Biomass waste-derived activated carbon for the removal of arsenic and manganese ions from aqueous solutions

The goal of this study is to investigate the preparation of low-cost activated carbon from bean pods waste and to explore their potential application for the removal of heavy metals from aqueous solutions. Conventional physical (water vapor) activation was used for synthesizing the adsorbent. The obtained carbon was employed for the removal of As (III) and Mn (II) from aqueous solutions at different initial concentrations and pH values. Adsorption for both ions follows Langmuir-type isotherm, the maximum loading capacities for arsenic (III) and Mn (II) ions being 1.01 and 23.4 mg g⁻¹, respectively. According to the experimental data, it can be inferred that the basic character of the surface, i.e. the high content of basic groups, favors adsorption of ions. Arsenic adsorption capacity on the carbon obtained from agricultural waste was found to be similar to this of more expensive commercial carbons showing high adsorption capability. Regarding manganese adsorption, herein obtained carbon presented higher uptake adsorption than that of activated carbons reported in the literature.     

Preparation of activated carbon from a renewable bio-plant of Euphorbia rigida by H2SO4 activation and its adsorption behavior in aqueous solutions

The use of activated carbon obtained from Euphorbia rigida for the removal of a basic textile dye, which is methylene blue, from aqueous solutions at various contact times, pHs and temperatures was investigated. The plant material was chemically modified with H₂SO₄. The surface area of chemically modified activated carbon was 741.2 m² g⁻¹. The surface characterization of both plant- and activated carbon was undertaken using FTIR spectroscopic technique. The adsorption process attains equilibrium within 60 min. The experimental data indicated that the adsorption isotherms are well described by the Langmuir equilibrium isotherm equation and the calculated adsorption capacity of activated carbon was 114.45 mg g⁻¹ at 40° C. The adsorption kinetics of methylene blue obeys the pseudo-second-order kinetic model and also followed by the intraparticle diffusion model up to 60 min. The thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated to estimate the nature of adsorption. The activation energy of the system was calculated as 55.51 kJ mol⁻¹. According to these results, prepared activated carbon could be used as a low-cost adsorbent to compare with the commercial activated carbon for the removal textile dyes from textile wastewater processes.     

Characterization and ethylene adsorption of natural and modified clinoptilolites

The ethylene adsorption of Turkey clinoptilolite-rich tuff from Gordes and Bigadic region of western of Anatolia and their exchanged forms (K⁺, Na⁺ and Ca²⁺) were investigated. The clinoptilolite samples were characterized using XRD, TG-DTA and nitrogen adsorption methods. Adsorption isotherms for ethylene on natural and modified forms of both adsorbents at 277 K and 293 K were obtained at pressures up to 38 kPa. Uptake of ethylene increased as Na-CLN < Ca-CLN < K-CLN < Natural CLN for Gordes zeolite at 277 K, 293 K and for Bigadic zeolite at 277 K. For Bigadic zeolites at 293 K, uptake of ethylene increased in the order Ca-CLN < Na-CLN < K-CLN < Natural CLN. It was found that ethylene adsorption capacity of Bigadic clinoptilolite samples was much greater than Gordes clinoptilolite samples except K⁺ modified forms at both temperatures. These results show that both natural clinoptilolites have a considerable potential for the removal of ethylene.     

Study on the electronic transport properties of the C14 monocyclic ring: The first-principles calculations

The transport properties of C₁₄ monocyclic ring sandwiched between two Al(1 0 0) electrodes are investigated by first-principle calculations. The variation of the equilibrium conductance as the function of the separation distance between the molecule and the electrodes is studied. C₁₄ monocyclic ring shows metallic behavior according to the calculated equilibrium conductance. Electron transmission occurs through the lowest unoccupied molecular orbital (LUMO). With gate-voltage applied, it is found that the positive and negative gate-voltages can bring very different effect on the variation of equilibrium conductance. We also calculate the effects of adsorbing other atoms on the carbon ring such as oxygen and sulfur atoms. The results indicate that adsorption of this kind of electron-accepting impurity will decrease the conductance of the system.     

Study on the adsorption of fluorescein on Ag(1 1 0) substrate

The adsorption of fluorescein on the Ag(1 1 0) surface has been investigated by the first-principles pseudopotential method. Various adsorption geometries have been calculated and the energetically most favorable structure of fluorescein/Ag(1 1 0) was identified. The fluorescein molecule, in most favorable structure, is on hollow site, and the adsorption energy is 2.34 eV. Here the adsorption sites refer to the positions at the first layer of the substrate where the middle carbon atom of the fluorescein molecule is located. The bonding strength of the fluorescein molecule to the Ag substrate is site selective, being determined by electron transfer to the oxygen atoms of the molecule and local electrostatic attraction between the oxygen atoms and the silver atoms.     

Invalidating mechanism of bis (3-sulfopropyl) disulfide (SPS) during copper via-filling process

The invalidating process and related mechanism of bis (3-sulfopropyl) disulfide (SPS) during copper via-filling process were investigated by means of electrochemical polarization measurement, and the mass spectrometry (MS) testing was employed to confirm the molecular weight (MW) and the structure of SPS invalidating products. Meanwhile, quantum chemistry calculation was used to verify the rationality of the proposed invalidating course. These results suggest that the solution containing SPS has invalidated after the passed charges (PC) reached 15 Ah L⁻¹ under electrifying condition. The adsorption ability of SPS decrease gradually with the increase of PC during the invalidating process. The invalidation of SPS is an oxidation process related to the dissolved oxygen in the solution, during which the active functional group -S-S- is oxidized to -SO_x-SO_y-. As a result, the accelerating effect of SPS on copper reduction will gradually diminish.     

Adsorption of octadecyltrichlorosilane on mesoporous SBA-15

Adsorption of octadecyltrichlorosilane (OTS) on mesoporous SBA-15 has been studied by using Brunauer-Emmett-Teller (BET) surface area analysis, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermo-gravimetric analysis (TGA) techniques. BET surface area analysis shows decrease of surface area from 930 to 416 m²/g after OTS adsorption. SEM pictures show close attachment of SBA-15 particles. EDAX measurements show increase of carbon weight percentage and decrease of oxygen and silicon weight percentage. XPS results closely support EDAX analysis. FTIR spectra shows presence of methyl (-CH₃) and methylene (-CH₂) bands and oriented OTS monolayer on SBA-15. Thermo-gravimetric analysis shows that the OTS adsorbed on SBA-15 are stable up to a temperature of 230 °C and that the OTS monolayers decompose between 230 and 400 °C.     

Chitin-humic acid hybrid as adsorbent for Cr(III) in effluent of tannery wastewater treatment

Adsorption of Cr(III) from both synthetic and real samples of tannery wastewater treatment's effluent on chitin-humic acid (chitin-HA) hybrid has been carried out. Rate constant and capacity of adsorption of Cr(III) from the synthetic sample were investigated and removal of Cr(III) from the real sample was tested at optimum medium acidity equivalent to pH 3.5. Characterization using Fourier transform infra red (FT-IR) spectroscopy revealed that both COO⁻ and N-acetyl originated from respectively humic acid (HA) and chitin were involved on the adsorption of Cr(III), and hence the Freundlich's multilayer and multi-energy adsorption model was more applicable to treat the adsorption data than the Langmuir's monolayer and mono-energy model. The quantification of adsorption capacity and rate constant using Freundlich isotherm model and first order adsorption reaching equilibrium yielded values of 6.84 × 10⁻⁴ mol g⁻¹ (35.57 mg g⁻¹) and 1.70 × 10⁻² min⁻¹, respectively. Removal test for the real wastewater treatment's effluent showed that the maximum amount of Cr(III) could be removed by 1 g of chitin-HA hybrid was 2.08 × 10⁻⁴ mol or equivalent to 10.82 mg.     

Infrared reflection absorption study of carbon monoxide adsorption on Pd/Cu(1 1 1)

Pd-Cu bimetallic surfaces formed through a vacuum-deposition of Pd on Cu(1 1 1) have been discussed on the basis of carbon monoxide (CO) adsorption: CO is used as a surface probe and infrared reflection absorption (IRRAS) spectra are recorded for the CO-adsorbed surfaces. Low energy electron diffraction (LEED) patterns for the bimetallic surfaces reveal six-fold symmetry even after the deposition of 0.6 nm. The lattice spacings estimated by the separations of reflection high-energy electron diffraction (RHEED) streaks increase with increasing Pd thickness. Room-temperature CO exposures to the bimetallic surfaces formed by the Pd depositions less than 0.3 nm thickness generate the IRRAS bands due to the three-fold-hollow-, bridge- and linear-bonded CO to Pd atoms. In particular, on the 0.1 nm-thick Pd surface, the linear-bonded CO band becomes apparent at an earlier stage of the exposure. In contrast, the bridge-bonded CO band dominates the IRRAS spectra for CO adsorption on the 0.6 nm-thick Pd surface, at which the lattice spacing corresponds to that of Pd(1 1 1). A 90 K-CO exposure to the 0.1 nm-thick Pd surface leads to the IRRAS bands caused not only by CO-Pd but also by CO-Cu, while the Cu-related band is almost absent from the spectra for the 0.3 nm-thick Pd surface. The results clearly reveal that local atomic structures of the outermost bimetallic surface can be discussed by the IRRAS spectra for the probe molecule.     

Adsorption performance and mechanism of 2,4,6-trinitrotoluene on a novel adsorption material polyvinylbenzyl acid/SiO2

Polyvinylbenzene (PVB, namely polystyrene, PSt) was grafted on the surface of silica gel particles by “grafting from” in solution polymerization system, and grafting particles PVB/SiO₂ were obtained. The chloromethylation reaction of the grafted polyvinylbenzene was performed using a novel chloromethylation reagent, 1,4-bis (chloromethyoxy) butane that is un-carcinogenic, and grafting particles CMPVB/SiO₂ were obtained. Subsequently, chloromethyl groups on grafting particles CMPVB/SiO₂ were hydrolyzed and oxidized, and finally adsorption material polyvinylbenzyl acid/SiO₂ (PVBA/SiO₂) was prepared. The adsorption performances and mechanism of 2,4,6-trinitrotoluene (TNT) on PVBA/SiO₂ were investigated through static methods. The experimental results showed that PVBA/SiO₂ possessed strong adsorption ability for TNT with adsorption amount of 26.84 mg g⁻¹. The empirical Freundlich isotherm was also found to agree well with the equilibrium adsorption data. In addition, pH was found to have great influence on the adsorption amount. Finally, PVBA/SiO₂ was observed to possess excellent reusability as well.     

Grand canonical Monte Carlo simulations of hydrogen adsorption in carbon cones

The Monte Carlo method in its grand ensemble variant (GCMC) is used in order to study the hydrogen adsorption (77 K) characteristics of novel carbon structures, namely Carbon Cones (CCs). CCs are conical shaped curved graphitic sheets, with five different apex angles. CC structures with correct bonding topology were developed via atomistic-molecular simulations, while GCMC simulations of hydrogen adsorption were carried out on the five different apex angle structures. Emphasis has been given on the adsorption properties inside the cones and it was found that cone tips are characterized by enhanced adsorbability. The results were also compared with similar calculations on carbon nanotubes.     

Preparation of activated carbon from cherry stones by chemical activation with ZnCl2

Cherry stones (CS), an industrial product generated abundantly in the Valle del Jerte (Cáceres province, Spain), were used as precursor in the preparation of activated carbon by chemical activation with ZnCl₂. The influence of process variables such as the carbonisation temperature and the ZnCl₂:CS ratio (impregnation ratio) on textural and chemical-surface properties of the products obtained was studied. Such products were characterised texturally by adsorption of N₂ at −196 °C, mercury porosimetry and density measurements. Information on the surface functional groups and structures of the carbons was provided by FT-IR spectroscopy. Activated carbon with a high development of surface area and porosity is prepared. When using the 4:1 impregnation ratio, the specific surface area (BET) of the resultant carbon is as high as 1971 m² g⁻¹. The effect of the increase in the impregnation ratio on the porous structure of activated carbon is stronger than that of the rise in the carbonisation temperature, whereas the opposite applies to the effect on the surface functional groups and structures.     

Characterization of nanoporous carbons by combining CO2 and H2 sorption data with the Monte Carlo simulations

The Monte Carlo method in its grand ensemble variant (GCMC) is used in combination with experimental data in order to characterize microporous carbons and obtain the optimal pore size distribution (PSD). In particular, the method is applied in the case of AX-21 carbon. Adsorption isotherms of CO₂ (253 and 298 K) and H₂ (77 K) up to 20 bar have been measured, while the computed isotherms resulted from the GCMC simulations for several pore widths up to 3.0 nm. For the case of H₂ at 77 K quantum corrections were introduced with the application of the Feynman-Hibbs (FH) effective potential. The adsorption isotherms were used either individually or in a combined manner in order to deduce PSDs and their reliability was examined by the ability to predict the experimental adsorption isotherms. The combined approach was found to be capable of reproducing more accurately all the available experimental isotherms.     

Characterization and adsorptive application of ordered mesoporous silicas

The adsorption behaviour of the n-octane/ethanol binary liquid mixture has been studied on ordered mesoporous silica materials. Adsorption excesses on SBA-15, SBA-16 and MCM-48 solids are measured and described by mathematical functions. The experimental adsorption excess isotherms are presented and discussed. The mesoporous silicas used for liquid-adsorption experiments are characterized by nitrogen adsorption before and after liquid adsorption by the powder X-ray diffraction (XRD) and by the sample controlled thermal analysis (SCTA).     

Microstructure related photoluminescence in a-CNx films deposited by reactive rf magnetron sputtering

We investigated the photoluminescence (PL) properties of carbon nitride films (CN_x) deposited by rf magnetron sputtering and compared them to their microstructure depending on the target self-bias. While many of the data are compatible with ‘a-C:H like’ PL properties the observed variation of the PL efficiency η with respect to the target bias cannot be easily explained by the standard models. It is suggested that the observed variation of η is rather dominated by a change in microstructure which depends on the bombardment intensity during growth than by the concentration of non-radiative centres.     

Adsorption and manipulation of carbon onions on highly oriented pyrolytic graphite studied with atomic force microscopy

Carbon onions produced by DC arc discharge method were deposited on highly oriented pyrolytic graphite (HOPG) surface and their adsorption and manipulation was studied using an atomic force microscopy (AFM). Well-dispersed adsorption of carbon onions on HOPG surface was obtained and aggregations of onions were not observed. The van der Waals interaction between the onion and HOPG surface and that between two onions, were calculated and discussed using Hamaker's theory. The manipulation of adsorbed onions on HOPG surface was realized using the AFM in both the raster mode and the vector mode. The controllability and precision of two manipulation modes were compared and the vector mode manipulation was found superior, and is a useful technique for the construction of nano-scale devices based on carbon onions.     

Monte Carlo simulation of hydrogen physisorption in K-doped single walled carbon nanotube array

Properties of hydrogen physisorption in K-doped single walled carbon nanotube array (SWCNTA) are investigated in detail by grand canonical Monte Carlo simulation. The optimization of hydrogen storage capacity at 293 K and 10 MPa as a function of K-doping schemes, K atoms’ doped-sites, and SWCNTA configuration is discussed.     

Interactions of xanthines with activated carbon: I. Kinetics of the adsorption process

Because of their pharmaceutical and industrial applications, we have studied the adsorption of xanthine derivates (caffeine and theophylline) by activated carbon. To this end, we examined kinetic, equilibrium and thermodynamic aspects of the process. This paper reports the kinetics results. The experimental results indicate that the process was first order in C and the overall process was assumed to involve a single, reversible adsorption-desorption process obeying a kinetic law postulated by us.     

Lithium and antimony adsorbed on graphene studied by first-principles calculations

We have investigated the Sb and Sb₂ doping of graphene and the effect of Li_n (n = 2-4) atoms in detail. We find chemisorption only when we replace C with Sb and Sb₂ and distort the lattice. The additional adsorption of Li atoms changes the electronic band structure of the system.     

Role of pH and calcium ions in the adsorption of an alkyl N-aminodimethylphosphonate on steel: An XPS study

The role of pH and calcium ions in the adsorption of an alkyl N-aminodimethylphosphonate on mild steel (E24) surfaces was investigated by XPS. Fe 2p_3/2 and O 1s spectra show that the oxide/hydroxide layer developed on the steel surface, immersed in the diphosphonate solution (7 ≤ pH ≤ 13, without Ca²⁺) or in a filtered cement solution (pH 13, 15.38 mmol l⁻¹ of Ca²⁺), consists of Fe₂O₃, covered by a very thin layer of FeOOH (goethite). The total thickness of the oxide/hydroxide layer is ∼3 nm and is independent of the pH and the presence/absence of Ca²⁺. In the absence of Ca²⁺ ions, the N 1s and P 2p spectra reveal that the adsorption of the diphosphonate on the outer layer of FeOOH takes place only for pH lower than the zero charge pH of goethite (7.55). At pH 7, the adsorbed diphosphonate layer is continuous and its equivalent thickness is ∼24 Å (monolayer). In the presence of Ca²⁺ ions, the C 1s and Ca 2p signals indicate that calcium is present on the steel surface as calcium phosphonate (and Ca(OH)₂, in very small amount). The adsorption of the diphosphonate molecules on the steel surface is promoted in alkaline solution (pH > 7.55) by the doubly charged Ca²⁺ ions that bridge the O⁻ of goethite and the P-O⁻ groups of the diphosphonate molecules. The measured values for the Ca/P intensity ratio are in the range 0.75-1, which suggests that the diphosphonate molecules are adsorbed on steel forming a polymer cross-linked by calcium ions through their phosphono groups. In the presence of Ca²⁺ ions in alkaline solution, the adsorbed diphosphonate layer is discontinuous and the surface coverage is found to be ∼34%.