Impact of the interaction with the positive charge in adsorption of benzene and other organic compounds from aqueous solutions on carbons

We present the results of benzene adsorption at the acidic pH level determined on the series of chemically modified activated carbons and at three temperatures. The influence of carbon surface chemical composition on benzene adsorption is discussed. It is shown that the decrease in the pH level from 7 up to 1.5 increases benzene adsorption and the only exception is carbon modified with gaseous ammonia. Basing on the results of current work and those published previously (for phenol, paracetamol, acetanilide and aniline) and using the results of quantum chemistry calculations (DFT, Gaussian 98) we show, that the value of the energy of interaction with unit positive charge is crucial during the analysis of the influence of pH level on adsorption. Obtained results allow to predict the changes in adsorption of aromatics on carbons with the decrease in the pH level.     

Removal of organic contaminants from aqueous solution by cattle manure compost (CMC) derived activated carbons

The activated carbons (ACs) prepared from cattle manure compost (CMC) with various pore structure and surface chemistry were used to remove phenol and methylene blue (MB) from aqueous solutions. The adsorption equilibrium and kinetics of two organic contaminants onto the ACs were investigated and the schematic models for the adsorptive processes were proposed. The result shows that the removal of functional groups from ACs surface leads to decreasing both rate constants for phenol and MB adsorption. It also causes the decrement of MB adsorption capacity. However, the decrease of surface functional groups was found to result in the increase of phenol adsorption capacity. In our schematic model for adsorptive processes, the presence of acidic functional groups on the surface of carbon is assumed to act as channels for diffusion of adsorbate molecules onto small pores, therefore, promotes the adsorption rate of both phenol and MB. In phenol solution, water molecules firstly adsorb on surface oxygen groups by H-bonding and subsequently form water clusters, which cause partial blockage of the micropores, deduce electrons from the π-electron system of the carbon basal planes, hence, impede or prevent phenol adsorption. On the contrary, in MB solution, the oxygen groups prefer to combine with MB⁺ cations than water molecules, which lead to the increase of MB adsorption capacity.     

Influence of activated carbon surface acidity on adsorption of heavy metal ions and aromatics from aqueous solution

Adsorption of toxic heavy metal ions and aromatic compounds onto activated carbons of various amount of surface C-O complexes were examined to study the optimum surface conditions for adsorption in aqueous phase. Cadmium(II) and zinc(II) were used as heavy metal ions, and phenol and nitrobenzene as aromatic compounds, respectively. Activated carbon was de-ashed followed by oxidation with nitric acid, and then it was stepwise out-gassed in helium flow up to 1273 K to gradually remove C-O complexes introduced by the oxidation. The oxidized activated carbon exhibited superior adsorption for heavy metal ions but poor performance for aromatic compounds. Both heavy metal ions and aromatics can be removed to much extent by the out-gassed activated carbon at 1273 K. Removing C-O complexes, the adsorption mechanisms would be switched from ion exchange to Cπ-cation interaction for the heavy metals adsorption, and from some kind of oxygen-aromatics interaction to π-π dispersion for the aromatics.     

Nanostructured carbons for solid phase extraction

Nanostructured carbons have been obtained by the template method using zeolite NaY and silica gels (SG60, Fluka and ZK, POCh) as structure directing agents. Texture and porous structure of carbons were characterized by TEM, XRD and nitrogen adsorption. Surface chemistry was investigated by the potentiometric titration method. It has been shown that all carbons show developed and uniform porous structure with mean size in the micropore range (1.1 nm) for zeolite derived carbon and in the mesopore range (3.4 and 4.8 nm) for silica gel derived carbons. The BET surface area of silica gel derived carbons is in the range 1230-1280 m²/g whereas zeolite derived carbon possesses very high BET surface area, 3000 m²/g. Potentiometric titration showed that carbons obtained by the template method contain significant amount of acid surface groups (carboxylic, lactone/enol and phenolic) with the total amount 1.1-1.5 mmol/g. To study adsorption-desorption properties of nanostructured carbons towards phenol and chlorophenols the solid phase extraction method was used. High recoveries of chlorophenols were obtained (80-93%) at the breakthrough volumes 1700-3000 mL. The recoveries are much higher than that obtained with commercially available carbon ACC (Supelco).     

Heterogeneity of activated carbons with different surface chemistry in adsorption of phenol from aqueous solutions

The heterogeneity of activated carbons is investigated on the basis of adsorption isotherms of phenol from dilute aqueous solutions at different values of pH in the solution. The original carbon studied was prepared from polyethyleneterephtalate (PET). Its various oxygen surface functionalities were systematically changed by additional nitric acid and heat treatments. The Dubinin-Astakhov adsorption-isotherm equation was used to evaluate the parameters characterizing the adsorption of phenol from dilute water solutions on activated carbon surfaces. Adsorption energy distribution functions were calculated by the INTEG algorithm, based on a regularization method. Analysis of distribution functions for activated carbons provides significant comparative information about their energetic heterogeneity. Moreover, a comparison of the resulting energies obtained from the distributions can be made with enthalpic data.     

Carbon dioxide-activated carbons from almond tree pruning: Preparation and characterization

Activated carbons were prepared from almond tree pruning by non-catalytic and catalytic gasification with carbon dioxide and their surface characteristics were investigated. In both series a two-stage activation procedure (pyrolysis at 800 °C in nitrogen atmosphere, followed by carbon dioxide activation) was used for the production of activated samples. In non-catalytic gasification, the effect of the temperature (650-800 °C for 1 h) and the reaction time (1-12 h at 650 °C) on the surface characteristics of the prepared samples was investigated. Carbons were characterized by means of nitrogen adsorption isotherms at 77 K. The textural parameters of the carbons present a linear relation with the conversion degree until a value of approximately 40%, when they come independent from both parameters studied. The highest surface area obtained for this series was 840 m² g⁻¹. In the catalytic gasification the effect of the addition of one catalyst (K and Co) and the gasification time (2-4 h) on the surface and porosity development of the carbons was also studied. At the same conditions, Co leads to higher conversion values than K but this last gives a better porosity development.     

Phenol adsorption on surface-functionalized iron oxide nanoparticles: modeling of the kinetics,isotherm, and mechanism

Phenol adsorption from aqueous solution was carried out using uncoated and methyl acrylic acid (MAA)-coated iron oxide nanoparticles (NPs), having size <10 nm, as adsorbents. Batch adsorption studies revealed that the phenol removal efficiency of MAA-coated NPs (950 mg g^?1) is significantly higher than that of uncoated NPs (550 mg g^?1) under neutral to acidic conditions. However, this improvement disappears above pH 9. The adsorption data under optimized conditions (pH 7) were modeled with pseudo-first- and pseudo-second-order kinetics and subjected to Freundlich and Langmuir isotherms. The analysis determined that pseudo-second-order kinetics and the Freundlich model are appropriate for both uncoated and MAA-coated NPs (all R ² > 0.98). X-ray photoelectron spectroscopy analysis of pristine and phenol-adsorbed NPs revealed core-level binding energy and charge for Fe(2s) and O(1s) on the NP surfaces. The calculations suggest that phenol adsorption onto MAA-coated NPs is a charge transfer process, where the adsorbate (phenol) acts as an electron donor and the NP surface (Fe, O) as an electron acceptor. However, a physisorption process appears to be the relevant mechanism for uncoated NPs.     

Study of the energetic heterogeneity of the adsorption of phenol onto activated carbons by TPD under supercritical conditions

The Temperature Programmed Desorption (TPD) technique with liquid and supercritical water was used to study the heterogeneity of the adsorption of phenol onto different activated carbons. The presence of several desorption peaks in the spectra clearly indicated that phenol was adsorbed onto the activated carbon with different interaction energies. Calculation of the desorption activation energies revealed that most of the phenol was physisorbed, although a small part was always chemisorbed. The study of the textural characteristics of the carbons suggests that the width of the micropores governs the thermal desorption of the physisorbed phenol.     

Liquid-phase adsorption and desorption of phenol onto activated carbons with ultrasound

The effect of 48-kHz ultrasound on the adsorption and desorption of phenol from aqueous solutions onto coconut shell-based granular activated carbons was studied at 25 degrees C. Experiments were performed at different carbon particle sizes (1.15, 2.5, 4.0 mm), initial phenol concentrations (1.06-10.6 mol/m3), and ultrasonic powers (46-133 W). Regardless of the absence and presence of ultrasound, the adsorption isotherms were well obeyed by the Langmuir equation. When ultrasound was applied in the whole adsorption process, the adsorption capacity decreased but the Langmuir constant increased with increasing ultrasonic power. According to the analysis of kinetic data by the Elovich equation, it was shown that the initial rate of adsorption was enhanced after sonication and the number of sites available for adsorption was reduced. The effect of ultrasonic intensity on the initial rate and final amount of desorption of phenol from the loaded carbons using 0.1 mol/dm3 of NaOH were also evaluated and compared.     

Water vapor adsorption onto activated carbons prepared from cattle manure compost (CMC)

Activated carbons were prepared from cattle manure compost (CMC) using zinc chloride activation. The structural and surface chemical characteristics of CMC-based activated carbons were determined by N₂ adsorption-desorption and Boehm titration, respectively. The water vapor adsorption properties of the prepared activated carbons with various pore structure and surface nature were examined, and the mechanism of water adsorbed onto activated carbon was also discussed. The results show that the adsorption of water vapor on carbons begins at specific active sites at low relative humidity (RH), followed by micropore filling at medium RH through the formation of pentamer cluster of water molecules in the narrow micropores. The water vapor adsorption capacity of activated carbon is predominantly dependent on its pore volume and surface area. Although capillary condensation is not the mechanism for water adsorption onto activated carbon, water can adsorb on narrow mesopore to some extent.     

Effect of combined activation on the preparation of high porous active carbons from granulated post-consumer polyethyleneterephthalate

Activated carbons were prepared from granulated post-consumer PET by combined activation including heat treatment with sulphuric acid (chemical activation) followed by steam activation. The effect of activation time, temperature, impregnation coefficient in the activation process was studied in order to optimize those reception parameters. One of the most important parameter in combined activation of crushed PET was found to be impregnation coefficient. It was defined that the optimal impregnation coefficient is equal 28%. Activation temperature is another variability which has a significant effect on the pore volume evolution. The increasing of activation temperature enhances the surface area and pore volumes of active carbons. The yield of final product which composes of nearly 15% is the factor limited the activation temperature above 800 °C. Textural characteristics of the samples were carried out by performing N₂ adsorption isotherm at −196 °C. The obtained active carbons were mainly micro- and mesoporous and with BET apparent surface areas of up to 1030 m²/g. The adsorption capacity on methylene blue reaches 1.0 mmol/g, the sorption activity on iodine comes to 77%.     

Investigation of the dissociative adsorption for cyclopropane on the copper surface by density functional theory and quantum chemical molecular dynamics method

The dissociative adsorption of cyclopropane on the copper surface was studied using quantum chemical molecular dynamics method with “Colors-Excite” code and density functional theory by Amsterdam Density Functional program (ADF2000). The excited state of cyclopropane was used as adsorbate to simulate the dissociated adsorption under an irradiation energy of ca. 10 eV. One of the C-C bonds in cyclopropane was broken and the two new bonds between cyclopropane and copper surface were formed. The electrons transferred from the copper atoms to cyclopropane with a value of about 0.2e. The shorter distances between the carbons and surface copper atoms showed the existence of strong interaction. Consistently, the results indicated metallacyclopentane was the most possible intermediate species in dissociative adsorption by ADF2000 and “Colors-Excite” method.     

Heterogeneity of activated carbons in adsorption of phenols from aqueous solutions—Comparison of experimental isotherm data and simulation predictions

Surface heterogeneity of activated carbons is usually characterized by adsorption energy distribution (AED) functions which can be estimated from the experimental adsorption isotherms by inverting integral equation. The experimental data of phenol adsorption from aqueous solution on activated carbons prepared from polyacrylonitrile (PAN) and polyethylene terephthalate (PET) have been taken from literature. AED functions for phenol adsorption, generated by application of regularization method have been verified. The Grand Canonical Monte Carlo (GCMC) simulation technique has been used as verification tool. The definitive stage of verification was comparison of experimental adsorption data and those obtained by utilization GCMC simulations. Necessary information for performing of simulations has been provided by parameters of AED functions calculated by regularization method.     

Analysis of the coexisting pathways for NO and N2O formation in Chernozem using the 15N-tracer SimKIM-Advanced model

The nitrogen (N) cycle consists of a variety of microbial processes. These processes often occur simultaneously in soils, but respond differently to local environmental conditions due to process-specific biochemical restrictions (e.g. oxygen levels). Hence, soil nitrogen cycling (e.g. soil N gas production through nitrification and denitrification) is individually affected through these processes, resulting in the complex and highly dynamic behaviour of total soil N turnover. The development and application of methods that facilitate the quantification of individual contributions of coexisting processes is a fundamental prerequisite for (i) understanding the dynamics of soil N turnover and (ii) implementing these processes in ecosystem models. To explain the unexpected results of the triplet tracer experiment (TTE) of Russow et al. (Role of nitrite and nitric oxide in the processes of nitrification and denitrification in soil: results from ¹⁵N tracer experiments. Soil Biol Biochem. 2009;41:785–795) the existing SimKIM model was extended to the SimKIM-Advanced model through the addition of three separate nitrite subpools associated with ammonia oxidation, oxidation of organic nitrogen (N_org), and denitrification, respectively. For the TTE, individual treatments with ¹⁵N ammonium, ¹⁵N nitrate, and ¹⁵N nitrite were conducted under oxic, hypoxic, and anoxic conditions, respectively, to clarify the role of nitric oxide as a denitrification intermediate during N₂O formation. Using a split nitrite pool, this analysis model explains the observed differences in the ¹⁵N enrichments in nitric oxide (NO) and nitrous oxide (N₂O) which occurred in dependence on different oxygen concentrations. The change from oxic over hypoxic to anoxic conditions only marginally increased the NO and N₂O release rates (1.3-fold). The analysis using the model revealed that, under oxic and hypoxic conditions, N_org-based N₂O production was the dominant pathway, contributing to 90 and 50 % of the total soil N₂O release. Under anoxic conditions, denitrification was the dominant process for soil N₂O release. The relative contribution of N_org to the total soil NO release was small. Ammonia oxidation served as the major pathway of soil NO release under oxic and hypoxic conditions, while denitrification was dominant under anoxic conditions. The model parameters for soil with moderate soil organic matter (SOM) content were not scalable to an additional data set for soil with higher SOM content, indicating a strong influence of SOM content on microbial N turnover. Thus, parameter estimation had to be re-calculated for these conditions, highlighting the necessity of individual soil-dependent parameter estimations.     

p-Chlorophenol adsorption on activated carbons with basic surface properties

The adsorption of p-chlorophenol (PCP) from aqueous solution on activated carbons (ACs) with basic surface properties has been studied. The ACs were prepared by two methods. The first method was based on the modification of a commercial CWZ AC by high temperature treatment in an atmosphere of ammonia, nitrogen and hydrogen. The second approach comprised the carbonization followed by activation of N-enriched polymers and coal tar pitch using CO₂ and steam as activation agent. The resultant ACs were characterized in terms of porous structure, elemental composition and surface chemistry (pH_PZC, acid/base titration, XPS). The adsorption of PCP was carried out from an aqueous solution in static conditions. Equilibrium adsorption isotherm was of L2 type for polymer-based ACs, whereas L3-type isotherm was observed for CWZ ACs series. The Langmuir monolayer adsorption capacity was related to the porous structure and the amount of basic sites. A good correlation was found between the adsorption capacity and the volume of micropores with a width < 1.4 nm for polymer-based ACs. Higher nitrogen content, including that in basic form, did not correspond to the enhanced adsorption of PCP from aqueous solution. The competitive effect of water molecule adsorption on the PCP uptake is discussed.     

On the mechanism of reactive adsorption of dibenzothiophene on organic waste derived carbons

The mechanism of reactive adsorption of dibenzothiophene (DBT) on a series of modified carbons derived from the recycled PET was investigated. The influence of the oxygen functionalities of the adsorbent on the DBT adsorption capacity was explored. The results revealed that adsorption of DBT on activated carbons is governed by two types of contributions: physisorption on the microporous network of the carbons and chemisorption. Introduction of surface acidic groups enhanced the performance of the carbons as a result of their specific interactions with DBT. The nature of the acidic groups is a decisive factor in the selectivity of the reactive adsorption process.     

Electronic structure of ultrathin Cs coatings on a Si(100)2×1 surface

The electronic structure and ionization energy of submonolayer Cs coatings on a Si(100)2×1 surface is investigated by threshold photo-emission spectroscopy. Two surface bands induced by Cs adsorption are observed, and their evolution is studied as a function of coverage. It is found that there are two “adsorption locations” for Cs atoms, where they interact with active dangling bonds at the surface. It has been determined that the Cs/Si(100)2×1 interface is semiconducting all the way down to monolayer coverage. The results show that Cs adsorption is predominantly of a covalent character. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 9, 699–702 (10 May 1997)     

Interpretation of kinetics of iron surface oxidation involving the real structure of single crystal samples

The kinetics of oxidation of iron surface has been studied by AES method. The effects of oxygen diffusion into the lattice defects have been considered in the discussion of the mechanism of the oxygen adsorption. The real sticking coefficient has been determined as a function of oxygen coverage (S=1?θ in the range of 0<θ<0.9). The oxidation of iron surface occurs in two steps. At the first step the dissociative oxygen adsorption occurs for the coverage 0<θ _O<1 and the rate of the oxygen molecule adsorption is limiting. At the second step, in the range of oxygen coverage 1<θ _O<2, the reconstruction of the iron surface occurs with the formation of free adsorption sites. At this step the sticking coefficient of oxygen is almost constant (S≈0.1).     

The influence of the carbon surface chemical composition on Dubinin-Astakhov equation parameters calculated from SF6 adsorption data-grand canonical Monte Carlo simulation

Using grand canonical Monte Carlo simulation we show, for the first time, the influence of the carbon porosity and surface oxidation on the parameters of the Dubinin-Astakhov (DA) adsorption isotherm equation. We conclude that upon carbon surface oxidation, the adsorption decreases for all carbons studied. Moreover, the parameters of the DA model depend on the number of surface oxygen groups. That is why in the case of carbons containing surface polar groups, SF(6) adsorption isotherm data cannot be used for characterization of the porosity.     

Characterisation under static and dynamic conditions of commercial activated carbons for their use in wastewater plants

The use of activated carbon for removing organic contaminants in fixed beds is increasing. This is a dynamic process in which the kinetics plays an important role. The aim of this paper is to get more insight into adsorption of p-nitrophenol (PNP) in activated carbon under equilibrium and dynamic conditions. Five commercial activated carbons were studied. The analysis carried out were PNP adsorption isotherms in aqueous solution at 20 °C, N₂ at 77 K isotherms, FT-IR and PNP adsorption under dynamic conditions. The results indicate that the external porous affinity toward the organic contaminants determines in large extent the adsorbents behaviour under dynamic conditions.