surface adsorptivity to aromatic adsorbates based on π-π interactions

Three activated carbons with different surface chemical groups were used to analyse the influence of these groups on their adsorption capacities towards aromatic-type molecules whose adsorption is based on π-π interactions with surface arene centres. The three activated carbons studied were a low-functionalized carbon (Merck), an oxygen-rich carbon obtained by HNO₃ oxidation of Merck, and a nitrogen-rich carbon also prepared from Merck by mild HNO₃ oxidation followed by treatment with a dicyanodiamide/dimethyl formamide mixture at 300 °C. The nature of the surface chemical groups of the three activated carbons was investigated by both physical and chemical techniques (TPD, XPS, Boehm analysis and pH potentiometric titration). A systematic study of the adsorptions of a series of analogous aromatic adsorbates on the three activated carbons was carried out to study the adsorption mechanisms. In all cases the adsorption mechanism is based on π-π interactions between the aromatic moiety of the adsorbates and the arene centres of the graphite sheets. The differences in the normalized adsorption capacities of the adsorbents for a set of adsorbates indicate that the π-donor or π-withdrawing character of the functional groups have a clear influence on the basicity of the arene centres.     

Adsorption characteristics of N-nitrosodimethylamine from aqueous solution on surface-modified activated carbons

This study investigated the removal of N-nitrosodimethylamine (NDMA) by an adsorption mechanism using commercially available activated carbons and surface-modified activated carbons. The effects of the modification on the properties of the activated carbon were studied by N₂ adsorption/desorption, Diffuse Reflectance Infrared Fourier Transmission (DRIFT) analysis and X-Ray Photoelectron Spectroscopy (XPS). Adsorption experiments revealed that the activated carbons demonstrated a greater capacity for NDMA adsorption capacity than can be achieved using zeolite. The equilibrium data was fitted to the Freundlich equation and it was found that the adsorption capacity was significantly influenced by the micropore size, relative pore volume and surface characteristics. Adsorption experiments were conducted using unmodified and modified activated carbons. The results indicated that the adsorption capacity of NDMA can be significantly improved by heat treatment and doping of TiO₂ particles. This was because the surface treatments yielded more hydrophobic sites and fewer oxygen-containing surface functional groups, and consequently an increased capacity for NDMA adsorption.     

Adsorption of aqueous metal ions on cattle-manure-compost based activated carbons

The objective of this study is to examine the suitability and performance of cattle-manure-compost (CMC) based activated carbons in removing heavy metal ions from aqueous solution. The influence of ZnCl₂ activation ratios and solution pH on the removal of Cu(II) and Pb(II) were studied. Pore texture, available surface functional groups, pH of point zero charge (pH_PZC), thermogravimetric analysis and elemental compositions were obtained to characterize the activated carbons. Batch adsorption technique was used to determine the metal-binding ability of activated carbons. The equilibrium data were characterized using Langmuir, Freundlich and Redlich–Peterson models. It was found that the uptake of aqueous metal ions by activated carbons could be well described by Langmuir equation. It is suggested that the increase of surface area and mesopore ratio as a result of increasing activation ratios favored the removal of Cu(II), while activated carbon rich in acidic groups showed selective adsorption towards Pb(II). The preferable removal of Cu(II) over Pb(II) could be due to the rich nitrogen content as well as the higher mesoporous surface area in the CMC activated carbons. The impregnated CMC activated carbons also showed a better performance for Cu(II) removal at varying solution pH than Filtrasorb 400 (F400), while a similar performance was observed for Pb(II) removal.     

Preparation of polyaniline coated activated carbon and their electrode performance for supercapacitor

Polyaniline coated mesoporous and microporous activated carbons were prepared by chemical oxidation polymerization of aniline adsorbed on activated carbons. BET and mesopore specific surface areas of the obtained activated carbons decreased by coating with polyaniline. The electrode performance of the polyaniline coated activated carbons for supercapacitor was investigated. The electrochemical pseudo-capacitances increased with increasing polyaniline content in activated carbons. The capacitances due to polyaniline in the mesoporous activated carbon are much higher than those in the microporous activated carbon. The uniform coating of polyaniline on mesopores of activated carbon plays an important role in pseudo-capacitance due to polyaniline.     

热处理活性半焦的表面性质和SO2脱除活性

前驱体和表面改性过程都影响着活性半焦脱除SO2的活性.在氮气中、800℃下对原料半焦进行热处理,并在固定床反应器上测试了其脱除SO2的活性.利用酸碱滴定、工业分析和元素分析、X-射线光电子能谱(XPS)、傅立叶转换红外光谱(FTIR)等表征原料半焦和活性半焦表面化学性质.结果表明:石墨碳是原料半焦和活性半焦样品表面的主要碳功能团.表面C=O基团(酮、内酯、羰和醌类中)和吡咯-N分别是原料半焦表面的氧、氮功能团.热处理导致半焦表面含氧基团分解、表面含氧和含氮基团分布改变、表面C=O基团(酮、内酯、羰和醌类中)明显下降;而化学吸附氧和水增加,吡咯-N变成类吡啶结构.醚类和π - π* 离域基团的增加提高了活性半焦表面的碱性.热处理提高了活性半焦脱除SO2的活性.影响SO2脱除活性的表面基团可能是具有碱性性质的醚类、π - π* 离域及含氮基团.     

Ozonation of benzothiazole saturated-activated carbons: influence of carbon chemical surface properties

The combined or sequential use of ozone and activated carbon to treat toxic effluents has increased in recent years. However, little is known about the influence of carbon surface active sites on ozonation of organic adsorbed pollutants. This paper presents experimental results on the effect of metal oxides and oxygenated surface groups on gaseous ozonation of spent activated carbons. Benzothiazole (BT) was selected as a target organic compound in this study due to its environmental concern. Activated carbons with different chemical surface composition were prepared from a Filtrasorb-400 activated carbon. Pre-treatment included: ozonation, demineralisation, and deoxygenation of activated carbon. Ozonation experiments of BT saturated-activated carbons were conducted in a fixed bed reactor loaded with 2 g of carbon samples. The reactor was fed with an O2/O3 gas mixture (2 dm3/min, 5 g O3/h), for a given exposure time, in the range 10-120 min, at 298 K and 1 atm. Results show that extended gaseous ozonation of activated carbon saturated with BT led to the effective destruction of the adsorbate by oxidation reactions. Oxidation of BT adsorbed on activated carbon seemed to occur via both direct reaction with ozone molecules, and by oxygen radical species generated by catalytic ozone decomposition on metallic surface sites.     

Textural and chemical properties of zinc chloride activated carbons prepared from pistachio-nut shells

The effects of activation temperature on the textural and chemical properties of the activated carbons prepared from pistachio-nut shells using zinc chloride activation under both inert nitrogen gas atmosphere and vacuum condition were studied. Relatively low temperature of 400 °C was beneficial for the development of pore structures. Too high an activation temperature would lead to sintering of volatiles and shrinkage of the carbon structure. The microstructures and microcrystallinity of the activated carbons prepared were examined by scanning electron microscope and powder X-ray diffraction techniques, respectively, while Fourier transform infrared spectra determined the changes in the surface functional groups at the various stages of preparation.     

One-pot synthetic method to prepare highly N-doped nanoporous carbons for CO2 adsorption

A one-pot synthetic method was used for the preparation of nanoporous carbon containing nitrogen from polypyrrole (PPY) using NaOH as the activated agent. The activation process was carried out under set conditions (NaOH/PPY = 2 and NaOH/PPY = 4) at different temperatures in 600–900 °C for 2 h. The effect of the activation conditions on the pore structure, surface functional groups and CO₂ adsorption capacities of the prepared N-doped activated carbons was examined. The carbon was analyzed by X-ray photoelectron spectroscopy (XPS), N2/77 K full isotherms, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The CO₂ adsorption capacity of the N-doped activated carbon was measured at 298 K and 1 bar. By dissolving the activation agents, the N-doped activated carbon exhibited high specific surface areas (755–2169 m² g⁻¹) and high pore volumes (0.394–1.591 cm³ g⁻¹). In addition, the N-doped activated carbons contained a high N content at lower activation temperatures (7.05 wt.%). The N-doped activated carbons showed a very high CO₂ adsorption capacity of 177 mg g⁻¹ at 298 K and 1 bar. The CO₂ adsorption capacity was found to be dependent on the microporosity and N contents.     

Preparation of fibrous activated carbons from wood fiber

Short fibrous hollow activated carbons with a high aspect ratio were prepared by carbonization and carbon dioxide activation of softwood and hardwood fibers. The softwood activated carbon consisted mostly of micropores even though the degree of burn-off during the activation became higher. In the case of the hardwood fiber, on the other hand, meso- and macropores as well as micropores were formed and the ratio of these large pores increased with an increasing degree of burn-off. The adsorbed amount of water and toluene vapor on these fibrous activated carbons was compared with that of the commercial activated carbon fibers (ACFs). These fibrous activated carbons showed a high adsorption capacity comparable to that of the ACFs.     

A new method for preparing hydrophilic-activated carbon through ester hydrolysis in an alkaline environment

Hydrophilic-activated carbon was prepared by ester hydrolysis reactions, and was characterized by surface area analysis, Fourier transform infrared spectroscopy, scanning electron microscopy energy dispersive X-ray spectroscopy, and X-ray diffraction. Hydrophilic groups that were introduced on activated carbon surface through ethyl acetate hydrolysis in an alkaline environment were more efficient than those introduced with sodium acetate. During adsorption, the hydrophilic groups on modified activated carbon surface bound with water molecules through H-bonding and increased the adsorption capacity of water vapor. The adsorption isotherms of water vapor were well fitted by the Do model. Water molecules generated larger water clusters around the functional groups at 303 and 313 K. In addition, water desorption from the samples was analyzed by thermogravimetry. Water molecules that were hydrogen-bonded to functional groups exhibited higher thermal stability than those adsorbed in the micropore of activated carbon. Besides, the process of sodium acetate formation on the surface of modified activated carbon was discussed.     

Surface modification of coconut shell based activated carbon for the improvement of hydrophobic VOC removal

In this study, coconut shell based carbons were chemically treated by ammonia, sodium hydroxide, nitric acid, sulphuric acid, and phosphoric acid to determine suitable modification for improving adsorption ability of hydrophobic volatile organic compounds (VOCs) on granular activated carbons (GAC). The saturated adsorption capacities of o-xylene, a hydrophobic volatile organic compound, were measured and adsorption effects of the original and modified activated carbons were compared. Results showed that GAC modified by alkalis had better o-xylene adsorption capacity. Uptake amount was enhanced by 26.5% and reduced by 21.6% after modification by NH₃H₂O and H₂SO₄, respectively. Compared with the original, GAC modified by acid had less adsorption capacity. Both SEM/EDAX and BET were used to identify the structural characteristics of the tested GAC, while IR spectroscopy and Boehm's titration were applied to analysis the surface functional groups. Relationships between physicochemical characteristics of GAC and their adsorption performances demonstrated that o-xylene adsorption capacity was related to surface area, pore volume, and functional groups of the GAC surface. Removing surface oxygen groups, which constitute the source of surface acidity, and reducing hydrophilic carbon surface favors adsorption capacity of hydrophobic VOCs on carbons. The performances of modified GACs were also investigated in the purification of gases containing complex components (o-xylene and steam) in the stream.     

Adsorption, desorption and bioregeneration in the treatment of 2-chlorophenol with activated carbon

This study aims to clarify the effect of activated carbon type on the extent of adsorbability, desorbability, and bioregenerability in the treatment of 2-chlorophenol. Four different activated carbon types; thermally activated and chemically activated powdered carbons (PAC), and their granular countertypes (GAC) with similar physical characteristics were used. Thermally activated carbons adsorbed 2-chlorophenol much better than chemically activated ones. However, adsorption was more reversible in the case of chemically activated ones. The use of powdered and granular activated carbon countertypes resulted in comparable adsorption and desorption characteristics. For each activated carbon type, 2-chlorophenol exhibited higher adsorbability and lower desorbability than phenol. Biodegradation of 2-chlorophenol took place very slowly when it was used as the sole carbon source in acclimated and non-acclimated activated sludges. Bioregeneration occurred only via desorption due to an initial concentration gradient and no further desorption took place due to low biodegradability. Bioregeneration of activated carbon loaded with 2-chlorophenol was not a suitable option when 2-chlorophenol was the only carbon source. It is suggested to remove 2-chlorophenol via adsorption onto activated carbon rather than applying biological treatment. Also in such cases, the use of thermally activated carbons with higher adsorption and lower desorption capacities is recommended rather than chemically activated carbons.     

Preparation of carbon supported platinum catalysts: role of π sites on carbon support surface

The role of the π sites in the adsorption of anionic platinum precursor (PtCl₆²⁻) on the carbon surface was studied. A set of carbon supports was prepared by the oxidative treatments of a commercial carbon black in liquid or thermal treatment in a nitrogen gas flow. The supports obtained had similar physical structure, but were different in their surface chemistry, e.g., the types and the amount of the surface functional groups. The Pt/C catalysts were prepared by the impregnation of the supports with an aqueous solution of hexachloroplatinic acid. N₂ adsorption, acid-base titration, X-ray photoelectron spectrometry (XPS), ICP, and TEM were used to characterize the supports and the catalysts. It was found that the absence of the surface acidic groups led to a higher platinum loading amount on the supports; and platinum loading amount would decrease when the higher H₂PtCl₆ impregnating solution concentration was used. The π sites in the basal planes play a more important role than the surface acidic groups in PtCl₆²⁻ ions adsorption on the carbon surface. Upon impregnation, the delocalized π electrons form coordination bonds with the platinum precursors, and further cause the reduction of Pt(IV) complex to Pt(II) complex, which was strongly chemisorbed on the surface of the supports. PtCl₆²⁻ ions adsorbing at the surface acidic groups would easily desorb during the washing process. However, when the impregnating solution was used at a higher concentration, a large amount of H₃O⁺ was firstly adsorbed in the π sites, leading to a decrease of the amount of strong PtCl₆²⁻ ions adsorption on the supports.     

High adsorption capacity NaOH-activated carbon for dye removal from aqueous solution

In this study, the surface coverage ratio (Sc/Sp) and monolayer cover adsorption amount per unit surface area (qmon/Sp) were employed to investigate the adsorption isotherm equilibrium of the adsorption of dyes (AB74, BB1 and MB) on NaOH-activated carbons (FWNa2, FWNa3 and FWNa4); the adsorption rate of the Elovich equation (1/b) and the ratio of 1min adsorption amount of adsorbate to the monolayer cover amount of adsorbate (q1/qmon) were employed to investigate adsorption kinetics. The qmon/Sp of NaOH-activated carbons was better than that of KOH-activated carbons prepared from the same raw material (fir wood). The Sc/Sp values of the adsorption of all adsorbates on adsorbent FWNa3 in this study were found to be higher than those in related literature. Parameters 1/b and q1 of the adsorption of dyes on activated carbons in this study were higher than those on KOH-activated carbons; the q1/qmon value of FWNa3 was the highest. The pore structure and the TPD measurement of the surface oxide groups were employed to explain the superior adsorption performance of FWNa3. A high surface activated carbon (FWNa3) with excellent adsorption performance on dyes with relation to adsorption isotherm equilibrium and kinetics was obtained in this study. Several adsorption data processing methods were employed to describe the adsorption performance.     

冷等离子处理对炭纤维表面及复合材料性能的影响

空气气氛下对T300炭纤维进行不同时间的等离子处理。对处理后的炭纤维表面进行了扫描电镜(SEM)观察,对表面活性基团进行了红外光谱测试。结果显示,随着处理时间的增长,纤维表面沟槽长度加长,程度加深,表面粗糙度增大。纤维表面并没有明显的活性基团产生。将处理后的炭纤维制备成单向增强板,测得试样的弯曲模量达到109GPa;弯曲强度在处理时间为16min之内增加较快达到1241.5MPa,超过16min之后开始下降。等离子处理前后的力学性能相比,弯曲模量提高了50.97%,弯曲强度提高了46.89%。实验结果显示,等离子处理16min能够得到比较好的界面结合性能和力学性能。     

预炭化对KOH活化石油焦的结构及电容性能的影响

以不同温度炭化的石油焦为原料、KOH为活化剂制备电化学电容器用炭电极材料. 采用XRD、TEM和N₂吸附法对前驱体及活化产物的结构进行了表征, 并考察了样品的电化学性能. 结果表明: 通过调整前驱体的预炭化温度, 可实现对石油焦基活性炭的微晶结构和孔结构的调控, 分别制得无晶体特性的高比表面积活性炭和由大量类石墨微晶构成的低比表面积活性炭. 低表面积活性炭依靠充电过程中电解质离子嵌入类石墨微晶层间而实现能量存储, 具有比高比面积活性炭高10倍的面积比电容和更大的体积比电容.     

Carbon spheres/activated carbon composite materials with high Cr(VI) adsorption capacity prepared by a hydrothermal method

Glucose and commercial activated carbon (AC) were used as starting materials to hydrothermally synthesize carbon spheres on the surface of AC, producing new carbon sphere–AC hybrid carbon materials. It was found that micrometer-sized carbon spheres, rich in oxygen-containing functional groups, can be effectively anchored to, and well-dispersed on, the surface and at the entrance to the macropores of AC. As the glucose concentration increased, the size and dispersion of carbon spheres changed, the porosity of the AC decreased, the number of oxygen-containing functional groups increased, and COH gradually became the dominant functional group. The carbon composites that were obtained exhibited a remarkably enhanced adsorption capacity for Cr(VI) per unit mass and per unit surface area. The highest adsorption capacity per unit mass achieved was 0.4834 mmol g^?1, about 4 times that of unmodified AC. The abundant surface oxygen-containing functional groups and relatively well-developed pore structure were the main causes of the high specific adsorption capacity of the carbon sphere/AC composites.     

活性炭硝酸表面改性对催化剂分散度的影响

无论是活性炭作为催化剂载体还是在活性炭本身的催化制备过程中,催化剂在活性炭或活性炭前体上的高度分散都是至关重要的。通过X射线能谱(EDX)和扫描电子显微镜(SEM)技术直接观察、研究了活性炭表面经硝酸氧化改性对硝酸铜在煤基活性炭中分散度的影响。此外,将经硝酸表面改性的商品活性炭采用浸渍法负载上硝酸铜催化剂,再经水蒸气二次活化制备了一种新的活性炭。结果表明,硝酸处理造成活性炭吸附性能的下降,并且硝酸处理的强度越高,活性炭吸附性能的下降程度越大。然而,对硝酸处理的活性炭经简单的水洗可恢复其吸附性能。研究结果还表明,活性炭经硝酸氧化提高了炭表面含氧官能团的数量,使催化剂在活性炭的内外表面均能均匀分布,提高了催化剂的分散度和抗烧结能力。活性炭经硝酸改性后再负载硝酸铜进行二次活化制备高性能活性炭,可使硝酸铜的催化性能得到进一步的提升。     

Physical and chemical properties and adsorption type of activated carbon prepared from plum kernels by NaOH activation

Activated carbon was prepared from plum kernels by NaOH activation at six different NaOH/char ratios. The physical properties including the BET surface area, the total pore volume, the micropore ratio, the pore diameter, the burn-off, and the scanning electron microscope (SEM) observation as well as the chemical properties, namely elemental analysis and temperature programmed desorption (TPD), were measured. The results revealed a two-stage activation process: stage 1 activated carbons were obtained at NaOH/char ratios of 0-1, surface pyrolysis being the main reaction; stage 2 activated carbons were obtained at NaOH/char ratios of 2-4, etching and swelling being the main reactions. The physical properties of stage 2 activated carbons were similar, and specific area was from 1478 to 1887m(2)g(-1). The results of reaction mechanism of NaOH activation revealed that it was apparently because of the loss ratio of elements C, H, and O in the activated carbon, and the variations in the surface functional groups and the physical properties. The adsorption of the above activated carbons on phenol and three kinds of dyes (MB, BB1, and AB74) were used for an isotherm equilibrium adsorption study. The data fitted the Langmuir isotherm equation. Various kinds of adsorbents showed different adsorption types; separation factor (R(L)) was used to determine the level of favorability of the adsorption type. In this work, activated carbons prepared by NaOH activation were evaluated in terms of their physical properties, chemical properties, and adsorption type; and activated carbon PKN2 was found to have most application potential.