Role of microporosity and surface chemistry in adsorption of 4,6-dimethyldibenzothiophene on polymer-derived activated carbons

Two carbon samples derived from poly(4-styrenesulfonic acid-co-maleic acid) based polymer by carbonization between 700 and 800 °C were oxidized to two different levels of surface acidity. The surfaces of resulting adsorbents were characterized by potentiometric titration, adsorption of nitrogen, FTIR, SEM/EDAX and thermal analysis. The materials were used as adsorbents of 4,6-dimethyldibenzothiophene (4,6-DMDBT) from hexadecane with initial concentration of sulfur between 10-150 ppmw. Although it was found that pores with diameter less than 10 Å govern the amount of 4,6-DMDBT adsorbed, that amount is enhanced when acidic groups are present in the larger pores owing to the contributions of specific interactions. Surface chemistry plays an important role in reactive adsorption and deposition of the products of surface reactions in the pore system.     

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 effect of activated carbon surface moisture on low temperature mercury adsorption

Experiments with elemental mercury (Hg⁰) adsorption by activated carbons were performed using a bench-scale fixed-bed reactor at room temperature (27°C) to determine the role of surface moisture in capturing Hg⁰. A bituminous-coal-based activated carbon (BPL) and an activated carbon fiber (ACN) were tested for Hg⁰ adsorption capacity. About 75-85% reduction in Hg⁰ adsorption was observed when both carbon samples’ moisture (∼2 wt.% as received) was removed by heating at 110°C prior to the Hg⁰ adsorption experiments. These observations strongly suggest that the moisture contained in activated carbons plays a critical role in retaining Hg⁰ under these conditions. The common effect of moisture on Hg⁰ adsorption was observed for both carbons, despite extreme differences in their ash contents. Temperature programmed desorption (TPD) experiments performed on the two carbons after adsorption indicated that chemisorption of Hg⁰ is a dominant process over physisorption for the moisture-containing samples. The nature of the mercury bonding on carbon surface was examined by X-ray absorption fine structure (XAFS) spectroscopy. XAFS results provide evidence that mercury bonding on the carbon surface was associated with oxygen. The results of this study suggest that surface oxygen complexes provide the active sites for mercury bonding. The adsorbed H₂O is closely associated with surface oxygen complexes and the removal of the H₂O from the carbon surface by low-temperature heat treatment reduces the number of active sites that can chemically bond Hg⁰ or eliminates the reactive surface conditions that favor Hg⁰ adsorption.     

The adsorption properties of surface modified activated carbon fibers for hydrogen storages

In this study, activated carbon fibers (ACFs) with high surface area and pore volume have been modified by Ni doping and fluorination. The surface modified ACFs were characterized by BET surface area, SEM/EDS, XRD, and Raman spectroscopy. The changes in pore structure and surface properties of these modified ACFs were correlated with hydrogen storage capabilities. After fluorination treatment, although the micropore volume of ACF was decreased, amounts of hydrogen storage were found to increase. Additionally, micropore volume on ACFs was found to be unchanged with Ni doping, hydrogen storage capacities were considerably increased due to the effect of catalytic activation of nickel. Though fluorination of ACFs increases hydrogen affinity, the effect of catalytic activation of nickel is more prominent, and thus led to better hydrogen storage. Hence, it was concluded that hydrogen storage capacity was related to micropore volumes, Pore size distribution (PSD) and surface properties of ACFs as well as specific surface areas.     

活性炭表面含氧官能团对水中卤乙酸吸附去除的影响

为了改善极性、亲水性卤乙酸(HAAs)分子在非极性、疏水性活性炭上的吸附性能,利用N₂等温吸附实验、X射线光电子能谱实验（XPS）、HAAs等温吸附实验等方法,对几种不同产地的活性炭孔隙结构、表面元素形态结构组成,以及HAAs吸附性能进行了研究,考察了活性炭孔结构及含氧官能团对HAAs吸附性能的影响.活性炭表面含氧官能团对HAAs的吸附性能影响显著,当活性炭表面含氧官能团组成较小时,其HAAs吸附能力较强.     

Characterization and adsorption properties of polymer-based microporous carbons with different surface chemistry

Polymers are promising activated carbon precursors due to their high percentage of carbon and also due to their abundance in a relatively pure state from waste recovery. Microporous activated carbons were prepared from poly(ethyleneterephthalate) (APETW, APETOX) and polyacrylonitrile (APAN). Their surface behaviour was characterized under dry and wet conditions by X-ray photoelectron spectroscopy (XPS), pH, pH_PZC and Boehm titration. The oxygen content of the nitrogen-free APETW and APETOX (S_BET = 1440 and 1509 m²/g) is 4.3 and 10.0 at.%, respectively. APAN (356 m²/g) contains 5.4 at.% oxygen and 5.3 at.% nitrogen. The ratios of the surface density of the titrated groups are approximately 20:28:65 in APETW, APETOX and APAN, respectively. The last has the most basic character. The larger oxygen content of APETOX yields greater affinity towards water, as does the presence of nitrogen functionalities in APAN. The higher the concentration of the functional groups, the higher is the water uptake at low relative humidity.

The greatest formaldehyde uptake per unit surface area was found in APAN, which is decorated with both nitrogen and oxygen functional surface groups. Due to the competitive adsorption of formaldehyde and water, increasing oxygen concentration in the APETW sample changed the kinetics of sorption but did not affect the formaldehyde uptake at saturation.     

Effect of chemical activation of an activated carbon using zinc chloride on elemental mercury adsorption

Hg⁰ adsorption experiments with different kinds of activated carbons (ACs) were conducted in nitrogen environment to study the effects of ACs with different surface characteristics on adsorption. Three kinds of ACs prepared by steam activation did not adsorb elemental mercury (Hg⁰) in nitrogen environment, while another kind of AC prepared by chemical activation using zinc chloride (ZnCl₂) showed significant Hg⁰ adsorption capability in the same experimental conditions because Hg⁰ was oxidized by the oxidative elements on the surface of AC. ACs without oxidative elements did not adsorb Hg⁰ through physical adsorption in nitrogen environment. It was therefore concluded that Hg⁰ adsorption by AC was a chemical adsorption process.     

Simulation of mercury emission control by activated carbon under confined-bed operations

Mercury emissions from coal-fired power plants have been a great environmental and regulatory concern due to the toxic nature of mercury and the significant amount of emissions from these plants. An effective method for controlling mercury emission is to employ activated carbon to adsorb mercury from the combustion flue gas. In this study, an activated carbon mercury sorption model was applied to simulate a confined-bed mercury emission control process. Model simulations were performed to generate dynamic mercury concentration profiles and the corresponding profiles of mercury uptake by activated carbon at various bed locations under various process conditions. The simulation parameters included flue gas flow rate, inlet mercury concentration, and adsorption bed temperature. The study has demonstrated the applicability of the model for simulating the process and provided insights into the mercury control process especially the effects of flue gas flow rate, inlet mercury concentration, and activated carbon bed temperature on the process. Such information is critically needed in the design and operation of a mercury emission control process involving activated carbon adsorption.     

In vitro adsorption study of fluoxetine in activated carbons and activated carbon fibres

We study the in vitro adsorption of fluoxetine hydrochloride by different adsorbents in simulated gastric and intestinal fluid, pH 1.2 and 7.5, respectively. The tested materials were two commercial activated carbons, carbomix and maxsorb MSC30, one activated carbon fibre produced in our laboratory and also three MCM-41 samples, also produced by us. Selected samples were modified by liquid phase oxidation and thermal treatment in order to change the surface chemistry without significant modifications to the porous characteristics. The fluoxetine adsorption follows the Langmuir model. The calculated Q₀ values range from 54 to 1112 mg/g. A different adsorption mechanism was found for the adsorption of fluoxetine in activated carbon fibres and activated carbons. In the first case the most relevant factors are the molecular sieving effect and the dispersive interactions whereas in the activated carbons the mechanism seams to be based on the electrostatic interactions between the fluoxetine molecules and the charged carbon surface. Despite the different behaviours most of the materials tested have potential for treating potential fluoxetine intoxications.     

Electrochemical enhancement of adsorption capacity of activated carbon fibers and their surface physicochemical characterizations

The adsorption of activated carbon fibers (ACFs) and their surface characteristics were investigated before and after electrochemical polarization. The adsorption kinetics of m-cresol showed the dependence on polarized potential, and the adsorption rate constant increased by 77.1%, from 6.38 × 10⁻³ min⁻¹ at open-circuit (OC) to 1.13 × 10⁻² min⁻¹ at polarization of 600 mV. The adsorption isotherms at different potentials were in good agreement with Langmuir isotherm model, and the maximum adsorption capacity increased from 2.28 mmol g⁻¹ at OC to 3.67 mmol g⁻¹ at polarized potential of 600 mV. These indicated that electrochemical polarization could effectively improve the adsorption rate and capacity of ACFs. The surface characteristics of ACFs before and after electrochemical polarization were evaluated by N₂ adsorption-desorption isotherms, scanning electron microscope (SEM), zeta potential and Fourier transform infrared spectroscopy (FTIR). The results showed that the BET specific surface area and pore size increased as the potential rose. However, the surface chemical properties of ACFs hardly changed under electrochemical polarization of less than 600 mV. This study was beneficial to understand the mechanism of electrochemically enhanced adsorption.     

Catalytic properties of activated carbon surface in the process of adsorption/oxidation of methyl mercaptan

Activated carbons of different origins were used as adsorbents of methyl mercaptan (MM). Before the MM breakthrough capacity tests were carried out, the surface of carbons was characterized from the point of view of its chemistry (Boehm titration) and porosity (adsorption of nitrogen at its boiling point). The results showed that the ability of carbon to adsorb methyl mercaptan depends strongly on its surface chemistry, particularly on the presence of basic oxygen-containing groups and ash content. Catalytic effect of one metal, iron, was studied in more details. It was found that introduction of iron enhances the removal capacity significantly as a result of electron transfer reaction in which thiolate ion is oxidized to dimethyl disulfide (DMDS). This reaction likely involves the reduction of iron sites, which are regenerated after further re-exposure to oxygen. DMDS as a main reaction product is strongly adsorbed in small pores. Water is required for the formation of DMDS since it facilitates the dissociation of MM. That dissociation occurs in water film when the pH of the local system is greater than the apparent pK_a of MM in the confined pore space.     

Adsorption of sulphur dioxide onto activated carbon prepared from oil-palm shells with and without pre-impregnation

Adsorption of sulphur dioxide (SO₂), a common gaseous pollutant, on oil-palm-shell activated carbon in a fixed bed was studied in this paper. Oil-palm shell is an abundant agricultural solid waste in tropical countries like Malaysia and Thailand. The effects of fixed-bed length, SO₂ gas superficial velocity, adsorbent particle size and internal pore structure on fixed-bed performance were investigated. Some characteristic parameters such as the breakthrough time, τ_0.05, exhaustion time, τ_0.95, length of mass transfer zone, L_MTZ, adsorptive capacity, W, and adsorption rate constant, K, were derived from the breakthrough curves. Tests of SO₂ adsorption onto activated carbons prepared from oil-palm shells pre-impregnated with potassium hydroxide (KOH) and phosphoric acid (H₃PO₄) of different concentrations were also carried out. It was found that the fixed-bed performance was not only dependent on the operating conditions and the textural properties of the adsorbent but was also influenced by the surface chemistry of the adsorbent, which was related to the type and concentration of the impregnating agent. In general, the quality of oil-palm-shell activated carbon prepared by CO₂ activation is comparable to that of a commercial product, and the samples prepared from oil-palm shell with KOH pre-impregnation are more suitable for the removal of SO₂ gas.     

Nitrogen and hydrogen adsorption of activated carbon fibers modified by fluorination

In this study, activated carbon fibers (ACFs) were surface modified with fluorine and mixed oxygen and fluorine gas to investigate the relationship between changes in surface properties by nitrogen and hydrogen adsorption capacity. The changes in surface properties of modified activated carbon fibers were investigated using X-ray photoelectron spectroscopy (XPS) and compared before and after surface treatment. The specific surface area and pore structures were characterized by the nitrogen adsorption isotherm at liquid nitrogen temperature. Hydrogen adsorption isotherms were obtained at 77 K and 1 bar by a volumetric method. The hydrogen adsorption capacity of fluorinated activated carbon fibers was the smallest of all samples. However, the bulk density in this sample was largest. This result could be explained by virial coefficients. The interaction of hydrogen-surface carbon increased with fluorination as the first virial coefficient. Also, the best fit adsorption model was found to explain the adsorption mechanism using a nonlinear curve fit. According to the goodness-of-fit, the Langmuir–Freundlich isotherm model was in good agreement with experimental data from this study.     

Hydrophobisation of active carbon surface and effect on the adsorption of water

A technique of surface hydrophobisation has been applied to two microporous carbonaceous adsorbents. A granular active carbon and an activated carbon fibre, both formerly chemically treated in order they preferentially present hydroxyl surface functions, were modified by action of vinyltrimethoxysilane (vtmos) in liquid phase. The resulting samples were characterised using sorption of nitrogen, FTIR, XPS and ²⁹Si MAS-NMR spectroscopy, and elemental analysis. Their stability and heat treatment have also been investigated through thermal analysis.The efficiency of the hydrophobisation treatment was evaluated by static adsorption of water vapour and vapours of chlorinated volatile organic compounds (VOCs): dichloromethane and trichloroethylene. Grafting of the vtmos and development of a “coating” of polysiloxane onto the adsorbent induced a modification of the carbon surface but also a partial filling of the porosity. These modifications accounted for a decrease of both the amounts of water and VOC adsorbed by the hydrophobised materials. However, water uptakes were found to be much lower than those of the VOCs, evidencing an enhanced selectivity of the hydrophobised adsorbents toward VOCs.     

Powdered activated carbon and carbon paste electrodes: comparison of electrochemical behaviour

Commercial activated carbon (Norit R3ex), de-mineralised with conc. HF and HCl, was oxidised (conc. HNO₃) and heat-treated at various temperatures (180, 300 and 420 °C). The physicochemical properties of the samples obtained were characterised by selective neutralisation and pH-metric titration of surface functional groups (acid–base properties), thermogravimetry (thermal stability—TG), FTIR spectroscopy (chemical structure) and low-temperature nitrogen adsorption (BET surface area). Thermal treatment of the carbon materials caused the surface functional groups to decompose; in consequence, the chemical properties of the carbon surfaces changed. Cyclic voltammetric studies were carried out on all samples using a powdered activated carbon electrode (PACE) and a carbon paste electrode (CPE), as were electrochemical measurements in aqueous electrolyte solutions (0.1 M HNO₃ or NaNO₃) in the presence of Cu²⁺ ions acting as a depolariser. The shapes of the cyclic voltammograms varied according to the form of the electrodes (powder or paste) and to the changes in the surface chemical structure of the carbons. The electrochemical behaviour of the carbons depended on the presence of oxygen-containing surface functional groups. The peak potentials and their charge for the redox reactions of copper ions depended on their interaction with the carbon surface.     

Effect of porous structure and surface functionality on the mercury capacity of a fly ash carbon and its activated sample

The effect of porous structure and surface functionality on the mercury capacity of a fly ash carbon and its activated sample has been investigated. The samples were tested for mercury adsorption using a fixed‐bed with a simulated flue gas. The activated fly ash carbon sample has lower mercury capacity than its precursor fly ash carbon (0.23 vs. 1.85 mg/g), although its surface area is around 15 times larger, 863 vs. 53 m²/g. It was found that oxygen functionality and the presence of halogen species on the surface of fly ash carbons may promote mercury adsorption, while the surface area does not seem to have a significant effect on their mercury capacity.     

Hydrogen adsorption in different carbon nanostructures

Hydrogen adsorption in different carbonaceous materials with optimized structure was investigated at room temperature and 77 K. Activated carbon, amorphous carbon nanotubes, SWCNTs and porous carbon samples all show the same adsorption properties. The fast kinetics and complete reversibility of the process indicate that the interaction between hydrogen molecules and the carbon nanostructure is due to physisorption. At 77 K the adsorption isotherm of all samples can be explained with the Langmuir model, while at room temperature the storage capacity is a linear function of the pressure. The surface area and pore size of the carbon materials were characterized by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. A linear relation between hydrogen uptake and specific surface area (SSA) is obtained for all samples independent of the nature of the carbon material. The best material with a SSA of 2560 m²/g shows a storage capacity of 4.5 wt% at 77 K.     

Effects of carbon surface chemistry and solution pH on the adsorption of binary aromatic solutes

Adsorption of p-cresol, nitrobenzene and p-nitrophenol on treated and untreated carbons is investigated systematically. The effects of carbon surface chemistry and solution pH are studied and discussed. All adsorption experiments were carried out in pH-controlled solutions to examine the adsorption properties of the adsorption systems where the solutes are in molecular as well as ionic forms. Using the homogeneous Langmuir equation, the single solute parameters are determined. These parameters are then used to predict the binary solute adsorption isotherms and gain further insights into the adsorption process.     

Elemental mercury vapor capture by powdered activated carbon in a fluidized bed reactor

A bubbling fluidized bed of inert material was used to increase the activated carbon residence time in the reaction zone and to improve its performance for mercury vapor capture. Elemental mercury capture experiments were conducted at 100 °C in a purposely designed 65 mm ID lab-scale pyrex reactor, that could be operated both in the fluidized bed and in the entrained bed configurations. Commercial powdered activated carbon was pneumatically injected in the reactor and mercury concentration at the outlet was monitored continuously. Experiments were carried out at different inert particle sizes, bed masses, fluidization velocities and carbon feed rates. Experimental results showed that the presence of a bubbling fluidized bed led to an increase of the mercury capture efficiency and, in turn, of the activated carbon utilization. This was explained by the enhanced activated carbon loading and gas-solid contact time that establishes in the reaction zone, because of the large surface area available for activated carbon adhesion/deposition in the fluidized bed. Transient mercury concentration profiles at the bed outlet during the runs were used to discriminate between the controlling phenomena in the process. Experimental data have been analyzed in the light of a phenomenological framework that takes into account the presence of both free and adhered carbon in the reactor as well as mercury saturation of the adsorbent.     

Effects of thermal treatment of activated carbon on the electrochemical behaviour in supercapacitors

This paper studies the electrochemical behaviour of activated carbons with different oxygen content and investigates the contribution of pseudocapacitance to the global behaviour of the samples. A mesophase-derived activated carbon was further heat treated to 600 or 1000 °C in nitrogen. The changes in texture and surface chemistry induced by the thermal treatment were deeply studied. The electrochemical behaviour of the samples was studied in two- and three-electrode cells. The contribution of pseudocapacitance was evaluated by cyclic voltammetry and by the differences of specific capacitance obtained from galvanostatic tests performed in acidic (H₂SO₄) and basic (KOH) media. The presence of an extra capacitance due to redox reactions has been proved both in acidic and basic media for the samples with high oxygen content, although its contribution in basic media is significantly lower. The results obtained clearly indicate that the oxygen responsible for CO-evolution participates in redox reactions, whereas the oxygen responsible for the CO₂-evolution is of minor importance.