Search results for: adsorption isotherms

Authors: Souhila Bendenia, Chahrazed Bendenia, Hanaa Merad-Dib, Sarra Merabet, Samia Moulebhar, Sid Ahmed Khantar

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Today, environmental pollution is a major concernworldwide, threateninghumanhealth. Various techniques have been used, includingdegradation, filtration, advancedoxidationprocesses, ion exchange, membrane processes, and adsorption. The latter is one of the mostsuitablemethods, usinghighly efficient materials. In this study, NaX zeolite was modified with Cu or Ni at various rates. Following ion exchange, the samples were characterized by XRD, BET and SEM/EDX. After characterization, the exchanged zeolites were used for adsorption of various pollutants as CO2. Different thermodynamic parameters were studied such as Qst. XRD results show that the most intense peaks characteristic of 13X persist after the exchange reaction for all samples. The SEM images of our samples have uniform and regular crystal shapes. The results show that ion exhange with Cu or Ni affect the textural properties of X zeolites and prove that the exchange zeolites can be used as an adsorbent for depollution.

Keywords: X zeolites (NaX), ion exchange, characterization, adsorption

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Authors: Nadjib Dahdouh, Samira Amokrane, Elhadj Mekatel, Djamel Nibou

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The removal of Basic Yellow 28 (BY28) from aqueous solutions by plastic wastes PMMA was investigated. The characteristics of plastic wastes PMMA were determined by SEM, FTIR and chemical composition analysis. The effects of solution pH, initial Basic Yellow 28 (BY28) concentration C, solid/liquid ratio R, and temperature T were studied in batch experiments. The Freundlich and the Langmuir models have been applied to the adsorption process, and it was found that the equilibrium followed well Langmuir adsorption isotherm. A comparison of kinetic models applied to the adsorption of BY28 on the PMMA was evaluated for the pseudo-first-order and the pseudo-second-order kinetic models. It was found that used models were correlated with the experimental data. Intraparticle diffusion model was also used in these experiments. The thermodynamic parameters namely the enthalpy ∆H°, entropy ∆S° and free energy ∆G° of adsorption of BY28 on PMMA were determined. From the obtained results, the negative values of Gibbs free energy ∆G° indicated the spontaneity of the adsorption of BY28 by PMMA. The negative values of ∆H° revealed the exothermic nature of the process and the negative values of ∆S° suggest the stability of BY28 on the surface of SW PMMA.

Keywords: removal, Waste PMMA, BY28 dye, equilibrium, kinetic study, thermodynamic study

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Authors: Tsung-Lin Hsieh, Jiun-Jen Chen, Yuhao Kang

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Metal-organic frameworks (MOFs) have drawn scientists’ attention for decades due to its high specific surface area, tunable pore size, and relatively low temperature for regeneration. Bearing with those mentioned properties, MOFs has been widely used in various applications, such as adsorption/separation and catalysis. However, the current challenge for practical use of MOFs is to effectively shape these crystalline powder material into controllable forms such as pellets, granules, and monoliths with sufficient mechanical and chemical stability, while maintaining the excellent properties of MOFs powders. Herein, we have successfully synthesized an Al-based MOF powder which exhibits a high water capacity at relatively low humidity conditions and relatively low temperature for regeneration. Then the synthesized Al-MOF was shaped into granules with particle size of 2-4 mm by (1) tumbling granulation, (2) High shear mixing granulation, and (3) Extrusion techniques. Finally, the water vapor adsorption rate and crush strength of Al-MOF granules by different shaping techniques were measured and compared.

Keywords: granulation, granules, metal-organic frameworks, water vapor adsorption

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Authors: Saad Mohamed Elsaid Abdelrahman

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The adsorption method is one of the best modern techniques used in removing pollutants, especially organic hydrocarbon compounds, from polluted water. Through this research, bentonite clay can be used to remove organic hydrocarbon compounds, such as heptane and octane, resulting from oil spills in seawater. Bentonite clay can be obtained from the Kholayaz area, located north of Jeddah, at a distance of 80 km. Chemical analysis shows that bentonite clay consists of a mixture of silica, alumina and oxides of some elements. Bentonite clay can be activated in order to raise its adsorption efficiency and to make it suitable for removing pollutants using an ionic organic solvent. It is necessary to study some of the factors that could be in the efficiency of bentonite clay in removing oily organic compounds, such as the time of contact of the clay with heptane and octane solutions, pH and temperature, in order to reach the highest adsorption capacity of bentonite clay. The temperature can be a few degrees Celsius higher. The adsorption capacity of the clay decreases when the temperature is raised more than 4°C to reach its lowest value at the temperature of 50°C. The results show that the friction time of 30 minutes and the pH of 6.8 is the best conditions to obtain the highest adsorption capacity of the clay, 467 mg in the case of heptane and 385 mg in the case of octane compound. Experiments conducted on bentonite clay were encouraging to select it to remove heavy molecular weight pollutants such as petroleum compounds under study.

Keywords: adsorbent, bentonite clay, oil spills, removal

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Authors: Sudarshan Kalsulkar, Sunil S. Bhagwat

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Biosorption is a physiochemical process that occurs naturally in certain biomass which allows it to passively concentrate and bind contaminants onto its cellular structure. Activated carbons (AC) are one such efficient biosorbents made by utilizing lignocellulosic materials from agricultural waste. Steam activated carbon (AC) was synthesized from Barley husk. Its synthesis parameters of time and temperature were optimized. Its physico-chemical properties like density, surface area, pore volume, Methylene blue and Iodine values were characterized. BET surface area was found to be 42 m²/g. Batch Adsorption tests were carried out to determine the maximum adsorption capacity (qmax) for various metal ions. Cd+2 48.74 mg/g, Pb+2 19.28 mg/g, Hg+2 39.1mg/g were the respective qmax values. pH and time were optimized for adsorption of each ion. Column Adsorptions were carried for each to obtain breakthrough data. Microbial adsorption was carried using E. coli K12 strain. 78% reduction in cell count was observed at operating conditions. Thus the synthesized Barley husk AC can be an economically feasible replacement for commercially available AC prepared from the costlier coconut shells. Breweries and malting industries where barley husk is a primary waste generated on a large scale can be a good source for bulk raw material.

Keywords: activated carbon, Barley husk, biosorption, decontamination, heavy metal removal, water treatment

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Authors: Sudipt Agarwal, Siddharth Verma, S. M. Iqbal, Hitik Kalra

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Natural gas as a fuel has created wonders, but on the contrary, the ill-effects of methane have been a great worry for professionals. The largest source of methane emission is the oil and gas industry among all industries. Methane depletes groundwater and being a greenhouse gas has devastating effects on the atmosphere too. Methane remains for a decade or two in the atmosphere and later breaks into carbon dioxide and thus damages it immensely, as it warms up the atmosphere 72 times more than carbon dioxide in those two decades and keeps on harming after breaking into carbon dioxide afterward. The property of a fluid to adhere to the surface of a solid, better known as adsorption, can be a great boon to minimize the hindrance caused by methane. Adsorption of methane during upstream processes can save the groundwater and atmospheric depletion around the site which can be hugely lucrative to earn profits which are reduced due to environmental degradation leading to project cancellation. The paper would deal with reasons why casing and cementing are not able to prevent leakage and would suggest methods to adsorb methane during upstream processes with mathematical explanation using volumetric analysis of adsorption of methane on the surface of activated carbon doped with copper oxides (which increases the absorption by 54%). The paper would explain in detail (through a cost estimation) how the proposed idea can be hugely beneficial not only to environment but also to the profits earned.

Keywords: adsorption, casing, cementing, cost estimation, volumetric analysis

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Authors: Bukunola K. Oguntade, Gareth M. Watkins

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The synthesis and characterization of metal-organic frameworks (MOFs) is an area of coordination chemistry which has grown rapidly in recent years. Worldwide there has been growing concerns about future energy supplies, and its environmental impacts. A good number of MOFs have been tested for the adsorption of small molecules in the vapour phase. An important issue for potential applications of MOFs for gas adsorption and storage materials is the stability of their structure upon sorption. Therefore, study on the thermal stability of MOFs upon adsorption is important. The incorporation of two or more transition metals in a coordination polymer is a current challenge for designed synthesis. This work focused on the synthesis, characterization and small molecule adsorption properties of three microporous (one zinc monometal and two bimetallics) complexes involving Cu(II), Zn(II) and 1,2,4,5-benzenetetracarboxylic acid using the ambient precipitation and solvothermal method. The complexes were characterized by elemental analysis, Infrared spectroscopy, Scanning Electron microscopy, Thermogravimetry analysis and X-ray Powder diffraction. The N2-adsorption Isotherm showed the complexes to be of TYPE III in reference to IUPAC classification, with very small pores only capable for small molecule sorption. All the synthesized compounds were observed to contain water as guest. Investigations of their inclusion properties for small molecules in the vapour phase showed water and methanol as the only possible inclusion candidates with 10.25H2O in the monometal complex [Zn4(H2B4C)2.5(OH)3(H2O)]·10H2O but not reusable after a complete structural collapse. The ambient precipitation bimetallic; [(CuZnB4C(H2O)2]·5H2O, was found to be reusable and recoverable from structure collapse after adsorption of 5.75H2O. In addition, Solvo-[CuZnB4C(H2O)2.5]·2H2O obtained from solvothermal method show two cycles of rehydration with 1.75H2O and 0.75MeOH inclusion while structure remains unaltered upon dehydration and adsorption.

Keywords: adsorption, characterization, copper, metal -organic frameworks, zinc

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Authors: Ahmed I. Shehab, Sabah M. Abdel Basir, M. A. Abdel Khalek, M. H. Soliman, G. Elgemeie

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Spent bleaching earth (SBE) recycling and utilization as an adsorbent to eliminate dyes from aqueous solution was studied. Organic solvents and subsequent thermal treatment were carried out to recover and reactivate the SBE. The effect of pH, temperature, dye’s initial concentration, and contact time on the dye removal using recycled spent bleaching earth (RSBE) was investigated. Recycled SBE showed better removal affinity of cationic than anionic dyes. The maximum removal was achieved at pH 2 and 8 for anionic and cationic dyes, respectively. Kinetic data matched with the pseudo second-order model. The adsorption phenomenon governing this process was identified by the Langmuir and Freundlich isotherms for anionic dye while Freundlich model represented the sorption process for cationic dye. The changes of Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were computed and compared through thermodynamic study for both dyes.

Keywords: Spent bleaching earth, reactivation, regeneration, thermal treatment, dye removal, thermodynamic

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Authors: Carlos Alberto Rivera-corredor, Angie Dayana Vargas-Ceballos, Edison Gilpavas, Izabela Dobrosz-Gómez, Miguel Ángel Gómez-García

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Hexavalent chromium, Cr (VI) is present in the effluents from different industries such as electroplating, mining, leather tanning, etc. This compound is of great academic and industrial concern because of its toxic and carcinogenic behavior. Its dumping to both environmental and public health for animals and humans causes serious problems in water sources. The amount of Cr (VI) in industrial wastewaters ranges from 0.5 to 270,000 mgL-1. According to the Colombian standard for water quality (NTC-813-2010), the maximum allowed concentration for the Cr (VI) in drinking water is 0.05 mg L-1. To comply with this limit, it is essential that industries treat their effluent to reduce the Cr (VI) to acceptable levels. Numerous methods have been reported for the treatment removing metal ions from aqueous solutions such as: reduction, ion exchange, electrodialysis, etc. Adsorption has become a promising method for the purification of metal ions in water, since its application corresponds with an economic and efficient technology. The absorbent selection and the kinetic and thermodynamic study of the adsorption conditions are key to the development of a suitable adsorption technology. The Ce0.25Zr0.75O2.nH2O presents higher adsorption capacity between a series of hydrated mixed oxides Ce1-xZrxO2 (x = 0, 0.25, 0.5, 0.75, 1). This work presents the kinetic and thermodynamic study of Cr (VI) adsorption on Ce0.25Zr0.75O2.nH2O. Experiments were performed under the following experimental conditions: initial Cr (VI) concentration = 25, 50 and 100 mgL-1, pH = 2, adsorbent charge = 4 gL-1, stirring time = 60 min, temperature=20, 28 and 40 °C. The Cr (VI) concentration was spectrophotometrically estimated by the method of difenilcarbazide with monitoring the absorbance at 540 nm. The Cr (VI) adsorption over hydrated Ce0.25Zr0.75O2.nH2O models was analyzed using pseudo-first and pseudo-second order kinetics. The Langmuir and Freundlich models were used to model the experimental data. The convergence between the experimental values and those predicted by the model, is expressed as a linear regression correlation coefficient (R2) and was employed as the model selection criterion. The adsorption process followed the pseudo-second order kinetic model and obeyed the Langmuir isotherm model. The thermodynamic parameters were calculated as: ΔH°=9.04 kJmol-1,ΔS°=0.03 kJmol-1 K-1, ΔG°=-0.35 kJmol-1 and indicated the endothermic and spontaneous nature of the adsorption process, governed by physisorption interactions.

Keywords: adsorption, hexavalent chromium, kinetics, thermodynamics

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Authors: Özge Alptoğa, Nuray Uçar, Nilgün Karatepe Yavuz, Ayşen Önen

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Sulfur dioxide (SO₂) is a very toxic air pollutant gas and it causes the greenhouse effect, photochemical smog, and acid rain, which threaten human health severely. Thus, the capture of SO₂ gas is very important for the environment. Graphene which is two-dimensional material has excellent mechanical, chemical, thermal properties, and many application areas such as energy storage devices, gas adsorption, sensing devices, and optical electronics. Further, graphene oxide (GO) is examined as a good adsorbent because of its important features such as functional groups (epoxy, carboxyl and hydroxyl) on the surface and layered structure. The SO₂ adsorption properties of the fibers are usually investigated on carbon fibers. In this study, potential adsorption capacity of GO fibers was researched. GO dispersion was first obtained with Hummers’ method from graphite, and then GO fibers were obtained via wet spinning process. These fibers were converted into a disc shape, dried, and then subjected to SO₂ gas adsorption test. The SO₂ gas adsorption capacity of GO fiber discs was investigated in the fields of utilization of different coagulation baths and reduction by hydrazine hydrate. As coagulation baths, single and triple baths were used. In single bath, only ethanol and CaCl₂ (calcium chloride) salt were added. In triple bath, each bath has a different concentration of water/ethanol and CaCl₂ salt, and the disc obtained from triple bath has been called as reference disk. The fibers which were produced with single bath were flexible and rough, and the analyses show that they had higher SO₂ adsorption capacity than triple bath fibers (reference disk). However, the reduction process did not increase the adsorption capacity, because the SEM images showed that the layers and uniform structure in the fiber form were damaged, and reduction decreased the functional groups which SO₂ will be attached. Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD) analyzes were performed on the fibers and discs, and the effects on the results were interpreted. In the future applications of the study, it is aimed that subjects such as pH and additives will be examined.

Keywords: coagulation bath, graphene oxide fiber, reduction, SO2 gas adsorption

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Authors: A. Ghribi, M. Bagane

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The discharge of dye in industrial effluents is of great concern because their presence and accumulation have a toxic or carcinogenic effect on living species. The removals of such compounds at such low levels are a difficult problem. Physicochemical technique such as coagulation, flocculation, ozonation, reverse osmosis and adsorption on activated carbon, manganese oxide, silica gel and clay are among the methods employed. The adsorption process is an effective and attractive proposition for the treatment of dye contaminated wastewater. Activated carbon adsorption in fixed beds is a very common technology in the treatment of water and especially in processes of decolouration. However, it is expensive and the powdered one is difficult to be separated from aquatic system when it becomes exhausted or the effluent reaches the maximum allowable discharge level. The regeneration of exhausted activated carbon by chemical and thermal procedure is also expensive and results in loss of the sorbent. Dye molecules also have very high affinity for clay surfaces and are readily adsorbed when added to clay suspension. The elimination of the organic dye by clay was studied by serval researchers. The focus of this research was to evaluate the adsorption potential of the raw clay in removing congo red from aqueous solutions using a laboratory fixed-bed column. The continuous sorption process was conducted in this study in order to simulate industrial conditions. The effect of process parameters, such as inlet flow rate, adsorbent bed height and initial adsorbate concentration on the shape of breakthrough curves was investigated. A glass column with an internal diameter of 1.5 cm and height of 30 cm was used as a fixed-bed column. The pH of feed solution was set at 7.Experiments were carried out at different bed heights (5-20 cm), influent flow rates (1.6- 8 mL/min) and influent congo red concentrations (10-50 mg/L). The obtained results showed that the adsorption capacity increases with the bed depth and the initial concentration and it decreases at higher flow rate. The column regeneration was possible for four adsorption–desorption cycles. The clay column study states the value of the excellent adsorption capacity for the removal of congo red from aqueous solution. Uptake of congo red through a fixed-bed column was dependent on the bed depth, influent congo red concentration and flow rate.

Keywords: adsorption, breakthrough curve, clay, congo red, fixed bed column, regeneration

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Authors: A. Ghribi, M. Bagane

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The discharge of dye in industrial effluents is of great concern because their presence and accumulation have a toxic or carcinogenic effect on living species. The removal of such compounds at such low levels is a difficult problem. The adsorption process is an effective and attractive proposition for the treatment of dye contaminated wastewater. Activated carbon adsorption in fixed beds is a very common technology in the treatment of water and especially in processes of decolouration. However, it is expensive and the powdered one is difficult to be separated from aquatic system when it becomes exhausted or the effluent reaches the maximum allowable discharge level. The regeneration of exhausted activated carbon by chemical and thermal procedure is also expensive and results in loss of the sorbent. The focus of this research was to evaluate the adsorption potential of the raw clay in removing rhodamine B from aqueous solutions using a laboratory fixed-bed column. The continuous sorption process was conducted in this study in order to simulate industrial conditions. The effect of process parameters, such as inlet flow rate, adsorbent bed height, and initial adsorbate concentration on the shape of breakthrough curves was investigated. A glass column with an internal diameter of 1.5 cm and height of 30 cm was used as a fixed-bed column. The pH of feed solution was set at 8.5. Experiments were carried out at different bed heights (5 - 20 cm), influent flow rates (1.6- 8 mL/min) and influent rhodamine B concentrations (20 - 80 mg/L). The obtained results showed that the adsorption capacity increases with the bed depth and the initial concentration and it decreases at higher flow rate. The column regeneration was possible for four adsorption–desorption cycles. The clay column study states the value of the excellent adsorption capacity for the removal of rhodamine B from aqueous solution. Uptake of rhodamine B through a fixed-bed column was dependent on the bed depth, influent rhodamine B concentration, and flow rate.

Keywords: adsorption, breakthrough curve, clay, fixed bed column, rhodamine b, regeneration

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Authors: Neha Kanodia, M. Kamil

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Properties of mono layers of Pluronic F127 at air/water interface have been investigated by using Langmuir trough method. Pluronic F127 is a triblock copolymer of poly (ethyleneoxide) (PEO groups)– poly (propylene oxide) (PO groups)–poly(ethylene oxide) (PEO groups). Surface pressure versus mean molecular area isotherms is studied. The isotherm of the mono layer showed the characteristics of a pancake-to-brush transition upon compression of the mono layer. The effect of adding surfactant (SDS) to polymer and the effect of increasing loading on polymer was also studied. The effect of repeated compression and expansion cycle (or hysteresis curve) is investigated to know about stability of the film formed. Static elasticity of mono layer gives information about molecular arrangement, phase structure and phase transition.

Keywords: surface-pressure, mean molecular area isotherms, hysteresis, static elasticity

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Authors: Omid Moradi, Mostafa Rajabi

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Graphene oxide (GO), reduced graphene oxide (rGO), multi-walled carbon nanotubes MWCNT), multi-walled carbon nanotube functionalized carboxyl (MWCNT-COOH), and multi-walled carbon nanotube functionalized thiol (MWCNT-SH) were used as efficient adsorbents for the rapid removal two dyes methyl orange (MO) and malachite green (MG) from the aqueous phase. The impact of several influential parameters such as initial dye concentrations, contact time, temperature, and initial solution pH was well studied and optimized. The optimize time for adsorption process of methyl orange dye on GO, rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were determined at 100, 100, 60, 25, and 60 min, respectively and The optimize time for adsorption process of malachite green dye on GO, rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were determined at 100, 100, 60, 15, and 60 min, respectively. The maximum removal efficiency for methyl orange dye by GO, rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were occurred at optimized pH 3, 3, 6, 2, and 6 of aqueous solutions, respectively and for malachite green dye were occurred at optimized pH 3, 3, 6, 9, and 6 of aqueous solutions, respectively. The effect of temperature showed that adsorption process of malachite green dye on GO, rGO, MWCNT, and MWCNT-SH surfaces were endothermic and for adsorption process of methyl orange dye on GO, rGO, MWCNT, and MWCNT-SH surfaces were endothermic but while adsorption of methyl orange and malachite green dyes on MWCNT-COOH surface were exothermic.On increasing the initial concentration of methyl orange dye adsorption capacity on GO surface was decreased and on rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were increased and with increasing the initial concentration of malachite green dye on GO, rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were increased.

Keywords: adsorption, graphene oxide, reduced graphene oxide, multi-walled carbon nanotubes, methyl orange, malachite green, removal

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Authors: Opeyemi Atiba-Oyewo, Taile Y. Leswfi, Maurice S. Onyango, Christian Wolkersdorfer

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This paper describes the preparation of surface modified montmorillonite using hexadecyltrimethylammonium bromide (HDTMA-Br) for the removal of vanadium from mine water. The adsorbent before and after adsorption was characterised by Fourier transform infra-red (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM), while the amount of vanadium adsorbed was determined by ICP-OES. The batch adsorption method was employed using vanadium concentrations in solution ranging from 50 to 320 mg/L and vanadium tailings seepage water from a South African mine. Also, solution pH, temperature and sorbent mass were varied. Results show that the adsorption capacity was affected by solution pH, temperature, sorbent mass and the initial concentration. Electrical conductivity of the mine water before and after adsorption was measured to estimate the total dissolved solids in the mine water. Equilibrium isotherm results revealed that vanadium sorption follows the Freundlich isotherm, indicating that the surface of the sorbent was heterogeneous. The pseudo-second order kinetic model gave the best fit to the kinetic experimental data compared to the first order and Elovich models. The results of this study may be used to predict the uptake efficiency of South Africa montmorillonite in view of its application for the removal of vanadium from mine water. However, the choice of this adsorbent for the uptake of vanadium or other contaminants will depend on the composition of the effluent to be treated.

Keywords: adsorption, vanadium, modified montmorillonite, equilibrium, kinetics, mine water

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Authors: Mohamed Habila, Ahmed Mohamed El-Toni, Mohamed Sheikh Moshab, Abdulrhman Al-Awadi, Zeid AL Othman

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Water pollution with dyes is a critical environmental issue because off the huge amount of dyes disbarred annually, which cause severe damage for the ecosystem and human life. The main raison for this severs pollution is the rapid industrial development which led to more production of harmful pollutants. on the other hand, the core shell based magnetic materials have showed amazing character for controlling the material synthesis with the targeted structure to enhance the adsorptive removal of pollutants. Herein, the Fe3O4core-meso SiO2/TiO2 double shell have been prepared for methylene blue dye adsorption. the preparation procedure is controlled to prepare the magnetic core with further coating layers from silica and titania. The prepared Fe3O4core-meso SiO2/TiO2 double shell showed adsorption capacity for methylene blue removal about 50 mg/g at pH 6 after 80 min contact time form 50 ppm methylene blue solution. The adsorption process of methylene blue onto Fe3O4core-meso SiO2/TiO2 double shell was well fitted with the pseudo-second-order kinetic model and freundlish isotherm, indicating a quick and multilayer adsorption mechanism.

Keywords: magnetic core, silica shell, titania shell, water treatment, methylene blue, solvo-thermal process, adsorption

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Authors: Cedillo Ortiz Cesar Isaac, Marañón-Ruiz Virginia-Francisca, Lozano-Alvarez Juan Antonio, Jáuregui-Rincón Juan, Roger Chiu Zarate

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Introduction: The contamination of water with the azo-dye is a problem worldwide as although wastewater contaminate is treated in a municipal sewage system, still contain a considerable amount of dyes. In the present, there are different processes denominated tertiary method in which it is possible to lower the concentration of the dye. One of these methods is by adsorption onto various materials which can be organic or inorganic materials. The xanthan is a biomaterial as removal agents to decrease the dye content in aqueous solution. The Zimm-Bragg model described the experimental isotherms obtained when this biopolymer was used in the removal of textile dyes. Nevertheless, it was not established if a possible correlation between dye structure and removal efficiency exists. In this sense, the principal objective of this report is to propose a qualitative relationship between the structure of three azo-dyes (Congo Red (CR), Methyl Red (MR) and Methyl Orange (MO)) and their removal efficiency from aqueous environment when xanthan are used as dye sequestering agents. Methods: The dyes were subjected to different pH and ionic strength values to obtain the conditions of maximum dye removal. Afterward, these conditions were used to perform the adsorption isotherm as was reported in the previous study in our group. The Zimm-Bragg model was used to describe the experimental data and the parameters of nucleation (Ku) and cooperativity (U) were obtained by optimization using the R statistical software. The spectra from UV-Visible (aqueous solution), Infrared absorption and Raman spectroscopies (dry samples) were obtained from the biopolymer-dye complex. Results: The removal percent with xanthan in each dye are as follows: with CR had 99.98 % when the pH is 12 and ionic strength is 10.12, with MR had 84.79 % when the pH is 9.5 and ionic strength is 43 and finally the MO had 30 % in pH 4 and 72. It can be seen that when xanthan is used to remove the dyes, exists a lower dependence between structure and removal efficiency. This may be due to the different tendency to form aggregates of each dye. This aggregation capacity and the charge of each dye resulting from the pH and ionic strength values of aqueous solutions are key factors in the dye removal. The experimental isotherm of MR was only that adequately described by Zimm-Bragg model. Because with the CR had the 100 % of remove thus is very difficult obtain de experimental isotherm and finally MO had results fluctuating and therefore was impossible get the accurate data. Conclusions: The study of the removal of three dyes with xanthan as dye sequestering agents suggests that aggregation capacity of dyes and the charge resulting from structural characteristics such as molecular weight and functional groups have a relationship with the removal efficiency. Acknowledgements: We are gratefully acknowledged support for this project by Consejo Nacional de Ciencia y Tecnología, México (CONACyT, Grant No. 632694.)

Keywords: adsorption, azo dyes, xanthan gum, Zimm Bragg theory

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Authors: Manisha Choudhary, Sudarsan Neogi

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Malachite green (MG), an organic basic dye, has been widely used for the dyeing purpose, as well as a fungicide and antiseptic in aquaculture industry to control fish parasites and disease. However, MG has now turned out to be an extremely controversial compound due to its adverse impact on living beings. Due to high toxicity, proper treatment of wastewater containing MG is utmost important. Among different available technologies, adsorption process is one of the most efficient and cost-effective treatment method due to its simplicity of design, ease of operation and regeneration of used materials. Nonetheless, commercial activated carbon is expensive leading the researchers to focus on utilizing natural resources. In the present work, a species of cactus, Opuntia ficus-indica (OFI), was used to develop a highly efficient, low-cost powdered activated carbon by chemical activation using NaOH. The biosorbent was characterized by Fourier-transform infrared spectroscopy, field emission scanning electron microscope, energy-dispersive X-ray spectroscopy, Brunauer–Emmett–Teller (BET) and X-ray diffraction analysis. Batch adsorption studies were performed to remove MG from an aqueous solution as a function of contact time, initial solution pH, initial dye concentration, biosorbent dosages, the presence of salt and temperature. By increasing the initial dye concentration from 100 to 500 mg/l, adsorption capacity increased from 165.45 to 831.58 mg/g. The adsorption kinetics followed the pseudo-second-order model and the chemisorption mechanisms were revealed. The electrostatic attractions and chemical interactions were observed between amino and hydroxyl groups of the biosorbent and amine groups of the dye. The adsorption was solely controlled by film diffusion. Different isotherm models were used to fit the adsorption data. The excellent recovery of adsorption efficiency after the regeneration of biosorbent indicated the high potential of this adsorbent to remove MG from aqueous solution and an excellent cost-effective biosorbent for wide application in wastewater treatment.

Keywords: adsorption, biosorbent, cactus, malachite green

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Authors: Vijay K. Tomer, Ritu Malik, Satya P. Nehra, Anshu Sharma

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Highly ordered mesoporous WO₃-TiO₂ nanohybrids with large intrinsic surface area and highly ordered pore channels were synthesized using mesoporous silica, KIT-6 as hard template using a nanocasting strategy. The nanohybrid samples were characterized by a variety of physico-chemical techniques including X-ray diffraction, Nitrogen adsorption-desorption isotherms, and high resolution transmission electron microscope. The nanohybrids were tested for detection of important indoor Volatile Organic Compounds (VOCs) including acetone, ethanol, n-butanol, toluene, and xylene. The sensing result illustrates that the nanocomposite sensor was highly responsive towards xylene gas at relatively lower operating temperature. A rapid response and recovery time, highly linear response and excellent stability in the concentration ranges from 1 to 100 ppm was observed for xylene gas. It is believed that the promising results of this study can be utilized in the synthesis of ordered mesoporous nanostructures which can extend its configuration for the development of new age e-nose type sensors with enhanced gas-sensing performance.

Keywords: nanohybrids, response, sensor, VOCs, xylene

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Authors: Tizi Hayet, Berrama Tarek, Bounif Nadia

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Phenol and its derivatives are organic compounds utilized in the chemical industry. They are introduced into the environment by accidental spills and the illegal release of industrial and municipal wastewater. Phenols are organic intermediaries that are considered potential pollutants. Adsorption is one of the purification and separation techniques used in this area. Algeria annually produces 131000 tons of fig; therefore, a large amount of fig leaves is generated, and the conversion of this waste into adsorbent allows the valorization of agricultural residue. The main purpose of this present work is to describe an application of a statistical method for modeling and to optimize the conditions of the phenol adsorption from agricultural by-products, locally available (fig leaves). The best experimental performance of phenol elimination on the adsorbent was obtained with: Adsorbent concentration (X₂) = 200 mg L⁻¹; Initial concentration (X₃) = 150 mg L⁻¹; Speed agitation (X₁) = 300 rpm.

Keywords: low-cost adsorbents, adsorption, fig leaves, phenol, factorial design

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Authors: Fatima Zahra Mahjoubi, Abderrahim Khalidi, Mohammed Abdennouri, Noureddine Barka

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Zn-Al layered double hydroxides containing carbonate, nitrate and dodecylsulfate as the interlamellar anions have been prepared through a coprecipitation method. The resulting compounds were characterized using XRD, ICP, FTIR, TGA/DTA, TEM/EDX and pHPZC analysis. The XRD patterns revealed that carbonate and nitrate could be intercalated into the interlayer structure with basal spacing of 22.74 and 26.56 Å respectively. Bilayer intercalation of dodecylsulfate molecules was achieved in Zn-Al LDH with a basal spacing of 37.86 Å. The TEM observation indicated that the materials synthesized via coprecipitation present nanoscale LDH particle. The average particle size of Zn-AlCO3 is 150 to 200 nm. Irregular circular to hexagonal shaped particles with 30 to 40 nm in diameter was observed in the Zn-AlNO3 morphology. TEM image of Zn-AlDs display nanostructured sheet like particles with size distribution between 5 to 10 nm. The sorption characteristics and mechanisms of methyl orange dye on organic LDH were investigated and were subsequently compared with that on the inorganic Zn-Al layered double hydroxides. Adsorption experiments for MO were carried out as function of solution pH, contact time and initial dye concentration. The adsorption behavior onto inorganic LDHs was obviously influenced by initial pH. However, the adsorption capacity of organic LDH was influenced indistinctively by initial pH and the removal percentage of MO was practically constant at various value of pH. As the MO concentration increased, the curve of adsorption capacity became L-type onto LDHs. The adsorption behavior for Zn-AlDs was proposed by the dissolution of dye in a hydrophobic interlayer region (i.e., adsolubilization). The results suggested that Zn-AlDs could be applied as a potential adsorbent for MO removal in a wide range of pH.

Keywords: adsorption, dodecylsulfate, kinetics, layered double hydroxides, methyl orange removal

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Authors: Thidarat Imyen, Paisan Kongkachuichay

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Cu-Zn/core-shell Al-MCM-41 catalyst with various copper species, prepared by a combination of three methods—substitution, ion-exchange, and impregnation, was studied for the selective catalytic reduction (SCR) of NO with NH3 at 300 °C for 150 min. In order to investigate the effects of Zn introduction on the nature of the catalyst, Cu/core-shell Al-MCM-41 and Zn/core-shell Al-MCM-41 catalysts were also studied. The roles of Zn promoter in the acidity and the NOx adsorption properties of the catalysts were investigated by in situ Fourier transform infrared spectroscopy (FTIR) of NH3 and NOx adsorption, and temperature-programmed desorption (TPD) of NH3 and NOx. The results demonstrated that the acidity of the catalyst was enhanced by the Zn introduction, as exchanged Zn(II) cations loosely bonded with Al-O-Si framework could create Brønsted acid sites by interacting with OH groups. Moreover, Zn species also provided the additional sites for NO adsorption in the form of nitrite (NO2–) and nitrate (NO3–) species, which are the key intermediates for SCR reaction. In addition, the effect of Zn on the nature of copper was studied by in situ FTIR of CO adsorption and in situ X-ray adsorption near edge structure (XANES). It was found that Zn species hindered the reduction of Cu(II) to Cu(0), resulting in higher Cu(I) species in the Zn promoted catalyst. The Cu-Zn/core-shell Al-MCM-41 exhibited higher catalytic activity compared with that of the Cu/core-shell Al-MCM-41 for the whole reaction time, as it possesses the highest amount of Cu(I) sites, which are responsible for SCR catalytic activity. The Cu-Zn/core-shell Al-MCM-41 catalyst also reached the maximum NO conversion of 100% with the average NO conversion of 76 %. The catalytic performance of the catalyst was further improved by using Zn promoter in the form of ZnO instead of reduced Zn species. The Cu-ZnO/core-shell Al-MCM-41 catalyst showed better catalytic performance with longer working reaction time, and achieved the average NO conversion of 81%.

Keywords: Al-MCM-41, copper, nitrogen oxide, selective catalytic reduction, zinc

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Authors: Qian Zhao

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With global increasing demand for phosphorus and intensively depleting reserves, it is urgent need to explore innovative approaches towards capturing phosphate from sewage, which is also an effective way to reduce phosphate contamination and avoid eutrophication of water bodies. In the present article, the superparamagnetic nano-sorbents containing Fe₃O₄ core and hafnium-modified MgAl/MgFe layered double hydroxides shell (abbreviated as MgAlHf-NP and MgFeHf-NP) was developed using a simple and low-cost synthesis protocol. The obtained Hf-coated nano-materials showed well-defined crystal structure and sufficient saturation magnetization and exhibited higher adsorption capacity for phosphate. Meanwhile, high selectivity was also confirmed since coexisting foreign anions and biomacromolecules showed little competitive effect on phosphate adsorption. The enhancement via doping with Hf should be explained by the stronger ligand complexation built by the pair of hard acid Hf ion and hard base phosphate that matched up the bonding preferences. Sufficient OH⁻ concentration and clear pH shift during the desorption/regeneration allowed for regeneration rate of higher than 90% after 5 cycles of adsorption desorption. This article attempts to provide a competitive candidate for phosphate-capture, which is highly effective, easily separable and repeatedly usable.

Keywords: phosphate recovery, nanoparticles, superparamagnetic, adsorption, reusability

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Authors: Mohsen Padervand

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Functionalized magnetic core-zeolitic shell nanostructures were prepared by the hydrothermal and coprecipitation methods. The products were characterized by Vibrating Sample Magnetometer (VSM), X-ray powder diffraction (XRD), Fourier Transform Infrared spectra (FTIR), nitrogen adsorption-desorption isotherms (BET) and Transmission Electron Microscopy (TEM). The growth of mordenite nanoparticles on the surface of silica coated nickel ferrite nanoparticles at the presence of organic templates was well approved. The antibacterial activity of prepared samples was investigated by the inactivation of E.coli as a gram negative bacterium. A new mechanism was proposed to inactivate the bacterium over the prepared samples. Minimum Inhibitory Concentration (MIC) and reuse ability were studied too. TEM images of the destroyed microorganism after the treatment time were applied to illustrate the inactivation mechanism. The interaction of the noble metals with organic components on the surface of nanostructures studied theoretically and the results were used to interpret the experimental results.

Keywords: nickel ferrite nanoparticles, magnetic core-zeolitic shell, antibacterial activity, E. coli

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Authors: Rasha Al-Saedi, Anthony Meijer

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The progress of new porous materials has increased rapidly over the past decade for use in applications such as catalysis, gas storage and removal of environmentally unfriendly species due to their high surface area and high thermal stability. In this work, a theoretical study of the zirconium-based metal organic framework (MOFs) were examined in order to determine their potential for gas adsorption of various guest molecules: CO2, N2, CH4 and H2. The zirconium cluster consists of an inner Zr6O4(OH)4 core in which the triangular faces of the Zr6- octahedron are alternatively capped by O and OH groups which bound to nine formate groups and three benzoate groups linkers. General formula is [Zr(μ-O)4(μ-OH)4(HCOO)9((phyO2C)3X))] where X= CH2OH, CH2NH2, CH2CONH2, n(NH2); (n = 1-3). Three types of adsorption sites on the Zr metal center have been studied, named according to capped chemical groups as the ‘−O site’; the H of (μ-OH) site removed and added to (μ-O) site, ‘–OH site’; (μ-OH) site removed, the ‘void site’ where H2O molecule removed; (μ-OH) from one site and H from other (μ-OH) site, in addition to no defect versions. A series of investigations have been performed aiming to address this important issue. First, density functional theory DFT-B3LYP method with 6-311G(d,p) basis set was employed using Gaussian 09 package in order to evaluate the gas adsorption performance of missing-linker defects in zirconium cluster. Next, study the gas adsorption behaviour on different functionalised zirconium clusters. Those functional groups as mentioned above include: amines, alcohol, amide, in comparison with non-substitution clusters. Then, dispersion-corrected density functional theory (DFT-D) calculations were performed to further understand the enhanced gas binding on zirconium clusters. Finally, study the water effect on CO2 and N2 adsorption. The small functionalized Zr clusters were found to result in good CO2 adsorption over N2, CH4, and H2 due to the quadrupole moment of CO2 while N2, CH4 and H2 weakly polar or non-polar. The adsorption efficiency was determined using the dispersion method where the adsorption binding improved as most of the interactions, for example, van der Waals interactions are missing with the conventional DFT method. The calculated gas binding strengths on the no defect site are higher than those on the −O site, −OH site and the void site, this difference is especially notable for CO2. It has been stated that the enhanced affinity of CO2 of no defect versions is most likely due to the electrostatic interactions between the negatively charged O of CO2 and the positively charged H of (μ-OH) metal site. The uptake of the gas molecule does not enhance in presence of water as the latter binds to Zr clusters more strongly than gas species which attributed to the competition on adsorption sites.

Keywords: density functional theory, gas adsorption, metal- organic frameworks, molecular simulation, porous materials, theoretical chemistry

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Authors: Indrasen Raghupatruni, Michael Glora, Ralf Diekmann, Thomas Demmer

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As the trend in automotive technology is fast moving towards hybridization and electrification to curb emissions as well as to improve the fuel efficiency, air-conditioning systems in passenger cars have not caught up with this trend and still remain as the major energy consumers amongst others. Adsorption based air-conditioning systems, e.g. with silica-gel water pair, which are already in use for residential and commercial applications, are now being considered as a technology leap once proven feasible for the passenger cars. In this paper we discuss a methodology, challenges and feasibility of implementing an adsorption based air-conditioning system in a passenger car utilizing the exhaust waste heat. We also propose an optimized control strategy with interfaces to the engine control unit of the vehicle for operating this system with reasonable efficiency supported by our simulation and validation results in a prototype vehicle, additionally comparing to existing implementations, simulation based as well as experimental. Finally we discuss the influence of start-stop and hybrid systems on the operation strategy of the adsorption air-conditioning system.

Keywords: adsorption air-conditioning, feasibility study, optimized control strategy, prototype vehicle

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Authors: H. Hammoudi, S. Bendenia, I. Batonneau-Gener, J. Comparot, K. Marouf-Khelifa, A. Khelifa

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X zeolites were prepared by ion-exchange with Cu2+ and/or Zn2+ cations, at different concentrations of the exchange solution, and characterised by thermal analysis and nitrogen adsorption. The acidity of the samples was investigated by pyridine adsorption–desorption followed by in situ Fourier transform infrared (FTIR) spectroscopy. Desorption was carried out at 150, 250 and 350 °C. The objective is to estimate the nature and concentration of acid sites. A comparison between the binary (Cu(x)X, Zn(x)X) and ternary (CuZn(x)X) exchanges was also established (x = level of exchange) through the Cu(43)X, Zn(48)X and CuZn(50)X samples. Lewis acidity decreases overall with desorption temperature and the level of exchange. As the latter increases, there is a conversion of some Lewis sites into those of Brønsted during thermal treatment. In return, the concentration of Brønsted sites increases with the degree of exchange. The Brønsted acidity of CuZn(50)X at 350 °C is more important than the sum of those of Cu(43)X and Zn(48)X. The found values were 73, 32 and 15 μmol g-1, respectively. Besides, the concentration of Brønsted sites for CuZn(50)X increases with desorption temperature. These features indicate the presence of a synergistic effect amplifying the strength of these sites when Cu2+ and Zn2+ cations compete for the occupancy of sites distributed inside zeolitic cavities.

Keywords: acidity, adsorption, pyridine, zeolites

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Authors: Nedal N. Marei, Nashaat Nassar

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Many treatment techniques have been used to remove the soluble pollutants from wastewater as; dyes and metal ions which could be found in rich amount in the used water of the textile and tanneries industry. The effluents from these industries are complex, containing a wide variety of dyes and other contaminants, such as dispersants, acids, bases, salts, detergents, humectants, oxidants, and others. These techniques can be divided into physical, chemical, and biological methods. Adsorption has been developed as an efficient method for the removal of heavy metals from contaminated water and soil. It is now recognized as an effective method for the removal of both organic and inorganic pollutants from wastewaters. Nanosize materials are new functional materials, which offer high surface area and have come up as effective adsorbents. Nano alumina is one of the most important ceramic materials widely used as an electrical insulator, presenting exceptionally high resistance to chemical agents, as well as giving excellent performance as a catalyst for many chemical reactions, in microelectronic, membrane applications, and water and wastewater treatment. In this study, methylene blue (MB) dye has been used as model dye of textile wastewater in order to synthesize a synthetic MB wastewater. NiO nanoparticles were added in small percentage in the sand packed bed adsorption columns to remove the MB from the synthetic textile wastewater. Moreover, different parameters have been evaluated; flow of the synthetic wastewater, pH, height of the bed, percentage of the NiO to the sand in the packed material. Different mathematical models where employed to find the proper model which describe the experimental data and help to analyze the mechanism of the MB adsorption. This study will provide good understanding of the dyes adsorption using metal oxide nanoparticles in the classical sand bed.

Keywords: adsorption, column, nanoparticles, methylene

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Authors: Bienvenu Gael Fouda Mbanga

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This study reports a new approach of preparation of carbon nanoparticles coated cerium oxide nanorods (CNPs/CeONRs) nanocomposite and reusing the spent adsorbent of Cd2+- CNPs/CeONRs nanocomposite for latent fingerprint detection (LFP) after removing Cd2+ ions from aqueous solution. CNPs/CeONRs nanocomposite was prepared by using CNPs and CeONRs with adsorption processes. The prepared nanocomposite was then characterized by using UV-visible spectroscopy (UV-visible), Fourier transforms infrared spectroscopy (FTIR), X-ray diffraction pattern (XRD), scanning electron microscope (SEM), Transmission electron microscopy (TEM), Energy-dispersive X-ray spectroscopy (EDS), Zeta potential, X-ray photoelectron spectroscopy (XPS). The average size of the CNPs was 7.84nm. The synthesized CNPs/CeONRs nanocomposite has proven to be a good adsorbent for Cd2+ removal from water with optimum pH 8, dosage 0. 5 g / L. The results were best described by the Langmuir model, which indicated a linear fit (R2 = 0.8539-0.9969). The adsorption capacity of CNPs/CeONRs nanocomposite showed the best removal of Cd2+ ions with qm = (32.28-59.92 mg/g), when compared to previous reports. This adsorption followed pseudo-second order kinetics and intra particle diffusion processes. ∆G and ∆H values indicated spontaneity at high temperature (40oC) and the endothermic nature of the adsorption process. CNPs/CeONRs nanocomposite therefore showed potential as an effective adsorbent. Furthermore, the metal loaded on the adsorbent Cd2+- CNPs/CeONRs has proven to be sensitive and selective for LFP detection on various porous substrates. Hence Cd2+-CNPs/CeONRs nanocomposite can be reused as a good fingerprint labelling agent in LFP detection so as to avoid secondary environmental pollution by disposal of the spent adsorbent.

Keywords: Cd2+-CNPs/CeONRs nanocomposite, cadmium adsorption, isotherm, kinetics, thermodynamics, reusable for latent fingerprint detection

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Authors: Trevor C. Brown, David J. Miron

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Gas-solid physical adsorption methods are central to the characterization and optimization of the effective surface area, pore size and porosity for applications such as heterogeneous catalysis, and gas separation and storage. Properties such as adsorption uptake, capacity, equilibrium constants and Gibbs free energy are dependent on the composition and structure of both the gas and the adsorbent. However, challenges remain, in accurately calculating these properties from experimental data. Gas adsorption experiments involve measuring the amounts of gas adsorbed over a range of pressures under isothermal conditions. Various constant-parameter models, such as Langmuir and Brunauer-Emmett-Teller (BET) theories are used to provide information on adsorbate and adsorbent properties from the isotherm data. These models typically do not provide accurate interpretations across the full range of pressures and temperatures. The Langmuir adsorption isotherm is a simple approximation for modelling equilibrium adsorption data and has been effective in estimating surface areas and catalytic rate laws, particularly for high surface area solids. The Langmuir isotherm assumes the systematic filling of identical adsorption sites to a monolayer coverage. The BET model is based on the Langmuir isotherm and allows for the formation of multiple layers. These additional layers do not interact with the first layer and the energetics are equal to the adsorbate as a bulk liquid. This BET method is widely used to measure the specific surface area of materials. Both Langmuir and BET models assume that the affinity of the gas for all adsorption sites are identical and so the calculated adsorbent uptake at the monolayer and equilibrium constant are independent of coverage and pressure. Accurate representations of adsorption data have been achieved by extending the Langmuir and BET models to include pressure-varying uptake capacities and equilibrium constants. These parameters are determined using a novel regression technique called flexible least squares for time-varying linear regression. For isothermal adsorption the adsorption parameters are assumed to vary slowly and smoothly with increasing pressure. The flexible least squares for pressure-varying linear regression (FLS-PVLR) approach assumes two distinct types of discrepancy terms, dynamic and measurement for all parameters in the linear equation used to simulate the data. Dynamic terms account for pressure variation in successive parameter vectors, and measurement terms account for differences between observed and theoretically predicted outcomes via linear regression. The resultant pressure-varying parameters are optimized by minimizing both dynamic and measurement residual squared errors. Validation of this methodology has been achieved by simulating adsorption data for n-butane and isobutane on activated carbon at 298 K, 323 K and 348 K and for nitrogen on mesoporous alumina at 77 K with pressure-varying Langmuir and BET adsorption parameters (equilibrium constants and uptake capacities). This modeling provides information on the adsorbent (accessible surface area and micropore volume), adsorbate (molecular areas and volumes) and thermodynamic (Gibbs free energies) variations of the adsorption sites.

Keywords: Langmuir adsorption isotherm, BET adsorption isotherm, pressure-varying adsorption parameters, adsorbate and adsorbent properties and energetics

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