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.     

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.     

The impact of carbon surface chemical composition on the adsorption of phenol determined at the real oxic and anoxic conditions

The results of phenol adsorption-desorption isotherms (at 310 K) measured on the series of activated carbons (D43/1, NORIT RO 0.8, D55/2) are presented. The effect of carbon surface chemical composition on phenol adsorption determined at real oxic and anoxic conditions is discussed. To obtain the real anoxic conditions the two station controlled atmosphere chamber with two catalyst heater units (Plas Labs, Lansing, MI, USA) was applied. It is shown that the adsorption under oxic conditions is always larger than that determined for anoxic ones for all studied carbons. The analysis of those differences shows that in the range of micropore filling they decrease with the equilibrium phenol mole fraction in solution. Contrary they increase after micropores being filled. The average differences between the adsorption properties are the linear function of the concentration of surface acidic groups (assigned from the Boehm's method as “carboxylic”) calculated per the apparent BET surface area of studied carbons.     

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.     

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.     

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.     

Adsorption of iodoalkanes on graphite

In this work, we present a study of linear iodoalkanes physisorbed from their bulk liquid and at submonolayer coverages onto a graphite substrate by combining calorimetry, incoherent neutron scattering and synchrotron diffraction techniques. We identify that there is solid monolayer formation for these molecules for alkyl chain lengths of 5–12 carbons at high surface coverages. The monolayer structures of the odd homologues (5, 7, 9 and 11) have been addressed using synchrotron X-ray and neutron scattering at sub-monolayer coverages and indicate that the molecules lie with their carbon backbone parallel to the graphite surface with a Pgb plane group. Evidence for a non-bonded I–I interaction in the monolayers is also discussed.     

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.     

Hydrogen adsorption in microporous alkali-doped carbons (activated carbon and single wall nanotubes)

Adsorption of hydrogen gas was tested in microporous doped carbons: activated carbon (1600 m²/g) and single wall carbon nanotubes (SWNTs). The isotherms of adsorption of LiC₁₈ and KC₂₄ doped microporous activated carbons were determined in the range [0–30 bar] at room temperature and 77 K. The chemisorption ratio observed at room temperature increases with increasing the alkali/carbon rate. The isotherm profiles of doped activated carbon at 77 K show no clear enhancement of the sorption ratio compared to the raw activated carbon.The adsorption sites of potassium doped SWNTs with closed end were determined by neutron diffraction experiment using deuterium gas. The K-doped SWNTs were found only slightly intercalated by K ions so that empty cavities are preserved in between the tubes. At room temperature, the chemisorption of deuterium was not observed in doped SWNTs bundles, but only in the KC₈ graphite intercalation compound impurities. At low temperature, the isotherms analysis and neutron diffraction experiments have shown that D₂ molecules are physisorbed in the free interstitial voids in between the tubes within the bundles.     

Reaction of oxygen with gallium surfaces

The adsorption of oxygen molecules on evaporated gallium films has been studied by UV photoelectron spectroscopy between 10 and 300 K. In addition to the oxygen levels, the chemical shift of the Ga 3d core level has been investigated using monochromatized light from a He discharge lamp at ?ω = 40.8 eV. Four different states of oxygen have been found depending on temperature. At 10 K the molecules of the first layer are physisorbed onto which several additional layers can be condensed. The rigid relaxation shifts to smaller binding energies are 2.7 eV for physisorbed and 1.3 eV for condensed oxygen. During warming-up the oxygen reacts with the gallium surface. Between 70 and 130 K an oxygen species develops which is interpreted as chemisorbed molecular oxygen. This is concluded from the valence band UP spectra, the chemical shift of the Ga 3d level, and the work function change. At 300 K oxygen is dissociatively bound and the bulk oxide grows.     

Preparation of microporous activated carbon and its electrochemical performance for electric double layer capacitor

Microporous activated carbons were prepared by microwave heating petroleum coke with potassium hydroxide as activation agent. Microporous activated carbons were characterized by infrared spectroscopy, X-ray diffraction and nitrogen adsorption/desorption isotherms. Electrochemical properties of an electric double layer capacitor using microporous activated carbon as electrode materials were investigated by constant current charge-discharge and electrochemical impedance spectroscopic techniques. The results show that the specific surface area and the pore volume of microporous activated carbon increase with increasing activation time before the activation time reaches 37 min. The microporous volume totals 94.0% in the microporous activated carbons and the average pore diameter of microporous activated carbon is 2.00 nm. Microporous activated carbons prepared in the activation time of 31, 35 and 37 min are named as AC-31, AC-35 and AC-37, respectively. Compared with AC-27 electrode, the internal resistance for ions transferring in AC-31, AC-35 or AC-37 electrode is relatively small. The specific capacitance of AC-31 is the biggest among the microporous activated carbons, and it retains 279.6 F g^?1 maintaining 93.5% capacity after 200 recycling number.     

The detection by SERS of resonantly excited desorption of pyridine from silver island films by IR laser absorption

We have shown that when a very thin film of pyridine about two or three monolayers thick on a silver island film is exposed to a pulsed CO₂ laser line whose frequency corresponds to that of a pyridine vibrational mode the physisorbed molecules within the pyridine film can be desorbed even at liquid He temperatures. It is interesting that this observation was first made using surface enhanced Raman scattering. Experimental results are presented from which it is concluded that the phenomenon can be described as resonantly excited desorption. The absorbed IR energy seems to be localized within the pyridine film and the silver film and thermallized to some degree causing some of the physisorbed molecules to desorb. Analysis of the SERS spectra before and after the resonantly excited desorption has enabled us to separate out the SERS spectra due to the physisorbed pyridine and the chemisorbed pyridine.     

Ammonia modification of activated carbon to enhance carbon dioxide adsorption: Effect of pre-oxidation

A commercial granular activated carbon (GAC) was subjected to thermal treatment with ammonia for obtaining an efficient carbon dioxide (CO₂) adsorbent. In general, CO₂ adsorption capacity of activated carbon can be increased by introduction of basic nitrogen functionalities onto the carbon surface. In this work, the effect of oxygen surface groups before introduction of basic nitrogen functionalities to the carbon surface on CO₂ adsorption capacity was investigated. For this purpose two different approaches of ammonia treatment without preliminary oxidation and amination of oxidized samples were studied. Modified carbons were characterized by elemental analysis and Fourier Transform Infrared spectroscopy (FT-IR) to study the impact of changes in surface chemistry and formation of specific surface groups on adsorption properties. The texture of the samples was characterized by conducting N₂ adsorption/desorption at −196 °C. CO₂ capture performance of the samples was investigated using a thermogravimetric analysis (TGA). It was found that in both modification techniques, the presence of nitrogen functionalities on carbon surface generally increased the CO₂ adsorption capacity. The results indicated that oxidation followed by high temperature ammonia treatment (800 °C) considerably enhanced the CO₂ uptake at higher temperatures.     

New model of electron stimulated desorption from physisorbed monolayers application to Ar and N2O on Ru(001)

A new model of electron stimulated desorption from monolayers physisorbed on metal surfaces is proposed in which the excited surface state potential is due to a chemical rather than an image force acting on the adsorbed particle after the initial electronic excitation is completed. The equilibrium positions of the excited and the ground state potentials may nearly coincide and desorption is a purely quantum mechanical effect. It is demonstrated that, unlike for the commonly accepted Antoniewicz model, both, the kinetic energy distributions of desorbing neutral particles and the total desorption yields calculated in the model proposed here are consistent with the existing experimental data for Ar and N₂O physisorbed on Ru(001).     

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.     

Reactive ion scattering study of physisorbed adsorbates: experiment and theory

We have studied reactive ion scattering (RIS) of hyperthermal (1–100 eV) Cs⁺ projectiles from physisorbed surfaces. RIS experiments from physisorbed water on Pt(1 1 1) reveal scattering products of Cs(H₂O)_n⁺ (n=1–3) cluster ions. The yields for RIS products are extremely high compared to those with chemisorbed species. Classical molecular dynamics simulations provide a new mechanism that explains the enhanced RIS yields with physisorbed species. Slow Cs⁺ projectiles pick up physisorbed molecules via an ion–surface abstraction reaction, preferably without direct collisions between projectile and adsorbate. This RIS process is very efficient and mechanistically different from the RIS process responsible for chemisorbed species that occurs through direct collision-induced desorption.     

Physisorption of positronium on quartz surfaces

Whether positronium (Ps) can be physisorbed on a material surface is of great fundamental interest, since it can lead to new insight regarding quantum sticking and is a necessary first step to try to obtain a Ps2 molecule on a material host. Experiments in the past have produced evidence for physisorbed Ps on a quartz surface, but firm theoretical support for such a conclusion was lacking. We present a first-principles density-functional calculation of the key parameters determining the interaction potential between Ps and an alpha-quartz surface. We show that there is indeed a bound state with an energy of 0.14 eV, a value which agrees very well with the experimental estimate of approximately 0.15 eV. Further, a brief energy analysis invoking the Langmuir-Hinshelwood mechanism for the reaction of physisorbed atoms shows that the formation and desorption of a Ps2 molecule in that picture is consistent with the above results.     

Trapping of V(benzene)2 sandwich clusters in a n-alkanethiol self-assembled monolayer matrix

V(benzene)₂ sandwich cluster cations produced in the gas phase were size-selectively deposited onto a self-assembled monolayer of n-hexadecanethiols (HDT-SAM) chemisorbed on a Au(111) surface as well as onto a bare Au(111) surface. The thermal chemistry of the neutralized clusters on each substrate was studied with temperature programmed desorption (TPD). From the analyses of the threshold in the TPD, the desorption activation energies of the clusters deposited were determined to be 64.4 ±12.8 kJ/mol for the Au(111) and 130 ±10 kJ/mol for the HDT-SAM. The remarkably large desorption activation energy from the SAM suggests that the deposited clusters are incorporated into the SAM matrix and firmly trapped inside the alkyl chains of the SAM.     

Isothermal desorption of hydrogen molecules from a W(110) surface at temperature ∼5 K

Isothermal desorption of hydrogen molecules from a W(110) surface atT _s ～ 5 K upon rapid shuttering of the molecular beam is observed in a “black chamber” type of ultrahigh-vacuum apparatus. Desorption was detected from three different states, identified as a multilayer condensation state and physisorbed states in the form of a two-dimensional gas and a two-dimensional condensate. The distribution of the physisorbed molecules between these states depends on the intensity of the flux of molecules on the surface; this appears to be responsible for the anomalous decrease of the number of isothermally desorbed molecules as the flux increases.     

Artificial neural network (ANN) approach for modeling and formulation of phenol adsorption onto activated carbon

In this study, a three-layer feed-forward back propagation network with Levenberg-Marquardt (LM) learning algorithm was applied to predict adsorption of phenol onto activated carbon (AC). Batch experiments were carried out to obtain experimental data. The neural network was trained considering the amount of adsorbent, initial concentration of phenol, temperature, contact time and pH as input parameters and the final concentration of phenol as a desired parameter. Different transfer functions for hidden and output layers and different number of neurons in a hidden layer were tested to optimize the network structure. An empirical equation for final concentration of phenol was developed by using the weights of optimized network. Accuracy of the developed ANN model was also measured using statistical parameters, such as mean absolute error (MAE), mean square error (MSE), root mean square error (RMSE) and correlation coefficient (R²). Results showed that MAE, MSE, RMSE, and R² values of the ANN model were 0.1540, 0.0565, 0.2378, and 0.9998, respectively, which indicate high accuracy of the ANN model. In the equilibrium study, predicted results of the ANN model were also compared with experimental data and the results of other conventional isotherm models.