Optimizing methanol synthesis from CO2 using graphene-based heterogeneous photocatalyst under RSM and ANN-driven parametric optimization for achieving better suitability.

Assessment of the performance of linear and nonlinear regression-based methods for estimating in situ catalytic CO2 transformations employing TiO2/Cu coupled with hydrogen exfoliation graphene (HEG) has been investigated. The yield of methanol was thoroughly optimized and predicted using response surface methodology (RSM) and artificial neural network (ANN) model after rigorous experimentation and comparison. Amongst the different types of HEG loading from 10 to 40 wt%, the 30 wt% in the HEG-TiO2/Cu assisted photosynthetic catalyst was found to be successful in providing the highest conversion efficiency of methanol from CO2. The most influencing parameters, HEG dosing and inflow rate of CO2, were found to affect the conversion rate in the acidic reaction regime (at pH of 3). According to RSM and ANN, the optimum methanol yields were 36.3 mg g-1 of catalyst and 37.3 mg g-1 of catalyst, respectively. Through the comparison of performances using the least squared error analysis, the nonlinear regression-based ANN showed a better determination coefficient (overall R2 > 0.985) than the linear regression-based RSM model (overall R2 ∼ 0.97). Even though both models performed well, ANN, consisting of 9 neurons in the input and 1 hidden layer, could predict optimum results closer to RSM in terms of agreement with the experimental outcome.

Diamondoid Ni(II) Coordination Polymer as an Electrocatalyst for Hydrogen and Oxygen Evolution Reactions and Overall Water Splitting.

We have successfully synthesized a new Ni(II)-based coordination polymer (CP) [Ni2(cis-1,4-chdc)2(4,4'-bpy)3(H2O)2] (1); (cis-1,4- H2chdc=cis-1,4-cyclohexanedicarboxylic acid and 4,4'-bpy=4,4'-bipyridine) employing slow diffusion method in a single pot technique. The connectivity of Ni(II) ions and bridging cis-1,4-chdc ligand gives rise to a three-dimensional (3D) framework with 2-fold interpenetrated diamondoid topology. Interestingly, the synthesized CP acts as efficient catalyst for electrocatalytic water splitting. The water oxidation activity of compound 1 exhibits Tafel slope equivalent to 361.48 mV.dec-1 for hydrogen evolution reaction (HER) and 353.53 mV.dec-1 for oxygen evolution reaction (OER) in an alkaline medium while almost similar values of Tafel slope for HER and OER equivalent to 287.33 mV.dec-1 and 289.93 mV.dec-1 respectively in acidic medium. Thus, the compound 1 has excellent efficacy in catalyzing HER and OER in acidic as well as alkaline medium, which is ascribed to its distinctive 3D architecture.

Advanced oxidation of polycyclic aromatic hydrocarbons in tropical soil: Self-catalytic utilization of natural iron contents in an oxygenation reactor supported with persulfate.

The catalysts derived from natural iron minerals in the advanced oxidation process offer several advantages. However, their utilization in soil remediation is restricted due to the presence of soil impurities, which can inhibit the catalytic activity of these minerals. The soils in tropical regions exhibit lower organic matter content, limited cation exchange capacity, and are non-saline, this enhances the efficiency of utilizing natural iron minerals from tropical soil as a catalyst. In this regard, the catalytic potential of naturally iron-bearing tropical soil was investigated to eliminate phenanthrene (PHE), pyrene (PYR), and benzo[α]pyrene (B[α]P) using an oxygenated reactor supported with persulfate (PS). The system showed an efficient performance, and the removal efficiencies under the optimum conditions were 81 %, 73 %, and 86 % for PHE, PYR, and B[α]P, respectively. This indicated that the catalytic activity of iron was working efficiently. However, there were changes in the soil characteristics after the remediation process such as a significant reduction in iron and aluminum contents. The scavenging experiments demonstrated that HO• had a minor role in the oxidation process, SO4•- and O2•- emerged as the primary reactive species responsible for the effective degradation of the PAHs. Moreover, the by-products were monitored after soil remediation to evaluate their toxicity and to propose degradation pathways. The Mutagenicity test showed that two by-products from each PHE and B[α]P had positive results, while only one by-product of PYR showed positive. The toxicity tests of oral rat LD50 and developmental toxicity tests revealed that certain PAHs by-products could be more toxic from the parent pollutant itself. This study represents a notable progression in soil remediation by providing a step forward in the application of the advanced oxidation process (AOP) without requiring additional catalysts to activate oxidants and degrade pollutant PAHs from the soil.

Two-Phase Crude Oil-Water Flow Through Different Pipes: An Experimental Investigation Coupled with Computational Fluid Dynamics Approach.

The present study deals with two-phase non-Newtonian pseudoplastic crude oil and water flow inside horizontal pipes simulated by ANSYS. The study helps predict velocity and velocity profiles, as well as pressure drop during two-phase crude-oil-water flow, without complex calculations. Computational fluid dynamics (CFD) analysis will be very important in reducing the experimental cost and the effort of data acquisition. Three independent horizontal stainless steel pipes (SS-304) with inner diameters of 1 in., 1.5 in., and 2 in. were used to circulate crude oil with 5, 10, and 15% v/v water for simulation purposes. The entire length of the pipes, along with their surfaces, were insulated to reduce heat loss. A grid size of 221,365 was selected as the optimal grid. Two-phase flow phenomena, pressure drop calculations, shear stress on the walls, along with the rate of shear strain, and phase analysis were studied. Moreover, velocity changes from the wall to the center, causing a velocity gradient and shear strain rate, but at the center, no velocity variation (velocity gradient) was observed between the layers of the fluid. The precision of the simulation was investigated using three error parameters, such as mean square error, Nash-Sutcliffe efficiency, and RMSE-standard deviation of observation ratio. From the simulation, it was found that CFD analysis holds good agreement with experimental results. The uncertainty analysis demonstrated that our CFD model is helpful in predicting the rheological parameters very accurately. The study aids in identifying and predicting fluid flow phenomena inside horizontal straight pipes in a very effective way.

Screening of different growth conditions of Bacillus subtilis isolated from membrane-less microbial fuel cell toward antimicrobial activity profiling.

Bacteriocins produced by Bacillus subtilis have gained recognition for their safe use in humans. In this study, we aimed to assess the inhibitory activity of an antimicrobial peptide synthesized by the wild-type strain of B. subtilis against the notorious pathogen Pseudomonas aeruginosa. Our investigation employed the broth microdilution method to evaluate the inhibitory potential of this peptide. Among the four different pathogen strains tested, P. aeruginosa exhibited the highest susceptibility, with an inhibition rate of 29.62%. In parallel, we explored the cultivation conditions of B. subtilis, recognizing the potential of this versatile bacterium for applications beyond antimicrobial production. The highest inhibitory activity was achieved at pH 8, with an inhibition rate of 20.18%, indicating the potential for optimizing pH conditions for enhanced antimicrobial peptide production. For the kinetics of peptide production, the study explored different incubation periods and agitation levels. Remarkably, the highest activity of B. subtilis was observed at 24 h of incubation, with an inhibition rate of 44.93%. Finally, the study focused on the isolation of the antimicrobial peptide from the cell-free supernatant of B. subtilis using ammonium sulfate precipitation at various concentrations. The highest recorded activity was an impressive 89.72% achieved at an 80% concentration.

Layer-by-Layer Assembly of CTAB-rGO-Modified MXene Hybrid Films as Multifunctional Electrodes for Hydrogen Evolution and Oxygen Evolution Reactions, Supercapacitors, and DMFC Applications.

Exceptional electrical conductivity and abundance of surface terminations like-F- and OH- leading to hydrophilicity make the family of 2D transition metal carbides/nitrides and carbonitrides (MXene) excellent candidates for energy storage and conversion applications. MXenes, however, undergo restacking of nanosheets via van der Waals interaction, hindering the active sites, leading to slow electronic and ionic kinetics, and ultimately affecting their electrochemical performance. Herein, we report binder-free cetyltrimethylammonium bromide-reduced graphene oxide (CTAB-rGO)-modified MXene hybrid films on nickel foam as a promising noble metal-free multifunctional electrode synthesized via layer-by-layer assembly and dip coating techniques, which effectively reduce restacking while improving the kinetics. The properties of the as-prepared electrocatalysts are investigated using various physiochemical characterizations and electrochemical measurements to accomplish the objective of "creating one kind of electrocatalyst for multiapplication" with a thorough understanding of the relationship between the material structure, morphology, and electrocatalytic performance. In energy conversion, the synergetic effect of MXene and the CTAB-rGO support helped increase the catalytic activity of the composite for electrochemical water splitting, demonstrating a current density of 10 mA/cm2 at an overpotential (η) of 360 V and a Tafel slope value of 56.6 mV/dec for hydrogen evolution reaction and a current density of 10 mA/cm2 at an overpotential (η) of 179 mV and a Tafel slope value of 47.03 mV/dec for oxygen evolution reaction in an alkaline medium. The electrode material also exhibited a higher oxidation current density (373.60 mA/cm2) compared to that of synthesized MXene toward methanol oxidation reaction in direct methanol fuel cell application. Additionally, the energy storage potential of CTAB-rGO modified MXene as electrode materials for supercapacitors with a high specific capacitance (544.50 F g-1 at 0.5 A g-1) and a good capacity retention of 87% after 5000 cycles was studied. These findings of this work showcase the potential of the electrocatalyst in both conversion and storage of electrochemical energy.

Efficiency of Fabricated Adsorptive Polysulfone Mixed Matrix Membrane for Acetic Acid Separation.

The ultrafiltration mixed matrix membrane (UF MMMs) process represents an applicable approach for the removal of diluted acetic acid at low concentrations, owing to the low pressures applied. The addition of efficient additives represents an approach to further improve membrane porosity and, subsequently, enhance acetic acid removal. This work demonstrates the incorporation of titanium dioxide (TiO2) and polyethylene glycol (PEG) as additives into polysulfone (PSf) polymer via the non-solvent-induced phase-inversion (NIPS) method to improve the performance of PSf MMMs performance. Eight PSf MMMs samples designated as M0 to M7, each with independent formulations, were prepared and investigated for their respective density, porosity, and degree of AA retention. Morphology analysis through scanning electron microscopy elucidated sample M7 (PSf/TiO2/PEG 6000) to have the highest density and porosity among all samples with concomitant highest AA retention at approximately 92.2%. The application of the concentration polarization method further supported this finding by the higher concentration of AA solute present on the surface of the membrane compared to that of AA feed for sample M7. Overall, this study successfully demonstrates the significance of TiO2 and PEG as high MW additives in improving PSf MMM performance.

The Use of Essential Oil Embedded in Polylactic Acid/Chitosan-Based Film for Mango Post-Harvest Application against Pathogenic Fungi.

Mango has a high global demand. Fruit fungal disease causes post-harvest mango and fruit losses. Conventional chemical fungicides and plastic prevent fungal diseases but they are hazardous to humans and the environment. Direct application of essential oil for post-harvest fruit control is not a cost-effective approach. The current work offers an eco-friendly alternative to controlling the post-harvest disease of fruit using a film amalgamated with oil derived from Melaleuca alternifolia. Further, this research also aimed to assess the mechanical, antioxidant, and antifungal properties of the film infused with essential oil. ASTM D882 was performed to determine the tensile strength of the film. The antioxidant reaction of the film was assessed using the DPPH assay. In vitro and in vivo tests were used to evaluate the inhibitory development of the film against pathogenic fungi, by comparing the film with different levels of essential oil together with the treatment of the control and chemical fungicide. Disk diffusion was used to evaluate mycelial growth inhibition, where the film incorporated with 1.2 wt% essential oil yielded the best results. For in vivo testing of wounded mango, the disease incidence was successfully reduced. For in vivo testing of unwounded mango to which the film incorporated with essential oil was applied, although some quality parameters such as the color index were not significantly affected, weight loss was reduced, soluble solid content was increased, and firmness was increased, compared to the control. Thus, the film incorporated with essential oil (EO) from M. alternifolia can be an environmentally friendly alternative to the conventional approach and the direct application of essential oil to control post-harvest disease in mango.

Hydrothermal Conversion of Food Waste to Carbonaceous Solid Fuel-A Review of Recent Developments.

This review critically discussed recent developments in hydrothermal carbonization (HTC) of food waste and its valorization to solid fuel. Food waste properties and fundamentals of the HTC reactor were also covered. The review further discussed the effect of temperature, contact time, pressure, water-biomass ratio, and heating rate on the HTC of food waste on the physiochemical properties of hydrochar. Literature review of the properties of the hydrochar produced from food waste in different studies shows that it possesses elemental, proximate, and energy properties that are comparable to sub-bituminous coal and may be used directly as fuel or co-combusted with coal. This work conclusively identified the existing research gaps and provided recommendation for future investigations.

Separation of Chromium (VI), Copper and Zinc: Chemistry of Transport of Metal Ions across Supported Liquid Membrane.

Prior to applying supported liquid membranes (SLM) with strip dispersion for separation of chromium (VI), copper and zinc, suitable chemical settings were determined through solvent extraction and stripping studies. More than 90% of copper and zinc could be simultaneously extracted with at least 3% (v/v) di-(2-ethylhexyl)phosphoric acid (D2EHPA) at a feed equilibrium pH in the range of 3.5-5.0. For stripping, theoretical model equations derived and experimental results revealed that suitable concentrations of lower acid strength reagents can strip metals that have weaker metal-extractant bond without significantly stripping metals that have a stronger metal-extractant bond. Therefore, in a setup comprising three compartments separated by two SLM, we propose to fill the three compartments in the following order: feed-strip dispersion containing low acid strength reagent-strong acid. An organic phase with 4% (v/v) D2EHPA was used. From stripping experiments, 0.2 mol/L pH 3 citrate buffer, which resulted in the highest copper recovery (88.8%) and solution purity (99.0%), was employed as the low acid strength reagent while the strong acid consisted of 1 mol/L sulfuric acid. In 26 h, 99.1% copper was recovered by citrate buffer with 99.8% purity and 95.1% zinc was recovered by sulfuric acid with 98.4% purity. Chromium (VI), copper and zinc could be separated effectively using this separation strategy.

Comparative Investigation of the Physicochemical Properties of Chars Produced by Hydrothermal Carbonization, Pyrolysis, and Microwave-Induced Pyrolysis of Food Waste.

This work presents a comparative study of the physicochemical properties of chars derived by three thermochemical pathways, namely: hydrothermal carbonization, HTC (at 180, 200 and 220 °C), pyrolysis, PY, (at 500, 600 and 700 °C) and microwave assisted pyrolysis, MW (at 300, 450 and 600 W). The mass yield of HTC samples showed a decrease (78.7 to 26.7%) as the HTC temperature increased from 180 to 220 °C. A similar decreasing trend in the mass yield was also observed after PY (28.45 to 26.67%) and MW (56.45 to 22.44%) of the food waste mixture from 500 to 700 °C and 300 to 600 W, respectively. The calorific value analysis shows that the best among the chars prepared by three different heating methods may be ranked according to the decreasing value of the heating value as: PY500, MW300, and HTC180. Similarly, a decreasing trend in H/C values was observed as: PY500 (0.887), MW300 (0.306), and HTC180 (0.013). The scanning electron microscope (SEM) analyses revealed that the structure of the three chars was distinct due to the different temperature gradients provided by the thermochemical processes. The results clearly show that the suitable temperature for the HTC and PY of food waste was 180 °C and 500 °C, respectively, while the suitable power for the MW of food waste was 300 W.

Metal-Based Nanocomposite Materials for Efficient Photocatalytic Degradation of Phenanthrene from Aqueous Solutions.

Polycyclic aromatic hydrocarbons (PAHs) are a class of naturally occurring chemicals resulting from the insufficient combustion of fossil fuels. Among the PAHs, phenanthrene is one of the most studied compounds in the marine ecosystems. The damaging effects of phenanthrene on the environment are increasing day by day globally. To lessen its effect on the environment, it is essential to remove phenanthrene from the water resources in particular and the environment in general through advanced treatment methods such as photocatalytic degradation with high-performance characteristics and low cost. Therefore, the combination of metals or amalgamation of bimetallic oxides as an efficient photocatalyst demonstrated its propitiousness for the degradation of phenanthrene from aqueous solutions. Here, we reviewed the different nanocomposite materials as a photocatalyst, the mechanism and reactions to the treatment of phenanthrene, as well as the influence of other variables on the rate of phenanthrene degradation.

Carbon Based Polymeric Nanocomposites for Dye Adsorption: Synthesis, Characterization, and Application.

Agglomeration and restacking can reduce graphene oxide (GO) activity in a wide range of applications. Herein, GO was synthesized by a modified Hummer's method. To minimize restacking and agglomeration, in situ chemical oxidation polymerization was carried out to embed polyaniline (PANI) chains at the edges of GO sheets, to obtain GO-PANI nanocomposite. The GO-PANI was tested for the adsorptive removal of brilliant green (BG) from an aqueous solution through batch mode studies. Infrared (FT-IR) analysis revealed the dominance of hydroxyl and carboxylic functionalities over the GO-PANI surface. Solution pH-dependent BG uptake was observed, with maximum adsorption at pH 7, and attaining equilibrium in 30 min. The adsorption of BG onto GO-PANI was fit to the Langmuir isotherm, and pseudo-second-order kinetic models, with a maximum monolayer adsorption capacity (qm) of 142.8 mg/g. An endothermic adsorption process was observed. Mechanistically, π-π stacking interaction and electrostatic interaction played a critical role during BG adsorption on GO-PANI.

Dinuclear uranium(VI) salen coordination compound: an efficient visible-light-active catalyst for selective reduction of CO2 to methanol.

A new dinuclear uranyl salen coordination compound, [(UO2)2(L)2]·2MeCN [L = 6,6'-((1E,1'E)-((2,2-dimethylpropane-1,3-diyl)bis(azaneylylidene))-bis(methaneylylidene))bis(2-methoxyphenol)], was synthesized using a multifunctional salen ligand to harvest visible light for the selective photocatalytic reduction of CO2 to MeOH. The assembling of the two U centers into one coordination moiety via a chelating-bridging doubly deprotonated tetradentate ligand allowed the formation of U centers with distorted pentagonal bipyramid geometry. Such construction of compounds leads to excellent activity for the photocatalytic reduction of CO2, permitting a production rate of 1.29 mmol g-1 h-1 of MeOH with an apparent quantum yield of 18%. Triethanolamine (TEOA) was used as a sacrificial electron donor to carry out the photocatalytic reduction of CO2. The selective methanol formation was purely a photocatalytic phenomenon and confirmed using isotopically labeled 13CO2 and product analysis by 13C-NMR spectroscopy. The spectroscopic studies also confirmed the interaction of CO2 with the molecule of the title complex. The results of these efforts made it possible to understand the reaction mechanism using ESI-mass spectrometry.

Development of Ultra-Performance Liquid Chromatography-Mass Spectrometry Method for Simultaneous Determination of Three Cationic Dyes in Environmental Samples.

Lower dye concentrations and the presence of several dyes along with other matrices in environmental samples restrict their determination. Herein, a highly sensitive and rapid ultra-performance tandem mass spectrometric method was developed for simultaneous determination of cationic dyes, namely methylene blue (MB), rhodamine B (RB) and crystal violet (CV), in environmental samples. To preconcentrate environmental samples, solid-phase extraction cartridges were developed by using hydrogen peroxide modified pistachio shell biomass (MPSB). The surface morphological and chemical functionalities of MPSB were well characterized. The developed method was validated considering different validation parameters. In terms of accuracy and precision, the %RSD for all three dyes at all four concentration points was found to be between 1.26 and 2.76, while the accuracy reported in terms of the recovery was found to be 98.02%-101.70%. The recovery was found to be in the range of 98.11% to 99.55%. The real sample analysis shows that MB, RB, and CV were found in the ranges of 0.39-5.56, 0.32-1.92 and 0.27-4.36 µg/mL, respectively.

Oil industry waste based non-magnetic and magnetic hydrochar to sequester potentially toxic post-transition metal ions from water.

Solid waste conversion to value-added products is a stepping stone towards sustainable environment. Herein, sesame oil cake (SOC), an oil industry waste was utilized as a precursor to develop hydrochar (HC) samples by varying reaction temperature (150-250 °C) and time span (2-8 h), chemically treated with 10% H2O2 to optimize a sample with maximum yield and Pb(II) adsorption. Highest yield (29.2 %) and Pb(II) (24.57 mg/g at Co: 15 mg/L) adsorption was observed on SOCHC@200 °C/6 h, magnetized (mSOCHC@200 °C/6 h) for comparative study. XRD displayed highly crystalline SOCHC@200 °C/6 h and amorphous mSOCHC@200 °C/6 h, both having a characteristic cellulose peak at 14.9°. mSOCHC@200 °C/6 h displayed superparamagnetic behavior with 11.2 emu/g saturation magnetization. IR spectra confirmed the development of samples rich in oxygen containing functionalities; an additional peak for iron oxides appeared at 586 cm-1 in mSOCHC@200°C/6 h spectrum. Four major peaks at 531.9, 399.9, 348.2 and 284.7 eV, assigned to O 1s, N 1s, Ca 2p and C 1s, respectively were observed during XPS analyses. An additional peak at 710.3 eV, ascribed to Fe 2p was observed in mSOCHC@200C/6 h XPS spectrum, while a peak at 143.2 eV for Pb 4f appeared in spectra of both Pb(II) saturated samples. pH dependent (maximum at ∼6.7), exothermic Pb(II) adsorption was found. About 50-70% (at Co: 25 mg/L) adsorption on both SOCHC@200 °C/6 h and mSOCHC@200 °C/6 h was accomplished in a minute, attaining equilibrium in 180 and 240 min, respectively. Error functions and superimposed qe, exp. and qe, cal. values supported Langmuir isotherm model applicability, with respective qm values of 304.9 and 361.7 mg/g at 25 °C for SOCHC@200 °C/6 h and mSOCHC@200 °C/6 h. Kinetic data was fitted to PSO model. Highest (between 92.2 and 88.9 %) amount of Pb(II) from SOCHC@200 °C/6 h and mSOCHC@200 °C/6 h was eluted by 0.01 M HCl.

Bioflocculants Produced by Bacterial Strains Isolated from Palm Oil Mill Effluent for Application in the Removal of Eriochrome Black T Dye from Water.

Four strains of bioflocculant-producing bacteria were isolated from a palm oil mill effluent (POME). The four bacterial strains were identified as Pseudomonas alcaliphila (B1), Pseudomonas oleovorans (B2), Pseudomonas chengduensis (B3), and Bacillus nitratireducens (B4) by molecular identification. Among the four bacterial strains, Bacillus nitratireducens (B4) achieved the highest flocculating activity (49.15%) towards kaolin clay suspension after eight hours of cultivation time and was selected for further studies. The optimum conditions for Eriochrome Black T (EBT) flocculation regarding initial pH, type of cation, and B4 dosage were determined to be pH 2, Ca2⁺ cations, and a dosage of 250 mL/L of nutrient broth containing B4. Under these conditions, above 90% of EBT dye removal was attained. Fourier transform infrared spectroscopic (FT-IR) analysis of the bioflocculant revealed the presence of hydroxyl, alkyl, carboxyl, and amino groups. This bioflocculant was demonstrated to possess a good flocculating activity, being a promissory, low-cost, harmless, and environmentally friendly alternative for the treatment of effluents contaminated with dyes.

Removal of Rhodamine B from Water Using a Solvent Impregnated Polymeric Dowex 5WX8 Resin: Statistical Optimization and Batch Adsorption Studies.

Herein, commercially available Dowex 5WX8, a cation exchange polymeric resin, was modified through solvent impregnation with t-butyl phosphate (TBP) to produce a solvent impregnated resin (SIR), which was tested for the removal of rhodamine B (RhB) from water in batch adsorption experiments. The effect of SIR dosage, contact time, and pH on RhB adsorption was studied and optimized by response surface methodology (RSM), interaction, Pareto, and surface plots. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were respectively used for characterizing SIR surface morphology and identifying active binding sites before and after RhB adsorption. SEM showed that the pristine SIR surface was covered with irregular size and shape spots with some pores, while RhB saturated SIR surface was non-porous. FTIR revealed the involvement of electrostatic and π-π interactions during RhB adsorption on SIR. Dosage of SIR, contact time, and their interaction significantly affected RhB adsorption on SIR, while pH and its interaction with dosage and contact time did not. The optimum identified experimental conditions were 0.16 g of SIR dose and 27.66 min of contact time, which allowed for 98.45% color removal. Moreover, RhB adsorption equilibrium results fitted the Langmuir isotherm with a maximum monolayer capacity (qmax) of 43.47 mg/g.

Heteroatom-doped magnetic hydrochar to remove post-transition and transition metals from water: Synthesis, characterization, and adsorption studies.

Efforts to improve water quality have led to the development of green and sustainable water treatment approaches. Herein, nitrogen-doped magnetized hydrochar (mSBHC-N) was synthesized, characterized, and used for the removal of post-transition and transition heavy metals, viz. Pb2+ and Cd2+ from aqueous environment. mSBHC-N was found to be mesoporous (BET surface area - 62.5 m2/g) and paramagnetic (saturation magnetization - 44 emu/g). Both, FT-IR (with peaks at 577, 1065, 1609 and 3440 cm-1 corresponding to Fe - O stretching vibrations, C - N stretching, N - H in-plane deformation and stretching) and XPS analyses (with peaks at 284.4, 400, 530, 710 eV due to C 1s, N 1s, O 1s, and Fe 2p) confirmed the presence of oxygen and nitrogen containing functional groups on mSBHC-N. The adsorption of Pb2+ and Cd2+ was governed by oxygen and nitrogen functionalities through electrostatic and co-ordination forces. 75-80% of Pb2+ and Cd2+ adsorption at Co: 25 mg/L, either from deionized water or humic acid solution was accomplished within 15 min. The data was fitted to pseudo-second-order kinetic and Langmuir isotherm models, with maximum monolayer adsorption capacities being 323 and 357 mg/g for Cd2+and Pb2+ at 318 K, respectively. Maximum Cd2+ (82.6%) and Pb2+ (78.7%) were eluted with 0.01 M HCl, simultaneously allowing minimum iron leaching (2.73%) from mSBHC-N. In conclusion, the study may provide a novel, economical, and clean route to utilize agro-waste, such as sugarcane bagasse (SB), for aquatic environment remediation.

Unary and binary adsorption studies of lead and malachite green onto a nanomagnetic copper ferrite/drumstick pod biomass composite.

Modern-day practices are the major contributors in water quality deterioration, consequently results in clean water scarcity. Herein, co-precipitation procedure was adopted to develop a nanomagnetic copper ferrite/drumstick pod biomass (CuFe2O4/DC) composite, which was characterized, and optimized to sequester malachite green (MG) and lead (Pb(II)) in unary and binary systems from aqueous environment. Mesoporous CuFe2O4/DC surface with 16.96 m2/g BET surface area and acid functionalities predominance was observed. Under the studied experimental conditions, MG adsorption on CuFe2O4/DC in unary system was comparatively higher than that of Pb(II). MG and Pb(II) equilibrium results were fitted to Langmuir isotherm model, their respective maximum monolayer adsorption capacities at 328 K being 952.4 and 921.1 mg/g. On the other hand, binary system (in presence of MG) fastened Pb(II) adsorption kinetics and increased its uptake capacity. Additionally, humic acid (HA) matrix enhanced Pb(II) adsorption kinetics. Recovery studies showed maximal MG and Pb(II) elution with C2H5OH and 0.1 mol/L HCl, respectively. An 82.7% drop in Pb(II) adsorption was found after the first regeneration cycle, while only 17.6% fall in MG adsorption was witnessed after five consecutive regeneration cycles. Hence, it could be concluded that CuFe2O4/DC is a cost-effective and promising adsorbent for an efficient and rapid removal of Pb(II) and MG from both unary and binary systems.