Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

Immobilisation of lead(II) ions from aqueous solutions on natural coal

The immobilisation of lead(II) ions from aqueous solutions on natural coal was investigated to compare calculated and measured adsorption enthalpies. For this purpose, adsorption isotherms were measured at temperatures of 303, 333 and 353 K. Adsorption enthalpy ΔH was evaluated from temperature dependence of the equilibrium constant of adsorption using the van‘t Hoff equation. Thus, the value of ΔH = 27 kJ mol^?1 was obtained manifesting endothermic effect of lead(II) immobilisation on the coal. However, based on the flow and immersion calorimetric measurements, the exothermic character of lead(II) adsorption on the studied coal was proven with a value of about ?7 kJ mol^?1.     

Equilibrium isotherms and isosteric heat for CO<Subscript>2</Subscript> adsorption on nanoporous carbons from polymers

Four nanoporous carbons obtained from different polymers: polypyrrole, polyvinylidene fluoride, sulfonated styrene–divinylbenzene resin, and phenol–formaldehyde resin, were investigated as potential adsorbents for carbon dioxide. CO₂ adsorption isotherms measured at eight temperatures between 0 and 60 °C were used to study adsorption properties of these polymer-derived carbons, especially CO₂ uptakes at ambient pressure and different temperatures, working capacity, and isosteric heat of adsorption. The specific surface areas and the volumes of micropores and ultramicropores estimated for these materials by using the density functional theory-based software for pore size analysis ranged from 840 to 1990 m² g^?1, from 0.22 to 1.47 cm³ g^?1, and from 0.18 to 0.64 cm³ g^?1, respectively. The observed differences in the nanoporosity of these carbons had a pronounced effect on the CO₂ adsorption properties. The highest CO₂ uptakes, 6.92 mmol g^?1 (0 °C, 1 atm) and 1.89 mmol g^?1 (60 °C, 1 atm), were obtained for the polypyrrole-derived activated carbon prepared through a single carbonization-KOH activation step. The working capacity for this adsorbent was estimated to be 3.70 mmol g^?1. Depending on the adsorbent, the CO₂ isosteric heats of adsorption varied from 32.9 to 16.3 kJ mol^?1 in 0–2.5 mmol g^?1 range. Overall, the carbons studied showed well-developed microporosity and exceptional CO₂ adsorption, which make them viable candidates for CO₂ capture, and for other adsorption and environmental-related applications.     

Adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto fine powder of Typha latifolia L. root: kinetics and isotherm studies

Fine powder of Typha latifolia L. root was used for adsorption of copper and zinc ions from buffered and nonbuffered aqueous solutions. The adsorption reached equilibrium in 60 min. During this time, more than 90 % of the adsorption process was completed. The effect of initial pH, initial concentration of metal ion, and contact time was investigated in a batch system at room temperature. The optimum adsorption performance was observed at pH 5.00 and 4.25 for nonbuffered solutions of Cu(II) and Zn(II), respectively, while for buffered solutions it occurred at pH 6.00. The total metal uptake decreased on application of ammonium acetate buffer, from 37.35 to 17.00 mg g^?1 and 28.80 to 9.90 mg g^?1 for Cu(II) and Zn(II) solutions, respectively, with 100 mg L^?1 initial concentration. The pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models were used to describe the adsorption kinetics. The experimental data followed the pseudo-second-order kinetic model. The biosorption equilibrium was well described by Langmuir and Freundlich isotherm models.     

The effect of surface modification of mesoporous carbons on Auramine-O dye removal from water

Mesoporous carbon of regular structure was subjected to oxidation by ammonium persulfate at 30, 60 or 100 °C. The mesostructure and pore evolution were characterised by XRD, TEM, and N₂ sorption techniques. The functional groups present on the surface of the carbon materials were identified by FTIR and thermogravimetric studies. It was established that the micropores and small mesopores could be blocked by the surface oxides attached under mild oxidation. High densities of surface oxygen complexes, especially carboxylic groups, were generated on the surface of mesoporous carbons. All materials obtained were tested for the removal of Auramine-O from aqueous solution. Adsorption experiments were carried out as batch studies at different contact time, pH and initial dye concentration. Removal of this cationic dye in basic solutions was more effective than in acidic solutions. The highest sorption capacity towards Auramine-O was obtained for the carbon sample oxidised by ammonium persulfate solution at 100 °C. Fitting equilibrium data to Langmuir and Freundlich isotherms showed that Langmuir model was more suitable to describe the Auramine-O adsorption. The changes in standard enthalpy (ΔH⁰), standard entropy (ΔS⁰) and Gibbs free energy (ΔG⁰) were analysed. Thermodynamic study showed that the adsorption of Auramine-O was a spontaneous and exothermic process.     

Adsorption of mercury from single and multicomponent metal systems on activated carbon developed from cherry stones

The adsorption of mercury from a single/multi-solute aqueous solution by activated carbon (AC) prepared from cherry stones (CS) by chemical activation with H₃PO₄, ZnCl₂ or KOH is studied. Three series of AC (i.e., P, H₃PO₄; Z, ZnCl₂; K, KOH) were prepared by controlling the impregnation ratio and carbonization temperature. The textural characterization of AC was carried out by gas adsorption, mercury porosimetry and density measurements. The surface chemistry was analyzed by the pH of the point of zero charge (pH_zpc), FT-IR spectroscopy and Boehm’s method. Experiments of mercury adsorption were conducted by the batch method, using aqueous solutions of mercury and of mercury, cadmium and zinc without pH adjustment. The ACs possess a wide range of pore volumes and sizes. Their microporosity is usually well developed. The meso- and macropore volumes are higher for the P carbons and K carbons, respectively. BET surface areas as a rule range between 1000 and 2000 m²?g^?1. The pH_zpc is much lower for the P carbons. The content of acidic oxygen surface groups is lower for the K carbons, whereas the content of basic groups is higher for these carbons. The kinetics of the adsorption process of mercury is faster for ACs with high volumes of large size pores. However, the surface groups have a marked unfavorable influence on the kinetics. The pseudo-second order rate constant (k₂×10^?3, g/mol?h) is higher by the order Z-4-800 (67.69)>K-3-800 (43.45)>P-3.44-400 (36.98). The incorporation of zinc and cadmium to the mercury solution usually decelerates the adsorption process for the P carbons and Z carbons and accelerates it for the K carbons. The amount adsorbed of mercury is much larger for the K carbons than for the other ACs. For the Z carbons, competition effects of zinc and cadmium on the adsorption of mercury are negligible, which indicates that mercury adsorbs specifically on surface active sites of these adsorbents.     

Structural and surface heterogeneity of phosphorus-containing polyimide-derived carbons: effect of heat treatment temperature

Phosphorus-containing carbons have been obtained by carbonization of porous copolymer of 4,4′-bis(maleimidodiphenyl)methane (50 mol%) and divinylbenzene (50 mol%) in presence of phosphoric acid at temperatures 400–1000 °C. Porous structure was analyzed by nitrogen adsorption isotherms while surface chemistry was investigated by potentiometric titration method. It has been shown that carbons obtained at 500–1000 °C are micro-mesoporous with pore sizes of 1–1.1, 2–3 and 5.4 nm. The most developed porosity was achieved at 600 °C reaching BET surface area 890 m²/g and total pore volume 0.45 cm³/g. Carbons obtained by carbonization of polyimide precursor in presence of phosphoric acid showed acidic character with 30–40 % of phosphate surface groups. Maximum total amount of acidic surface groups was achieved at 800 °C reaching 3.2 mmol/g. Assignment of strongly acidic surface groups to phosphates was corroborated by pK value, phosphorus content and thermal gravimetric analysis.     

Chitosan as a biosorbent for adsorption of iron (II) from fracking wastewater

In this work, porous chitosan (CS) was investigated as a biosorbent for the removal of iron (II) from the synthetic fracking wastewater. The underlying problem with the production water from fracking industries is that it contains iron (II) up to 55 mg/L, which needs to be eliminated. Porous CS had a specific surface area of 1.05 m²/g with the average pore diameter of 319 A, as determined by using Brunauer‐Emmett‐Teller surface area analysis. The kinetics, isotherms, and thermodynamic analysis confirm that the porous CS can be a potential candidate for iron (II) removal. Both the pseudo‐first‐order model and pseudo‐second‐order model have good fit on iron (II) adsorption with the porous CS. Kinetic studies revealed that the CS‐iron (II) adsorption system was controlled by intraparticle diffusion. The monolayer adsorption capacity of the porous CS from Langmuir model was found to be 51.81 mg/g. The experimental data were fitted against common adsorption isotherms and yielded excellent fits in the following order: Langmuir > Temkin > Freundlich > Dubinin‐Radushkevich isotherms. Thermodynamic studies revealed that the adsorption of iron (II) onto porous CS was feasible and spontaneous. The adsorption process is endothermic, and the entropy is the driving force.     

Preparation of activated carbon from waste Camellia oleifera shell for supercapacitor application

The cost-effective activated carbons derived from waste Camellia oleifera shell (COS) by ZnCl₂ activation method are investigated as the active electrode material in electric double-layer capacitors (EDLCs) for the first time. The activation temperature and ZnCl₂/COS impregnation ratio are two key factors affecting the surface area and pore structure of the prepared activated carbons, which accordingly affect their capacitive performances. Electrochemical investigations indicate that the activated carbon (AC-3-600) obtained at the activation temperature of 600 °C and impregnation ratio of 3 shows the maximum specific capacitance of 374 and 266 F?g^?1 in 1 mol L^?1 H₂SO₄ and 6 mol L^?1 KOH electrolytes at 0.2 A g^?1, respectively. The high capacitance of the AC-3-600 is attributed to its high surface area (1,935 m² g^?1), high total pore volume (1.02 cm³ g^?1), and especially the large percentage of micropores (735 m² g^?1). Meanwhile, the activated carbon presents good cycle stability in both acid and alkaline electrolytes during 5,000 cycles at a fair current density of 4 A g^?1. So, we had reasons to believe that the activated carbons from waste COS by ZnCl₂ activation might be one of the innovative carbon electrode materials for EDLCs application.     

Removal of uranium(VI) from aqueous solution by apricot shell activated carbon

Uranium is a toxic and radioactive heavy metal found in nuclear effluents and should be treated based on environmental considerations. The adsorption of uranyl cations (UO₂ ²⁺) by apricot shell activated carbon (ASAC) was investigated in a batch system. The effects of pH, contact time, temperature, adsorbent dosage on the adsorption kinetics and equilibrium adsorption isotherms of U(VI) were examined. The U(VI) uptake was fast within the first 60 min and reached an equilibrium state at 120 min. The adsorption process was highly pH dependent and the maximum adsorption was obtained at an initial solution pH of 6.0. Temperature over the range 25–45 °C had little effect on the U(VI) adsorption. The U(VI) removal efficiency increased concurrently with increasing ASAC dosage, whereas the U(VI) adsorption capacity decreased with increasing ASAC dosage. The adsorption process followed both Langmuir and Freundlich isotherms. On the basis of Langmuir model, the maximum adsorption capacity was found to be 59.17 mg U(VI)/g adsorbent. The adsorption kinetics can be very well defined by the pseudo-first-order rate model. The present results suggest that ASAC could be used as an adsorbent for an efficient removal of U(VI) from aqueous solution.     

A chelating polymer resin: synthesis,characterization, adsorption and desorption performance for removal of Hg(II) from aqueous solution

A chloromethylated polystyrene-N-methyl thiourea chelating resin (DMTUR) was successfully prepared by the reaction of chloromethylated polystyrene beads (PS-Cl) with N-methyl thiourea (DMTU). The DMTUR exhibited a high selective adsorption toward Hg(II) in the mixture of different metal ions containing Cu(II), Hg(II), Cd(II), Pb(II), Cr(III) and Ni(II), and the adsorption capacity of Hg(II) approached a maximum with a value of 347 mg/g at pH = 4.0. Moreover, the batch kinetic study showed that the adsorption behavior of Hg(II) presented as a pseudo-second-order manner. And the adsorption isotherms fitted well with Langmuir model, and the maximum uptake of Hg(II) could reach to be 476 mg g^?1 at 35 °C. The thermodynamics study ensured the adsorption process essentially as favorable and endothermic. Finally, an eluent of 4 M HNO₃ solution could completely remove the adsorbed Hg(II) and the adsorption capacity allowed a high level at least five cycles. As aforementioned appealing properties, the DMTUR with simple technology, high adsorption capacity, significant selectivity and good regenerability may have a potential application in industrial scale as a treatment of enriched Hg(II) in wastewater.     

Effects of Cetylpyridinium Chloride on Phase and Rheological Behavior of the Diluted C(12)E(4)/Benzyl Alcohol/Water System

The influence of the pore size distribution of activated carbon on the adsorption of phenol from aqueous solutions was explored. Activated carbons with different porous structures were prepared by gasifying a bituminous coal char to different extents of burn-off. The results of adsorption experiments show that the phenol capacity of these carbons does not proportionally increase with their BET surface area. This reflects the heterogeneity of the carbon surface for adsorption. The pore size distributions of these carbons, determined according to the Dubinin-Stoeckli equation, were found to vary with the burn-off level. By incorporating the distribution with the Dubinin-Radushkevich equation using an inverse proportionality between the micropore size and the adsorption energy, the isotherms for the adsorption of phenol onto these carbons can be well predicted. The present study has demonstrated that the heterogeneity of carbon surface for the phenol adsorption can be attributed to the different energies required for adsorption in different-size micropores. Copyright 2000 Academic Press.     

The effects of preparation temperature on microstructure and electrochemical performance of calcium carbide-derived carbon

Calcium carbide-derived carbons (CCDCs) produced by chlorination of CaC₂ at various temperatures (400–800 °C) possess highly controllable microstructure and porosity, allowing them to serve as excellent electrode materials for the application of supercapacitor. This paper focused on the effect of pore size and specific surface area (SSA) of CCDC on its electrochemical behavior. Microstructure and micropore characteristics of CCDC were characterized by N₂ adsorption/desorption isotherms, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that SSA and average pore size increased with the increase of synthesis temperature from 400 °C to 600 °C, and then decreased when temperature reached to 800 °C. Meanwhile, a correlation between specific capacitance and SSA of micropores (less than 2 nm in diameter) has been studied. It has been found that the supercapacitor using the CCDC prepared at 600 °C as electrode material in 6 M KOH showed the maximum specific capacitance and energy density (53.61 F g^?1 and 7.08 W h kg^?1), outstanding rate capability, lower IR drop and 96 % retention of initial capacity over 5,000 cycles.     

Adsorption of Cu(II), Zn(II), Ni(II), Pb(II), and Cd(II) from aqueous solution on Amberlite IR-120 synthetic resin

The adsorption of copper(II), zinc(II), nickel(II), lead(II), and cadmium(II) on Amberlite IR-120 synthetic sulfonated resin has been studied at different pH and temperatures by batch process. The effects of parameters such as amount of resin, resin contact time, pH, and temperature on the ion exchange separation have been investigated. For the determination of the adsorption behavior of the resin, the adsorption isotherms of metal ions have also been studied. The concentrations of metal ions have been measured by batch techniques and with AAS analysis. Adsorption analysis results obtained at various concentrations showed that the adsorption pattern on the resin followed Freundlich isotherms. Here we report the method that is applied for the sorption/separation of some toxic metals from their solutions.     

Efficient Adsorption and Recovery of Pb(II) from Aqueous Solution by a Granular pH-Sensitive Chitosan-based Semi-IPN Hydrogel

A series of granular pH-sensitive semi-interpenetrating polymer network (semi-IPN) hydrogels based on chitosan (CTS), acrylic acid (AA) and gelatine (GE) were utilized for the adsorption and recycle of Pb(II) from aqueous solutions. The composite hydrogels have been characterized by FT-IR and TGA. The effects of contact time, pH value and initial Pb(II) concentration on the adsorption were investigated. Results indicated that the adsorption capacity of the hydrogel increased with increasing pH value and initial Pb(II) concentration, and a pH-sensitive adsorption characteristic was presented. The adsorption rate of the semi-IPN hydrogels on Pb(II) is fast with an adsorption rate constant of 14.9790 mg/(g·s), and adsorption equilibrium could be reached within 10 min. The adsorption isotherms of the hydrogels for Pb(II) could be described well by the Langmuir equation, rather than the Freundlich equation. The as-prepared hydrogels showed good reusability with 0.05 mol/l HNO₃ solutions as the desorbing agent and 0.1 mol/l NaOH solutions as the regeneration agent, respectively. After five consecutive adsorption-desorption processes, the semi-IPN hydrogel with 20 wt% GE may reach 85.26% of its initial adsorption capacity. In addition, the adsorbed Pb(II) can be quantitatively recovered by simply eluting the hydrogel with dilute HNO₃ solution, and a recovery ratio of 89.27% was reached for the semi-IPN hydrogel. The satisfactory adsorption amount is mainly derived from the chelating of functional groups (i.e. –COO^? and –NH₂) with Pb(II) ions. The hydrogel adsorbents exhibited excellent affinity for Pb(II), and can be applied to treat wastewater containing heavy metal ion and simultaneously recover the valuable metal sources.     

Synthesis and application of a novel magnetic nanosorbent for determination of trace Cd(II), Ni(II), Pb(II), and Zn(II) in environmental samples

In this work for the first time, Fe₃O₄@SiO₂ core–shell nanoparticles functionalized with isatin groups as a magnetic nanosorbent was applied for the simultaneous extraction of trace amounts of cadmium(II), nickel(II), lead(II), and zinc(II). The characterization of this nanosorbent was studied using Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectrometry, X-ray diffraction, vibrating sample magnetometer and thermogravimetric analysis. The effect of several factors such as pH, amount of sorbent, extraction time, type and volume of the eluent, sample volume, sorption capacity, and potentially interfering ions was investigated. In the selected conditions, it was observed that the limits of detection were 0.11 ng mL^?1 for Cd(II), 0.28 ng mL^?1 for Ni(II), 0.47 ng mL^?1 for Pb(II), and 0.21 ng mL^?1 for Zn(II), and the maximum sorption capacity of this suggested magnetic nanosorbent was 120, 112, 100, and 100 mg g^?1 for Cd(II), Ni(II), Pb(II), and Zn(II), respectively. Also, the precision of the method (RSD%) for ten replicate measurements was found 2.5, 2.5, 2.8, and 3.1%, for Cd(II), Ni(II), Pb(II), and Zn(II) ions, respectively. Finally, the suggested procedure was applied for determination of cadmium(II), nickel(II), lead(II), and zinc(II) at trace levels in different water and agricultural products with satisfactory results.     

Kinetics and Equilibrium Models for Sorption of Cu(II) onto a Novel Manganese Nano-adsorbent

The studies of kinetics and equilibrium sorption of Cu(II) were undertaken using nanoscale zerovalent manganese (nZVMn) synthesized by chemical reduction in a single pot system. nZVMn was characterized using scanning electron microscopy, energy dispersive x-ray, and surface area determined by Brunauer–Emmett–Teller. The effect of pH, contact time, adsorbent dose, agitation speed, initial Cu(II) concentrations, temperature, and ionic strength on the sorption of Cu(II) onto nZVMn were investigated in a batch system. The kinetic data followed pseudo-second-order. The mechanism was governed by pore diffusion. The equilibrium sorption data were tested by Freundlich, Langmuir, Temkin, Dubinin–Kaganer–Raduskevich, and Halsey isotherm models. The Langmuir monolayer adsorption capacity (Q_max = 181.818 mg/g) is much greater compared to other nano-adsorbents used in sorption of Cu(II). The thermodynamic parameters (ΔH⁰, ΔS⁰, ΔG⁰) revealed a feasible, spontaneous, and endothermic adsorption process. nZVMn has a great potential for effective removal of copper (II) in aqueous solution.     

Equilibrium,kinetics and thermodynamics study of phenols adsorption onto activated carbon obtained from lignocellulosic material (<Emphasis Type="Italic">Eucalyptus Globulus labill</Emphasis> seed)

Activated carbon was prepared from lignocellulosic material (Eucalyptus Globulus labill seed) by chemical activation with ZnCl₂ at two different concentrations (10 and 25 % m/v) named ACS25 and ACS10. The textural characteristics of the activated carbons (ACs) were determined by N₂ adsorption isotherms; these exhibit B.E.T. surface areas of 250 and 300 m² g^?1 for ACS25 and ACS10, respectively, with micropore volume contents of 0.140 and 0.125 cm³ g^?1 in the same order. In addition, the FTIR and Boehm methods were conducted for the chemical characterisation of ACs, where many groups with basic character were found, which favours the adsorption of phenols. The prepared carbonaceous adsorbents were used in the adsorption of wide pollutants monosubstituted phenol derivatives: phenol, 4-nitrophenol and 4-chlorophenol. The effect of temperature on the thermodynamics, kinetic and equilibrium of phenols adsorption on ACs was thoroughly examined. The adsorption kinetics adjusted properly for a pseudo-second-order kinetic model. However, the Elovich model (chemisorption) confirms that phenols adsorption did not occur via the sharing of electrons between the phenolic ring and basal plane of ACs because is not properly adjusted, so the process is given by physisorption. The thermodynamic parameters [i.e. Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°)] were also evaluated. The overall adsorption process was exothermic and spontaneous in nature. The values found in the thermodynamic study, confirm that the adsorption process corresponds to a clearly physical process.     

Porous SiOC composites fabricated from preceramic polymers and wood powders for efficient dye adsorption and removal

Porous SiOC composites for efficient treatment of dye wastewater were prepared using polysiloxane preceramic polymer mixed with wood biomass by pyrolysis under Ar atmosphere. The influences of the pyrolysis temperature on the microstructure, pore feature and adsorption behavior were investigated. The composites contain the α-quartz, cristobalite, nanosized β-SiC and free carbon embedded in a SiOC matrix. The composite obtained at 1300 °C presents a high specific surface area up to 463 m²/g. The adsorption capacity is enhanced by increasing pyrolysis temperature. The adsorption for the removal of methylene blue on the composites follows the pseudo second-order kinetics, and the adsorption data can be described by the Langmuir and Freundlich adsorption isotherms very well. The composite at 1300 °C displays a maximum adsorption capacity up to 173.5 mg/g caused by the enhancement of specific surface area and the existence of sp² carbons, resulting in many favorable adsorption sites and strong electrostatic attraction.