Adsorption and desorption of different gases on Ru film in the dark and under UV irradiation

The adsorption and desorption of some vapors and gases (water, hydrogen, dinitrogen oxide, carbon monoxide, oxygen) on Ru film has been investigated at 305 K using a Tian-Calvet microcalorimeter. The initial heat of adsorption, the irreversible coverage and the temperature of maximum desorption rate indicate the following binding energy order: H₂>N₂O>H₂O>CO>O₂. The amount of photoadsorption (for H₂O, N₂O, H₂) and photodesorption (for CO and O₂) has also been determined by recording the pressure changes induced by UV irradiation of the Ru film.     

A new calorimeter for simultaneous measurement of isotherms and heats of adsorption

A new calorimeter designed for simultaneous measurements of heats and isotherms of gas adsorption and desorption systems is presented. It consists of a volumetric/manometric gas adsorption instrument, the adsorption vessel of which is placed within a second vessel filled with inert gas. This gas acts as a sensor, as not only its temperature but also its pressure is increased if heat is released from the adsorption vessel via the sensor gas to its thermostated surroundings. Indeed, the time integral of the sensor gas pressure signal turned out to be strongly related to the total heat released from the adsorption vessel.A basic theoretical equation of the measurement procedure is given. Results of numerous calibration measurements are presented. The question of what type and amount of sensor gas should be used to achieve high sensitivity of the instrument is discussed.Two examples of measurements of heats of adsorption and adsorption isotherms are given, namely adsorption of N₂ on alumina oxide (CRM-BAM-PM-104) at 77 K and CO₂ on zeolite Na13X and wessalite DAY both at 298 K.     

Synthesis,characterization and CO2 adsorption of NaA,NaX and NaZSM-5 from rice husk ash

NaA, NaX and NaZSM-5 zeolites were prepared by using silica extracted from rice hull ash as a raw material, and they were investigated for CO₂ adsorption performance as an adsorbent in order to solve the problem of suppressing the global warming. Three zeolites were synthesized by hydrothermal methods with seed technology, and a series of characterization methods, including XRD, FTIR, nitrogen adsorption-desorption and SEM, were used to demonstrate their advantages compared to traditional hydrothermal methods. The maximum equilibrium adsorption capacity of NaA-RS, NaX-RS and NaZSM-5-RS was 1.46, 3.12 and 2.20 mmol/g at 0 °C and 101.3 kPa, respectively. The CO₂ and N₂ adsorption isotherms recorded at different temperatures were perfectly fitted by the Dual-site Langmuir model. The CO₂/N₂ selectivity and Henry's law constants were calculated to demonstrate that the samples have a stronger affinity for CO₂, especially at low pressures. The isosteric heat of CO₂ and N₂ adsorption of the three zeolites was calculated, which was indicated that they were in an excellent potential for adsorption and separation of CO₂ in industrial flue gas.     

Adsorption of Cr(VI) using activated neem leaves: kinetic studies

In the present study, adsorbent is prepared from neem leaves and used for Cr(VI) removal from aqueous solutions. Neem leaves are activated by giving heat treatment and with the use of concentrated hydrochloric acid (36.5 wt%). The activated neem leaves are further treated with 100 mmol of copper solution. Batch adsorption studies demonstrate that the adsorbent prepared from neem leaves has a significant capacity for adsorption of Cr(VI) from aqueous solution. The parameters investigated in this study include pH, contact time, initial Cr(VI) concentration and adsorbent dosage. The adsorption of Cr(VI) is found to be maximum (99%) at low values of pH in the range of 1-3. A small amount of the neem leaves adsorbent (10 g/l) could remove as much as 99% of Cr(VI) from a solution of initial concentration 50 mg/l. The adsorption process of Cr(VI) is tested with Langmuir isotherm model. Application of the Langmuir isotherm to the system yielded maximum adsorption capacity of 62.97 mg/g. The dimensionless equilibrium parameter, R _L, signifies a favorable adsorption of Cr(VI) on neem leaves adsorbent and is found to be between 0.0155 and 0.888 (0<R _L<1). The adsorption process follows second order kinetics and the corresponding rate constant is found to be 0.00137 g/(mg) (min).     

Synthesis and characterization of CuFe2O4/NiMgAl-LDH composite for the efficient removal of oxytetracycline antibiotic

In this study, a modified copper ferrite/NiMgAl layered double hydroxide (CuFe₂O₄/NiMgAl-LDH) composite was developed for the adsorptive removal of oxytetracycline hydrochloride (OTC) antibiotic from aqueous solution. Material characterization by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier transforms infrared spectrum (FTIR) and X-ray photoelectron spectroscopy (XPS) confirms that the resultant material composes of a hexagonal layered doubled hydroxide structure with surficial deposits on CuFe₂O₄ cubes. The adsorption of OTC onto the prepared materials were studied as a function of solution pH, initial OTC concentration, reaction time and temperature. The OTC adsorption capacities of the prepared materials were as follows: CuFe₂O₄/NiMgAl-LDH composite > NiMgAl-LDH > CuFe₂O₄. The adsorption of OTC in the presence of salts like CuSO₄, NaHCO₃, NaCl were also studied and the results revealed that CuSO₄ has a positive effect on OTC adsorption while NaHCO₃ and NaCl showed the neutral and antagonistic effect. The results revealed that hydrogen bonding, anionic exchange, and electrostatic forces were mainly involved in the adsorption of OTC onto CuFe₂O₄/NiMgAl-LDH composite. OTC adsorption followed the pseudo-second-order kinetic model while the adsorption equilibrium data were well fitted to the Langmuir isotherm model with the maximum adsorption capacity of 192 mg/g at 323K. Furthermore, the thermodynamic study revealed that the adsorption process was spontaneous and endothermic.     

Removal of Thiram from Aqueous Solutions

In this study activated carbon was used for the removal of thiram from aqueous solutions. Adsorption experiments were carried out as a function of time, initial thiram concentration and temperature. Equilibrium data fitted well to the Freundlich and Langmuir equilibrium models in the studied concentration range. Adsorption kinetics followed a pseudo second‐order kinetic model rather than pseudo first‐order model. The results from kinetic experiments were used to describe the adsorption mechanism. Both boundary layer and intraparticle diffusion played important role in the adsorption mechanism of thiram. Thermodynamic parameters (ΔG₀, ΔH₀, and ΔS₀) were determined and the adsorption process was found to be an endothermic one. The negative values of ΔG⁰ at different temperatures were indicative of the spontaneity of the adsorption process.     

Prediction of adsorption isotherms of C3H6/C3H8 on hierarchical porous HP–Cu–BTC

The isotherms of C₃H₆ and C₃H₈ on three distinct HP–Cu–BTCs were determined using the static volumetric capacity technique across the pressure range 0–100 kPa, and the resulting experimental data set was regressed using the dual–site sips (DSS) model. The kinetics and thermodynamics of C₃H₆ and C₃H₈ on HP–Cu–BTCs were studied. The results show that the adsorption kinetics of the three samples conform to the pseudo–first–order kinetic model, indicating that the adsorption process of the HP–Cu–BTCs samples is the adsorption process with physical adsorption as the control step. The thermodynamic analysis results show that the adsorption of propylene and propane on the surface of HP–Cu–BTCs are a spontaneous exothermic process, because the transition of propylene and propane from three–dimensional motion to two–dimensional motion leads to a decrease in the system entropy. In addition, the isosteric heat of adsorption ($Q_{st}$) was used to predict the isotherms of C₃H₆ and C₃H₈ at 298 and 303 K, respectively. When the predicted and experimental values are compared, the predicted isotherms are shown to be fully associated with the experimental values, with mean relative errors (MRE%) of less than 2%. Additionally, the C₃H₆ and C₃H₈ adsorption isotherms and selectivity for C₃H₆ adsorption were predicted using a combination of the DSS model and ideal adsorbed solution theory (IAST). The findings suggest that the overall adsorption capacity of the mixes rose as the mole fraction of C₃H₆ increased, but the adsorption capacity of the equimolar C₃H₆ and C₃H₈ in the three HP–Cu–BTC combinations was smaller than the pure component. Additionally, an undetectable shift in C₃H₆/C₃H₈ selectivity was seen when the molar percentage of C₃H₆ increased.     

Degradation of the herbicide isoproturon by a photocatalytic process

In this study, the adsorption and photocatalytic degradation of isoproturon (one of the most widely used herbicides in agriculture) was investigated in an annular photoreactor packed with a TiO₂ photocatalyst. The results highlighted that the monolayer Langmuir adsorption isotherm model was well obeyed. The isoproturon adsorption equilibrium constant was determined experimentally. The codegradation of isoproturon and of other copollutants such as salicylic acid and phenol occurred, demonstrating that within the catalyst, the same type of sites can be involved in the adsorption of the two pollutants. The heat of adsorption fell in the range of 20 to 50 °C and was found to be ∼43 kJ/mol. As expected, the adsorption constant K_a decreased with increasing the fluid flow due to the temperature rise. The kinetics of the photocatalytic degradation of isoproturon revealed a first-order reaction for initial concentrations between 3 and 43 ppm. In our experimental conditions, no by-products were detected and total disappearance of isoproturon was observed.     

Adsorption of di-2-pyridyl ketone salicyloylhydrazone on silica gel: characteristics and isotherms

The adsorption of DPKSH onto silica gel was investigated, at 25±1 °C and pH 1, 4.7 and 12. For the same DPKSH concentration interval, the minimum required time of contact for adsorption maximum at pH 4.7 was smaller than at pH 1 and the maximum amount of DPKSH adsorbed per gram of silica at pH 1 is smaller than at pH 4.7. At pH 12 the DPKSH adsorption onto silica gel was not significant. The adsorption data followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The maximum amount of solute adsorbed (m_ads^max) and the adsorption constant, K_L, were derived from Langmuir isotherm. The Freundlich constants 1/n and K_F related, respectively, to the energetic heterogeneity of adsorption sites and an empirical constant were evaluated. The mean sorption free energy (E) of DPKSH adsorption onto silica gel was calculated from D-R isotherm indicating a physical adsorption mode. Finally, conductimetric titrations showed the silica particle basicity and acidity as 0.002 and 0.3 mmol g⁻¹, respectively.     

Study of carbon dioxide adsorption on a Cu-nitroprusside polymorph

A careful structural characterization was carried out to unequivocally determine the structure of the synthesized material. The TGA, DRIFTS and a Pawley fitting of the XRD powder profiles indicate that the hydrated and in situ dehydrated polymorph crystallizes in the orthorhombic space group Pnma. Meanwhile, the CO₂ isosteric heat of adsorption appears to be independent of loading with an average value of 30 kJ/mol. This translates to a physisorption type interaction, where the adsorption energy corresponding to wall and lateral interactions are mutually compensated to produce, an apparently, homogeneous adsorption energy. The somewhat high adsorption energy is probably due to the confinement of the CO₂ molecules in the nitroprusside pores. Statistical Physics and the Dubinin theory for pore volume filling allowed model the CO₂ equilibrium adsorption process in Cu-nitroprusside. A DRIFTS test for the adsorbed CO₂ displayed a peak at about 2338 cm⁻¹ that was assigned to a contribution due to physical adsorption of the molecule. Another peak found at 2362 cm⁻¹ evidenced that this molecule interacts with the Cu²⁺, which appears to act as an electron accepting Lewis acid site. The aim of the present paper is to report a Pnma stable Cu-nitroprusside polymorph obtained by the precipitation method that can adsorb carbon dioxide.     

Nanostructures’ study of chemisorptions of O2 molecule on Al (100) surface

In this study, oxygen molecule adsorption on the surface of aluminum at various positions (top, bridge, and central sites) was studied, and the binding energies of oxygen species adsorbed on aluminum were calculated using density functional theory (DFT) within the generalized gradient approximation (GGA). The potential of the adsorption of oxygen on aluminum was examined as a function of both surface coverage and adsorption site. The relative stabilities of oxygen chemisorptions were independent of both the transition metal surface and surface coverage. That is, oxygen exhibited insignificant selectivity with respect to positions on the metal surface. Our data O₂/Al surface chemisorptions revealed that the stables model for oxygen adsorption was that on the top site. The top site approach is important for the chemisorption processes because the adsorption energy for this model was lower than for the other sites. The paper presents the results of quantum chemical calculations using density functional theory method for adsorption of O₂ molecules on Al (100) surface at cubic structure with LANL2DZ, SDD and 6-31G¹ basis sets. We can extract energetic information about the stability of adsorption O₂ on aluminum surface and calculation adsorption energy.     

Adsorption behavior of organic halides on zeolites

The adsorption behavior and the differential heat of adsorption of chloroform were measured on various types of zeolite (faujasite, ZSM-5 and mordenite) with different Si/Al ratios. The results reveal that saturated adsorption is almost proportional to the micropore volume and is independent of the micropore structure or the Si/Al ratio. However, initial heat of adsorption was the highest (90 kJ mol⁻¹) on the mordenite with low Si/Al ratio, while low on the faujasite with high Si/Al ratio or ZSM-5 (50 kJ mol⁻¹). Change in initial heat of adsorption with Si/Al ratio is small for faujasite or mordenite and large for ZSM-5. For the comparison, trichloroethylene adsorption behavior of zeolite was also investigated. Saturated adsorption of trichloroethylene was almost constant for all types of zeolite, while the faujasite with high Si/Al ratio exhibited an adsorption isotherm of type V in BDDT (Brunauer, Deming, Deming and Teller) classification. The tendencies of heat of immersion are similar to the results of the initial heat of adsorption.     

Study on the difference in adsorption thermodynamics for water on swelling and non-swelling clays with implications for prevention and treatment of pneumoconiosis

Excessive inhalation of mineral dust can cause irreversible damage such as diffuse fibrosis of lung tissue. Water-based dust reduction technology can effectively control the dust concentration. The study of the interaction of water-clay mineral dust is helpful to the prevention and treatment of pneumoconiosis by water-based dust removal technology. To better understand the underlying adsorption mechanisms of water molecules on clay mineral dust, the detailed adsorption thermodynamics analysis is necessary. In this paper, we research the thermodynamics of adsorption of water molecules on swelling clay of montmorillonite and non-swelling clay of illite. First, the adsorption isotherms of water molecules on montmorillonite and illite at 293–313 K were measured by gravimetric method. Then, the key thermodynamic variables, including entropy change (ΔS), surface potential (Ω), isosteric heat of adsorption (Q_st) and variation of Gibbs free energy (ΔG), were analyzed. Results illustrate that the adsorption amount for water molecules on illite is one order of magnitude smaller than that on montmorillonite, suggesting that swelling clay plays a dominant role in water molecules adsorption process. For water molecules adsorption on montmorillonite, the contribution of secondary adsorption to total adsorption (a₂/a) is always less than 30%. For water molecules adsorption on illite, the contribution of primary adsorption to total adsorption (a₁/a) is greater than a₂/a at the low pressure region, while a₂/a can exceed 60% at the high pressure region. The difference in the uptakes of water molecules adsorption on non-swelling and swelling clays is mainly resulted from the difference in primary adsorption on two clays. The Henry’s constant (K_AA) for montmorillonite is in the range of 21.37–75.08 mmol/g/kPa, which is evidently larger than the K_AA values of 0.34–0.98 mmol/g/kPa for illite. Compared with non-swelling clay, the adsorption spontaneity degree for water molecules on swelling clay is higher, and the interaction of swelling clay-water molecules is stronger. Meanwhile, the movement of adsorbed water molecules in swelling clay is more confined than that in non-swelling clay. These findings can offer meaningful guidelines for the prevention and treatment of pneumoconiosis.     

Adsorption characteristics and surface free energy of AlPO4-5

The micropores and surface characteristics of aluminophosphate-type zeolite, AlPO₄-5, were analyzed by examining the adsorption behavior of water and other adsorbates. Water adsorption on AlPO₄-5 occurred on both structural defects and nonpolar surfaces. Adsorption on structural defects, accompanied by high heats of adsorption, is attributed to adsorption to surface hydroxyls. Water adsorption increased steeply at a certain relative pressure depending on the adsorption temperature, and this was considered attributable to capillary condensation. The contact angle of water on AlPO₄-5 micropore surfaces can be determined quantitatively by applying the Kelvin equation. The surface free energy of AlPO₄-5 calculated on the basis of the contact angle was revealed to be about 120 mJ/m², in agreement with accepted values of the dispersion component of the surface free energy of metal oxides. Adsorption heat values of adsorbates with different polarities indicate that the AlPO₄-5 surface is essentially nonpolar and interacts only with dispersion interaction. In the case of n-hexane the contact angle was assumed to be zero, showing high affinity with the result of enhanced adsorption due to pore filling. Received: 21 May 1998 Accepted: 28 July 1998     

Immobilization of papain on mesoporous silica: pH effect

The enzyme papain was adsorbed on mesoporous silica at 4°C and pH values between 3 and 11. From the adsorption kinetic data, the rate constant for the process was evaluated. The concentration of the enzyme in solution was calculated by monitoring the absorbance at 280 nm, and the quantity of papain bound to the solid was evaluated from the initial and residual soluble enzyme concentrations. The best results were observed for papain adsorption at pH 5.0; under these conditions, the desorption of the enzyme was <5%.     

Preparation,characterization and application of a CTAB-modified nanoclay for the adsorption of an herbicide from aqueous solutions: Kinetic and equilibrium studies

In this study, surfactant-modified pillared montmorillonites (MMT) were prepared using cetyltrimethylammonium bromide (CTAB) by the intercalation method and used as adsorbent to remove bentazon from aqueous solutions. The main compositions of MMT and CTAB/MMT were characterized by Fourier transform–infrared spectroscopy (FT–IR), X-ray diffraction (XRD), scanning electron micrography (SEM) and energy dispersive X-ray (EDX) spectroscopy. The removal efficiency of bentazon was studied as a function of adsorbent dosage, pH, initial bentazon concentration and ionic strength (sodium carbonate, sodium bicarbonate, sodium sulfate and sodium chloride). The removal efficiency of bentazon by CTAB/MMT was more than that of MMT in similar conditions. By increasing adsorbent dosage and initial bentazon concentration, the removal efficiency was increased and declined, respectively. The results showed that the maximum adsorption of organo-modified montmorillonite was obtained at pH 3. The maximum adsorption capacity was estimated to be 500 mg/g at pH 3 and room temperature. The study of the adsorption kinetic model revealed that the pseudo-second order model was the best applicable one to describe the adsorption of bentazon onto CTAB/MMT. Adsorption data were analyzed by both Langmuir and Freundlich adsorption isotherms and the results showed that it was better described by the Langmuir model. The adsorption capacities of the samples were found to increase with Na₂CO₃ anion saturation, while they decreased in the presence of NaHCO₃, Na₂SO₄ and NaCl.     

Physical immobilization of Rhizopus oryzae lipase onto cellulose substrate: activity and stability studies

Rhizopus oryzae lipase (ROL) was immobilized by adsorption onto oxidized cellulose fibers and regenerated films. The maximum adsorption level increases with the raise in the amount of carboxylic groups on cellulose surface confirming that adsorption is being governed mainly by electrostatic interaction between the enzyme and the substrate. This hypothesis was further confirmed by zeta-potential measurements showing a decrease in the zeta-potential of the fibers after enzyme adsorption. XPS analysis showed an intensification of the N 1s peak attesting the presence of the enzyme on the surface. The effect of temperature, pH and solvent polarity on the immobilized enzyme activity and stability was investigated. The catalytic esterification of oleic acid with n-butanol has been carried on using hexane as an organic solvent. A high conversion yield was obtained (about 80%) at 37 degrees C with a molar ratio of oleic acid to butanol 1:1 and 150IU immobilized lipase. The adsorption achieved two successive cycles with the same efficiency, and started to lose its activity during the third cycle.     

Polyamine chitosan adsorbent for the enhanced adsorption of anionic dyes from water

A simple synthesis route for amine protected-introduced-released chitosan (APIR-CS) was investigated to improve the adsorption of anionic dyes. The C₂ amine groups of the chitosan (CS) were initially protected via a Schiff-base reaction by benzaldehyde. They were then synthesized by the introduction of ethylenediamine into C₆ hydroxyl groups on CS via epichlorohydrin. The final product was obtained after removal of the Schiff base with dilute hydrochloride solution. Amine-introduced chitosan (AI-CS) was directly synthesized at the C₂ amine groups. The adsorbents were characterized by FTIR, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). For Congo red (CR) and methyl orange (MO), most of the amine groups in CS were converted to–N?CH₂ groups after the benzaldehyde treatment. Hydrochloric acid treatment after the cross-linking reaction released protected nitrogen atoms into the form of the primary amine again. APIR-CS had significantly greater adsorption capacities than AI-CS. The increased adsorption performance was attributed to the large number of primary amine groups on the surfaces. The adsorption mechanism was based on electrostatic interaction, while the adsorption process was mainly physisorption.     

Adsorption of Hg(II) Ions onto Binary Biopolymeric Beads of Carboxymethyl Cellulose and Alginate

The removal of Hg(II) ions from aqueous solution by adsorption onto cross-linked polymeric beads of carboxymethyl cellulose (CMC) and sodium alginate was studied at fixed pH (6) and room temperature 28 ± 0.2°C. The cross-linked polymeric beads were characterized by FTIR spectra. Sorption capacity of the polymer for the mercury ions was investigated in aqueous media consisting different amounts of mercury ions (2.5 to 100 mg dm^?3) and at different pH values (2 to 8). Adsorption behavior of Hg(II) ions could be modeled using both the Langmuir and Freundlich isotherms. The dynamic nature of adsorption was quantified in terms of several kinetic constants such as rate constants for adsorption (k₁) and Lagergreen rate constant (K_ad). The influence of various experimental parameters such as effect of pH, contact time, solid-to-liquid ratio, salt effect, and temperature effect etc. were investigated on the adsorption of Hg(II) ions.     

Selective Removal of Amikacin From Simulated Polluted Water Using Molecularly Imprinting Polymer (MIP)

In the present study, the antibiotic drug Amikacin has been used as template molecule to prepare poly(methacrylic acid) based molecularly imprinting polymer using acetonitrile (Acn) as a porogenic solvent. The polymer has been characterized by FTIR, SEM analysis. The poly(MAAc) MIP has been used for effective and selective removal of Amikacin (Amk) in batch mode process. The equilibrium uptake data was fitted to various isotherm models namely, Langmuir, Freundlich, Temkin and Dubinin-Redushkevich (RD). Based on the regression values obtained, the order of fitness was DR>Freundlich>Temkin>Langmuir. The maximum adsorption capacity (Q_o), as determined using Langmuir plot was 60.60 mg/g at 30°C. The presence of the drugs Streptomycin and Gentamycin in the solution did not affect the adsorption capacity of MIP. Finally, the adsorption capacity was found to be independent of the temperature of the adsorption system.