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.     

Peanut Shell Activated Carbon： Characterization,Surface Modification and Adsorption of Pb^2＋ from Aqueous Solution

Metal ion contamination of drinking water and waste water, especially with heavy metal ion such as lead, is a serious and ongoing problem. In this work, activated carbon prepared from peanut shell （PAC） was used for the removal of Pb^2＋ from aqueous solution. The impacts of the Pb25 adsorption capacities of the acid-modified carbons oxidized with HNO3 were also investigated. The surface functional groups of PAC were confirmed by Fourier transform infrared （FTIR） spectroscopy, X-ray photoelectron spectroscopy （XPS）, Boehm titration. The textural properties （surface area, total pore volume） were evaluated from the nitrogen adsorption isotherm at 77 K. The experimental results presented indicated that the adsorption data fitted better with the Langmuir adsorption model. A comparative study with a commercial granular activated carbon （GAC） showed that PAC was 10.3 times more efficient compared to GAC based on Langmuir maximum adsorption capacity. Further analysis results by the Langmuir equation showed that HNO3 [20% （by mass）] modified PAC has larger adsorption capacity of Pb^2＋ from aqueous solution （as much as 35.5 mg·g^-1）. The adsorption capacity enhancement ascribed to pore widening, increased cation-exchange capacity by oxygen groups, and the promoted hydrophilicity of the carbon surface.     

Importance of activated carbon's oxygen surface functional groups on elemental mercury adsorption

The effect of varying physical and chemical properties of activated carbons on adsorption of elemental mercury (Hg⁰) was studied by treating two activated carbons to modify their surface functional groups and pore structures. Heat treatment (1200 K) in nitrogen (N₂), air oxidation (693 K), and nitric acid (6N HNO₃) treatment of two activated carbons (BPL, WPL) were conducted to vary their surface oxygen functional groups. Adsorption experiments of Hg⁰ by the activated carbons were conducted using a fixed-bed reactor at a temperature of 398 K and under N₂ atmosphere. The pore structures of the samples were characterized by N₂ and carbon dioxide (CO₂) adsorption. Temperature-programmed desorption (TPD) and base-acid titration experiments were conducted to determine the chemical characteristics of the carbon samples. Characterization of the physical and chemical properties of activated carbons in relation to their Hg⁰ adsorption capacity provides important mechanistic information on Hg⁰ adsorption. Results suggest that oxygen surface complexes, possibly lactone and carbonyl groups, are the active sites for Hg⁰ capture. The carbons that have a lower carbon monoxide (CO)/CO₂ ratio and a low phenol group concentration tend to have a higher Hg⁰ adsorption capacity, suggesting that phenol groups may inhibit Hg⁰ adsorption. The high Hg⁰ adsorption capacity of a carbon sample is also found to be associated with a low ratio of the phenol/carbonyl groups. A possible Hg⁰ adsorption mechanism, which is likely to involve an electron transfer process during Hg⁰ adsorption in which the carbon surfaces may act as an electrode for Hg⁰ oxidation, is also discussed.     

The Characterization of the Micropore Structures of Some Activated Carbons of Plant Origin by N2 and CO2 Adsorptions

Abstract

In this study, active carbons prepared from almond and hazelnut shells under various experimental conditions were investigated. Merck-2514 and Merck-2184 active carbons were used for comparison. N₂ (77 K) gas and CO₂ (273 and 195 K) gas adsorptions were determined as comparison criteria. Regarding the specific surface area and micropore volume results obtained from these adsorption data, it is concluded that N₂ (77 K) adsorption by itself is inadequate in the characterization of active carbons which are low-sized microporous dominated. In addition, it is concluded that it would be useful to investigate CO₂ (195 and 273 K) adsorption. The iodine and methylene blue tests at 298 K were also applied for the characterization of the carbon adsorbents mentioned. From these data it was seen that the iodine test can be applied as a total porosity indicator and that the methylene blue test can be used as a developed microporosity indicator. These results indicate that the best adsorbents were those prepared from hazelnut shells. Depending on the preparation conditions, the physically activated carbon has an activation time up to 4 hours and has adsorption properties on the level of Merck commercial carbons.     

Surface modification and adsorption of eucalyptus wood-based activated carbons: Effects of oxidation treatment, carbon porous structure and activation method

The incorporation of oxygen functional groups onto the surface of eucalyptus activated carbon and its surface chemistry were investigated as a function of oxidation conditions, carbon porous properties and carbon preparation method. Under all treatment conditions of increasing time, temperature and oxidant concentration, liquid oxidation with HNO₃, H₂O₂ and (NH₄)₂S₂O₈ and air oxidation led to the increase of acidic group concentration, with carboxylic acid showing the largest percentage increase and air oxidation at the maximum allowable temperature of 350 °C produced the maximum content of both carboxylic acid and total acidic group. Nitric acid oxidation of chemically activated carbon produced higher total acidic content but a lower amount of carboxylic acid compared to the oxidized carbon from physical activation. The increased contents of acidic groups on oxidized carbons greatly enhanced the adsorption capacity of water vapor and heavy metal ions.     

Usefulness of CO2 adsorption at 273 K for the characterization of porous carbons

Characterization of microporous solids (activated carbons and carbon molecular sieves) has been carried out by N₂ (subatmospheric pressures) and CO₂ adsorption (at subatmospheric and high pressures) at 77 and 273 K, respectively. Because the relative fugacity range covered by our CO₂ study is similar to the relative pressure range covered with N₂, a suitable comparison of both adsorptives can be made. The results of such comparison show that both adsorptives give the same micropore size distribution (MPSD) for open porosity activated carbons. This observation confirms that the adsorption mechanism of both adsorptives is similar. However, carbon molecular sieves, with very narrow microporosity, cannot be characterized by N₂ at 77 K, due to the existence of diffusional problems. This is also extensive to many other carbon materials, such as carbon fibers and activated carbons with low degree of activation. As a consequence, in this type of samples, N₂ adsorption at 77 K is useless to determine neither the micropore volumes of the narrowest porosity nor their micropore size distributions (MPSD). In this work, the usefulness of CO₂ for the characterization of carbon molecular sieves and activated carbons with different activation degrees is demonstrated. In addition, examples of applications that cannot be explained from N₂ adsorption but yes by CO₂ are presented. As a result, we strongly encourage the use of CO₂ (i.e. at 273 K) as a complement to N₂ adsorption at 77 K.     

Characterization and application of activated carbon produced by H3PO4 and water vapor activation

Activated carbons have been prepared from woody biomass birch by using various activation procedures: a) treatment with phosphoric acid and pyrolysis at 600 °C in inert atmosphere, b) the same as in (a) followed by steam activation at the same temperature and c) treatment with phosphoric acid and direct pyrolysis in a stream of water vapor at 700 °C. The surface area and the porosity of the activated carbons were strongly dependent on the treatment after impregnation with H₃PO₄ (pyrolysis in inert atmosphere, steam pyrolysis or combination of both).Activated carbon, prepared by impregnation with phosphoric acid followed by steam pyrolysis (steam activation) had highly developed porous structure and the largest surface area among all prepared carbons (iodine number 1280 mg/g and BET surface area 1360 m²/g). The adsorption capacity of this sample for Hg(II) from aqueous solution was studied in varying treatment conditions: contact time, metal ion concentration and pH. The adsorption followed Langmuir isotherms and the adsorption capacity for Hg(II) at 293 K was 160 mg/g.     

Synthesis of polyaniline/mesoporous carbon nanocomposites and their application for CO<Subscript>2</Subscript> sorption

Ordered mesoporous carbons (OMC), were synthesized by nanocasting using ordered mesoporous silica as hard templates. Ordered mesoporous carbons CMK-1 and CMK-3 were prepared from MCM-48 and SBA-15 materials with pore diameters of 3.4 nm and 4.2 nm, respectively. Mesoporous carbons can be effectively modified for CO₂ adsorption with amine functional groups due to their high affinity for CO₂. Polyaniline (PANI)/mesoporous carbon nanocomposites were synthesized from in-situ polymerization by dissolving OMC in aniline monomer. The polymerization of aniline molecules inside the mesochannels of mesoporous carbons has been performed by ammonium persulfate. The nanocomposition, morphology, and structure of the nanocomposite were investigated by nitrogen adsorption-desorption isotherms, Fourier Transform Infrared (FT–IR), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and thermo gravimetric analysis (TGA). CO₂ uptake capacity of the mesoporous carbon materials was obtained by a gravimetric adsorption apparatus for the pressure range from 1 to 5 bar and in the temperature range of 298 to 348 K. CMK-3/PANI exhibited higher CO₂ capture capacity than CMK-1/PANI owing to its larger pore size that accommodates more amine groups inside the pore structure, and the mesoporosity also can facilitate dispersion of PANI molecules inside the pore channels. Moreover, the mechanism of CO₂ adsorption involving amine groups is investigated. The results show that at elevated temperature, PANI/mesoporous carbon nanocomposites have a negligible CO₂ adsorption capacity due to weak chemical interactions with the carbon nanocomposite surface.     

Role of microporosity and surface functionality of activated carbon in methylene blue dye removal from water

Activated carbons have been prepared from jute stick by both chemical and physical activation methods using zinc chloride and steam, respectively. They were characterized by evaluating surface area, iodine number, pore size distribution, and concentration of surface functional groups. The chemically activated carbon largely featured micropore structure, while the physically activated carbon mainly featured macropore structure. The specific surface area of chemically and physically activated carbons was 2,325 and 723 m ² /g, while the iodine number was 2,105 and 815mg/g, respectively. The concentration of surface functional groups was determined by Boehm titration method, which suggested that different types of surface functional groups are randomly distributed on chemical activated carbons, while it is limited for physical activated carbon. The microporosity along with surface functional groups provided a unique property to chemically activated carbon to adsorb Methylene Blue dye to a large extent. The adsorption of dye was also affected by the adsorption parameters such as adsorption time, temperature and pH. Comparatively, higher temperature and pH significantly facilitated dye adsorption on chemically activated carbon.     

Influence of HNO3 oxidation on the structure and adsorptive properties of corncob-based activated carbon

An investigation of the impact of strong oxidation with HNO₃ on the porosity and adsorption characteristics of char and activated carbons, derived from corncobs, is presented. Texture parameters, as obtained from N₂ adsorption at 77 K, showed a considerable decrease in surface area of the activated carbons with enhanced pore widening. The extent of porosity modification was found to depend on the scheme of activation of the precursor, simple carbonization, steam pyrolysis, steam gasification of the char, or chemical activation with H₃PO₄. Surface-chemical changes were detected by FTIR spectroscopy, where absorption bands assigned to carboxyl, carboxylate, carbonyl, and phenolic groups were observed. A SEM study demonstrated the erosive effect of HNO₃, detected by the presence of disintegration of the carbon grains, with the porous structure probably containing very large macropores. As a consequence of the oxidation process, elemental analysis showed high contents of O, H and N, and TG confirmed that the weight loss distribution in the thermogram becomes slower at higher temperatures. The removal of phenol decreased as a result of the formation of oxygen functionalities. Mono-nitrophenols were adsorbed in smaller amounts than phenol, and p-nitrophenol showed a relatively higher uptake than the other two mono-nitrophenols, whereas the uptake of Methylene Blue was improved. Removal of Pb²⁺ from aqueous non-buffered solution was considerably enhanced by chemical oxidation, which may be related to pore widening, increased cation-exchange capacity by oxygen groups, and the promoted hydrophilicity of the carbon surface.     

Removal of mercury from natural gas by a new activated adsorbent from olive stones

This study was devoted to the valorization of a plant waste (olive stones): that is widely available in Mediterranean countries in order to remove mercury from natural gas. The raw material from olive stones was prepared by pyrolysis, chemical activation with phosphoric acid, and physical activation under steam. Two olive stone‐based granular activated carbons were prepared: one with the virgin stones, while the other was impregnated with sulphur. After treatment, the adsorbents obtained were characterized by determining the iodine number, the methylene blue index, and by estimating the porous properties by N₂ adsorption at 77 K. Thermogravimetric analysis and infrared spectroscopy analysis were carried out to determine the functional groups before and after mercury adsorption. An experimental study of vapour‐phase mercury adsorption by the activated carbons (virgin and sulphur‐impregnated) and a comparison with a commercial material (HGR) were performed. The comparison, made by analyzing the adsorption in a continuous mode, showed that the proportion of sulphur and the porosity were important for the removal of mercury. In the conditions used, the mercury adsorption on the ACs studied follows a physisorption mechanism. The results showed that granular activated carbon‐based olive stones (sulphur‐impregnated) are very efficient to remove mercury (with 2864 μg/g) and also less expensive than commercial activated carbon due to their local availability.     

Lead(II) adsorption onto the graphene layer of carbonaceous materials in aqueous solution

Lead(II) adsorption from an aqueous solution onto a graphene layer (Cπ electrons) was investigated using activated carbon and charcoal. The carbonaceous materials were treated by several steps to prepare ash free and acidic oxygen free graphite surface by washing with HCl and H₂F₂ solution followed by out gassing at 1273 K. Changes in Pb(II) adsorption capacity were checked at each step to maximize the area of the graphene layer. As received activated carbon and charcoal and their HNO₃ oxidized counterparts were also used for the adsorption experiments for comparison with the ash free and the acidic oxygen free carbons. Boehm titration and Langmuir isotherms were used to evaluate the Pb(II) adsorption onto the adsorbents. The experimental results indicate that an acidic oxygen free graphene layer exhibits a basic character caused by Cπ electrons. When only a small amount of acidic oxygen groups was present, the Pb(II) adsorption strength onto the graphene layer (Cπ electrons) significantly diminished, and the Pb(II) adsorption sites were switched from the graphene layer to carboxylic and lactonic groups on the carbons in the results.     

Enhanced mercury adsorption in activated carbons from biomass materials and waste tires

Agricultural residues and waste tires constitute an important source of precursors for activated carbon production. Activated carbons offer a potential tool for mercury emissions control. In this work, pine and oak wood, olive seed and tire wastes have been used for the preparation of activated carbons, in order to be examined for their mercury removal capacity. In the case of activated carbons produced from pine/oak woods and tire wastes, a two stage physical activation procedure was applied. Activated carbons derived from olive seeds were prepared by chemical activation using KOH. Pore structure of the samples was characterized by N₂ and CO₂ adsorption, while TPD-IR experiments were performed in order to determine surface oxygen groups. Hg° adsorption experiments were realized in a bench-scale adsorption unit consisting of a fixed-bed reactor. The influence of activation technique and conditions on the resulted activated carbon properties was examined. The effects of pore structure and surface chemistry of activated carbons were also investigated. Activated carbons produced from olive seeds with chemical activation possessed the highest BET surface area with well-developed micropore structure, and the highest Hg° adsorptive capacity. Oxygen surface functional groups (mainly lactones) seem to be involved in Hg° adsorption mechanism.     

Adsorption of hydrogen sulphide (H2S) by activated carbons derived from oil-palm shell

Adsorption of hydrogen sulphide (H₂S) onto activated carbons derived from oil palm shell, an abundant solid waste from palm oil processing mills, by thermal or chemical activation method was investigated in this paper. Dynamic adsorption in a fixed bed configuration showed that the palm-shell activated carbons prepared by chemical activation (KOH or H₂SO₄ impregnation) performed better than the palm-shell activated carbon by thermal activation and a coconut-shell-based commercial activated carbon. Static equilibrium adsorption studies confirmed this experimental result. An intra-particle Knudsen diffusion model based on a Freundlich isotherm was developed for predicting the amount of H₂S adsorbed. Desorption tests at the same temperature as adsorption (298 K) and at an elevated temperature (473 K) were carried out to confirm the occurrence of chemisorption and oxidation of H₂S on the activated carbon. Surface chemistries of the palm-shell activated carbons were characterized by Fourier transform infrared spectroscopy and Boehm titration. It was found that uptaking H₂S onto the palm-shell activated carbons was due to different mechanisms, e.g. physisorption, chemisorption and/or H₂S oxidation, depending on the activation agent and activation method.     

Activated carbon based selective purification of medical grade NO starting from arc discharge method

Four activated carbons were tested under normal temperature and pressure to selectively adsorb nitrogen dioxide (NO₂) from medical nitric oxide (NO) formed by arc discharge. The samples’ pore structures were characterized by an automatic specific surface area and porosity analyzer based on the Brunauer–Emmett–Teller method, t-plot, and the Barrett–Joyner–Halenda method. Surface chemical properties both before and after adsorption, as well as the resultant nitro-compound (C-NO₂ or nitrate) after adsorption, were analyzed using the classic Boehm titration method and Fourier transform infrared spectroscopy. The selective adsorption amounts of NO₂ and NO were evaluated using specially designed equations. It was found that, with their large surface areas and highly acidic groups, spherical activated carbon from wood and activated carbon fibers had the best selective adsorption of NO₂. It was also shown that the large difference in acid–basic surface groups and the molecular polarity between NO and NO₂ accounted for their adsorption on different functional groups, and that those acidic groups enhanced the selective adsorption of NO₂. The research on regeneration and re-adsorption showed that regeneration had an obvious effect on the adsorption of NO₂, but little effect on NO.     

Catalytic oxidation of Fe(II) by activated carbon in the presence of oxygen.: Effect of the surface oxidation degree on the catalytic activity

The catalytic oxidation of Fe(II) species in aqueous solution by activated carbons with different degrees of surface oxidation is described. The parent activated carbon was oxidized with aqueous solutions of nitric acid or hydrogen peroxide, and submitted to thermal treatment at 373, 523 and 773 K. The activated carbons prepared were characterized by N₂ adsorption and temperature-programmed desorption, and their catalytic behavior was determined by measuring the oxidation rate of Fe(II) to Fe(III) and the generation of hydrogen peroxide. Catalytic activity is a function of the nature of oxygen surface groups generated by oxidation.     

Catalytic oxidation of Fe(II) by activated carbon in the presence of oxygen.: Effect of the surface oxidation degree on the catalytic activity

The catalytic oxidation of Fe(II) species in aqueous solution by activated carbons with different degrees of surface oxidation is described. The parent activated carbon was oxidized with aqueous solutions of nitric acid or hydrogen peroxide, and submitted to thermal treatment at 373, 523 and 773 K. The activated carbons prepared were characterized by N₂ adsorption and temperature-programmed desorption, and their catalytic behavior was determined by measuring the oxidation rate of Fe(II) to Fe(III) and the generation of hydrogen peroxide. Catalytic activity is a function of the nature of oxygen surface groups generated by oxidation.     

活性炭表面改性及吸附极性气体

活性炭的微结构和表面化学特性对其吸附性能产生显著影响。概述了通过调整活性炭孔隙结构。引入化学基团，改变其酸碱度和极性，提高其吸附极性分子能力的方法，介绍了炭表面化学结构，分析了炭微结构，表面基团和吸附质性质对吸附过程的影响。对近年来活性炭表面的改性在吸附SO2和VOCs的实验研究进行了讨论。     

Characterisation of surface oxides on carbon and their influence on dynamic adsorption

The aim of this work is to gain a better fundamental understanding of the nature of surface oxide sites present on carbon surfaces, and their role in the adsorption process. A number of model carbon substrates with different degrees of surface oxidation and similar textural properties were prepared using a wide range of solution and gaseous phase oxidation techniques. Some of the carbons were characterised using established techniques including flow microcalorimetry, thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The results showed that both carboxylic acid (-CO₂H) and ether/hydroxyl (C-O) surface oxygen complexes were introduced to all of these carbons as a result of the oxidation processes. The number, strength and thermal stability of the surface groups formed were dependent on the nature of the base material and the oxidation conditions employed. The dynamic adsorption performance of the carbons against hexane, under humid conditions, was found to be mainly determined by the quantity of acidic surface functional groups. However, the location, strength of interaction and availability of the surface oxygen complexes to the adsorbate molecules, are also thought to affect the breakthrough characteristics of the carbons used in this work.