Faculty Publications
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Item Kinetic and thermodynamic studies on the adsorption of heavy metals from aqueous solution by melanin nanopigment obtained from marine source: Pseudomonas stutzeri(Academic Press, 2018) Manirethan, V.; Raval, K.; Rajan, R.; Thaira, H.; Mohan Balakrishnan, R.M.The difficulty in removal of heavy metals at concentrations below 10 mg/L has led to the exploration of efficient adsorbents for removal of heavy metals. The adsorption capacity of biosynthesized melanin for Mercury (Hg(II)), Chromium (Cr(VI)), Lead (Pb(II)) and Copper (Cu(II)) was investigated at different operating conditions like pH, time, initial concentration and temperature. The heavy metals adsorption process was well illustrated by the Lagergren's pseudo-second-order kinetic model and the equilibrium data fitted excellently to Langmuir isotherm. Maximum adsorption capacity obtained from Langmuir isotherm for Hg(II) was 82.4 mg/g, Cr(VI) was 126.9 mg/g, Pb(II) was 147.5 mg/g and Cu(II) was 167.8 mg/g. The thermodynamic parameters revealed that the adsorption of heavy metals on melanin is favorable, spontaneous and endothermic in nature. Binding of heavy metals on melanin surface was proved by Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). Contemplating the results, biosynthesized melanin can be a potential adsorbent for efficient removal of Hg(II), Cr(VI), Pb(II) and Cu(II) ions from aqueous solution. © 2018 Elsevier LtdItem Adsorptive removal of trivalent and pentavalent arsenic from aqueous solutions using iron and copper impregnated melanin extracted from the marine bacterium Pseudomonas stutzeri(Elsevier Ltd, 2020) Manirethan, V.; Raval, K.; Mohan Balakrishnan, R.M.The metalloid arsenic is one of the most conspicuous groundwater contaminants in the Indian subcontinent and its removal from aqueous medium is the main focus of this study. The study aims at functionalising melanin using iron and copper for the efficient removal of arsenic and rendering water fit for consumption. Melanin obtained from the marine bacteria Pseudomonas stutzeri was functionalised by iron impregnation (Fe-melanin) and copper impregnation (Cu-melanin). Morphological studies using FESEM portrayed the impregnated iron and copper granules on the surface of melanin, while XRD analysis confirmed the presence of Fe2O3 and CuO on melanin. Adsorption studies on As (V) and As (III) were conducted using Fe-melanin and Cu-melanin for different operating variables like pH, temperature and contact time. More than 99% per cent of As (III) and As (V) from water was removed at a pH range between 4 and 6 within 50 min in the case of Fe-melanin and 80 min for Cu-melanin. Adsorption equilibrium studies showed better fit with Langmuir adsorption isotherm and had good agreement with Redlich-Peterson's three-parameter model. The maximum adsorption capacities of Fe-melanin and Cu-melanin obtained from Langmuir adsorption model are 50.12 and 20.39 mg/g, respectively, for As (V) and similarly 39.98 and 19.52 mg/g, respectively, for As (III). Arsenic-binding to the functionalised melanin was confirmed using FT-IR and the XPS analysis. Reuse of the adsorbent was effectively done by desorbing the iron and copper together with the bound As (III) and As (V) and further re-impregnation of iron and copper in melanin. Re-functionalised melanin showed 99% adsorption efficiency up to four cycles of adsorption/desorption. A novel iron and copper impregnated melanin was synthesized to remove As (III) and As (V) from groundwater and the adsorption process was optimized. © 2019 Elsevier LtdItem Removal of methylene blue dye using nano zerovalent iron, nanoclay and iron impregnated nanoclay-a comparative study(Royal Society of Chemistry, 2021) Tarekegn, M.M.; Mohan Balakrishnan, R.M.; Hiruy, A.M.; Hussen, A.H.There has been an increasing challenge from the emission of methylene blue (MB) dye-containing wastewater and its management methods in industry. The sorption process is one conventionally used method. In this study, nanoclay, nano zero valent iron (nZVI), and iron impregnated nanoclay were prepared and studied for the removal of MB dye in batch mode. The effects of operating parameters like pH, dye concentration, sorbent dosage, and contact time were investigated and optimized. The nZVI, nanoclay, and iron impregnated nanoclay sorbents showed zeta potentials of -32.1, -53.4, and -40.7 mV, respectively. All the nano adsorbents were crystalline. The nanoclay was characterized by an average surface area, pore volume and pore diameter of 43.49 m2 g-1, 0.104 cm3 g-1 and 2.806 nm, respectively. nZVI showed a surface area of 47.125 m2 g-1, pore volume of 0.119 cm3 g-1, and pore diameter of 3.291 nm. And iron impregnated nanoclay showed a surface area of 73.110 m2 g-1 with a pore volume of 15 cm3 g-1 and a pore diameter size of 3.83 nm. A Langmuir EXT nitrogen gas adsorption isotherm (R2 ? 0.99) was the best fit. The thermodynamics parameters, such as ?G° (-12.64 to -0.63 kJ mol-1), ?H° (+0.1 to +62.15 kJ mol-1) and ?S° (+0.10 to +0.22 kJ mol-1), confirmed that a spontaneous and endothermic adsorption process took place at a high rate of disorder. Iron impregnated nanoclay showed higher negative Gibbs free energy (-12.64 kJ mol-1), higher enthalpy change (+62.5 kJ mol-1) and entropy (+0.22 kJ mol-1) and gave a better MB removal performance. In addition, the lower negative heat of enthalpy for all adsorptions proved the dominance of physisorption. The methylene blue adsorption isotherm on nZVI and nanoclay showed the best fit with the Freundlich isotherm model with correlation coefficients (R2) ?0.98 and 0.99, respectively. Whereas the Langmuir adsorption isotherm was the best fit for iron impregnated nanoclay (R2 ? 0.98). The adsorption activities of nZVI, nanoclay and iron impregnated nanoclay were fitted to a pseudo-second-order kinetic model with correlation coefficients (R2) of 0.999, 0.997 and 0.983, respectively. The optimal pH 7.0 (RE: 99.1 ± 0.73%), initial MB concentration 40 ppm (RE: 99.9 ± 0.03%), contact time 120 min (RE: 99.9 ± 0.9%), and adsorbent dose 80 (99.9 ± 0.03%) were obtained for iron impregnated nanoclay. The optimal operational parameters of nanoclay and nZVI, respectively, were pH 11.0 and 13.0, initial MB concentration 20 and 20 ppm, adsorbent dose 100 and 140 mg, and contact time 120 and 140 min. In general, iron impregnated nanoclay has shown promising cationic dye adsorbance for industrial applications; but a recyclability test is suggested before scale-up. © The Royal Society of Chemistry.Item Adsorption of selective fluoroquinolones by cysteine modified silane magnetic nanocomposite from the aqueous phase(Institute for Ionics, 2023) Senathiraja, T.; Lolla, S.A.; Singh, Y.; Kollarahithlu, S.C.; Mohan Balakrishnan, R.M.Elevated levels of pharmaceutical pollutants in the aquatic environment have caused detrimental effects on water quality and biodiversity. Nanomaterials are among the most promising technologies to detect, adsorb, and remove these pollutants from the aqueous systems. The current work explores the applicability of nickel ferrite nanocomposite functionalized with L-cysteine attached 3-glycidyloxypropyltrimethoxysilane to remove a selective class of antibiotics known as fluoroquinolones (Lomefloxacin, Ciprofloxacin, and Norfloxacin). 20 mg of this nanocomposite achieve maximum removal efficiencies of 61%, 67%, and 75% for 40 mg L−1 of lomefloxacin, norfloxacin, and ciprofloxacin, respectively. The nanocomposites also show good regeneration capacity with negligible reduction in the efficiencies up to three cycles. Furthermore, adsorption isotherms such as Langmuir and Freundlich isotherms were used to characterize the removal of fluoroquinolones from the aqueous phase by the nanocomposites. The results show that the adsorption process was in good agreement with the Langmuir isotherm, thus confirming its monolayer sorption process and also reveals that adsorption kinetics follows a pseudo-second-order model. The maximum adsorption capacity of functionalized nickel ferrite nanocomposites are 122 mg g−1, 135 mg g−1, and 150 mg g−1 for lomefloxacin, norfloxacin, and ciprofloxacin, respectively. Overall, all the results obtained indicate that the nickel ferrite nanocomposite functionalized with L-cysteine attached 3-glycidyloxypropyltrimethoxysilane is an effective adsorbent to remove fluoroquinolones from the aqueous systems and could be potentially incorporated in water treatment processes under well-defined parameters. © 2022, The Author(s) under exclusive licence to Iranian Society of Environmentalists (IRSEN) and Science and Research Branch, Islamic Azad University.Item Functionalization of β-cyclodextrin onto NiFe2O4 nanoparticles for the removal of ketoprofen and diclofenac from the aqueous solutions(Institute for Ionics, 2024) Ilango, I.; Mohan Balakrishnan, R.M.; Visvanathan, C.; Bui, X.-T.; Velusamy, P.A new β-CD functionalized nickel ferrite nanocomposite was synthesized and used to remove pharmaceutical drugs, such as ketoprofen (KF) and diclofenac (DCF). The co-precipitation approach was utilised to synthesize nickel ferrite (NFO) nanoparticles, which were then functionalized with TEOS to form NFO@SiO2; β-cyclodextrin was then functionalized using GPTMS as an interface to form NFO@SiO2@β-CD. FTIR, ZD, FE-SEM, EDX, TGA/DTG, VSM, BET, zeta potential and particle size analysis were then used to characterise the nanocomposites. The NFO@SiO2@β-CD has an average diameter of 109.1 nm, superparamagnetic behaviour, a mesoporous surface and a specific surface of 20.78 m2/g. The functionalized NFO@SiO2@ β-CD nanocomposite removed 94% of diclofenac in 5 min and 80% of ketoprofen in 360 min with the adsorption capacities of 8.46 and 0.54 mg/g, respectively. The obtained experimental datum for both the pollutants was fitted in kinetic and isotherm models, with the pseudo-second-order kinetic model and Freundlich adsorption isotherm showing the best fit with the highest regression of R 2 = 0.99. The nanocomposite was regenerated using 0.1 M NaOH and recycled for about four consecutive cycles in which the reduction in the removal efficiency of ketoprofen and diclofenac was observed to be 51.36% and 64%, respectively. These results suggested that the NFO@SiO2@β-CD nanocomposite could be used specifically to target the low-concentrated pharmaceutical pollutants. Graphical Abstract: Schematic representation of Functionalization of β-Cyclodextrin onto NiFe2O4 nanoparticles for the removal of ketoprofen and diclofenac from the aqueous solutions. [Figure not available: see fulltext.] © 2023, The Author(s) under exclusive licence to Iranian Society of Environmentalists (IRSEN) and Science and Research Branch, Islamic Azad University.
