Synthesis of tri-metallic surface engineered nanobiochar from cynodon dactylon residues in a single step - Batch and column studies for the removal of copper and lead ions.

Superparamagnetic nanocomposites integrated with multiple metals, and surface engineered nanoparticles play a vital role in the removal of heavy metals. In the present study, amino-functional silica-coated magnetic nanocomposites with biochar synthesised from Cynodon dactylon plant residues are prepared in a single step reaction process. The synthesised nanocomposites are characterized using various analytical techniques such as FTIR to determine their functional entities, SEM, TEM, EDX and VSM to analyse the size (~50 nm), elements and magnetic nature of the nanocomposites. Characterization reveals that the prepared nanobiochar was coated with silica and a specific amine group. The magnetic saturation value of 50 emu/g confirms the prepared sorbent was superparamagnetic. Kinetics, isotherm and thermodynamics parameters are evaluated to study the metal interaction mechanism with the nanocomposites where the system follows pseudo-second-order kinetics and the four-parameter Fritz Schlunder model for both metal ions. The nanocomposites showed the enhanced adsorption capacity of copper (Cu(II)) ions with 220.4 mg/g and 185.4 mg/g for lead (Pb(II)) ions. The nanocomposites also showed the excessive reusing ability of 15 times with the maximum removal efficiency for Cu(II) and Pb(II) metal ions. Column studies are evaluated to demonstrate the vital performance in the removal of Cu(II) ions and the breakthrough point was inferred for the parameters such as concentration (100-300 mg/L), bed height (1-3 cm) and flow rate (2-4 mL/min). The breakthrough point was attained at 1400 min and the removal efficiency of about 64.58% was obtained.

Synthesis of novel adsorbent by incorporation of plant extracts in amino-functionalized silica-coated magnetic nanomaterial for the removal of Zn2+and Cu2+from aqueous solution.

Magnetic nanoparticles owing to their superparamagnetic behaviour and specific reactive sites are facilitated to regenerate and reuse. Our present study determines the cointegration of the plant extracts of Cynodon dactylon and Muraya koenigii with the magnetic nanoparticle coated with silica layer and surface engineered with a specific amine group. The cointegrated magnetic nano adsorbent is characterized for its analytical feature and batch studies are performed to remove zinc (Zn2+) copper (Cu2+) metal ions. Fourier transform infrared spectroscopy reveals the presence of functional entities such as NH2, Si-O-Si, C=C. The size of the cointegrated nano adsorbent (12-30 nm) was confirmed by field emission scanning electron microscopy whereas, a high-resolution transmission electron microscope affirms the nanosize of the particle constituted around 20 nm. Energy dispersive x-ray analysis confirms the presence of elements like Fe, N, Si and was confirmed by X-ray diffraction analysis and vibrating sample magnetometer affirms the superparamagnetic nature with the high magnetic saturation value (Ms - 30 emug-1). The cointegrated nano adsorbent reveals the maximum adsorption capacity of Zn2+ as 78.24 mg.g-1 and Cu2+ as 81.76 mg.g-1 of the adsorbent under the optimized conditions of contact time 45 min, pH 6.0 and temperature 35 °C. Kinetics such as pseudo-first-order, pseudo-second-order, Elovich, intraparticle diffusion and isotherm studies like Langmuir, Freundlich, Dubinin-Radushkevich and Temkin were performed to understand the mechanism of interaction between the nanoadsorbent and metal ions. The reaction system follows the pseudo-second-order kinetics and Langmuir isotherm model for both the Cu2+ and Zn2+ metal ions. To determine the reusing capacity of the cointegrated nanoadsorbent, the adsorption efficiency was studied for continuous twelve cycles with 80% recovery after subsequent acid treatment. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40201-021-00696-9.

Evaluation of column studies using Cynodon dactylon plant-mediated amino-grouped silica-layered magnetic nanoadsorbent to remove noxious hexavalent chromium metal ions.

Magnetic nanoparticles are desirable adsorbents because of their unique superparamagnetic nature with the enhanced binding specificity and surface material interaction. The above unique features attract researchers to use it for wider applications. Herein, the study focuses on the amino-induced silica-layered magnetic nanoparticles amalgamated with plant-extracted products of Cynodon dactylon in order to turn them into a potent adsorbing material in a continuous column set up for the elimination of noxiously distributed Cr(VI) ionsin the effluents. The selected plant-mediated magnetite nanoadsorbent, which was used in the fixed column studies, is optimised with the attributes of inlet concentration, adsorbent bed depth, and flow rate. Thomas, Yoon-Nelson and bed depth model showed the best experimental fit. Breakthrough adsorption time was reported for the various inlet concentrations of 100, 200 and 300 mg/L, adsorbent bed depths 2, 3 and 4 cm and volumetric flow rates of 4, 5 and 6 mL/min. The breakthrough point evaluated for the optimised attribute of inlet concentration of 100 mg/L, packed adsorbent depth 4 cm and flow rate 4 mL/min was 1400 min and the maximum removal efficiency was 60.6%. A better insight of the adsorption of metal ions for large-scale industrial effluents is provided.

Integration of Cynodon dactylon and Muraya koenigii plant extracts in amino-functionalised silica-coated magnetic nanoparticle as an effective sorbent for the removal of chromium(VI) metal pollutants.

Immobilised magnetic nanoparticles are extensively used owing to their superparamagnetic nature, surface interaction, and binding specificity with the appropriate portentous substances. The present research focuses on the development of a portentous, robust carrier, which integrates the silica-coated amino-functionalised magnetic nanoparticle (AF-MnP) with the plant extracts of Cynodon dactylon (L1) and Muraya koenigii (L2) for the stable and enhanced removal of hazardous hexavalent chromium pollutant in the wastewater. Vibrating sample magnetometer (Ms - 45 emu/g) determines the superparamagnetic properties; Fourier-transform infrared spectroscopy determines the presence of functional groups such as NH2, Si-O-Si, C=C; high-resolution transmission electron microscopy, field emission scanning electron microscope and energy-dispersive X-ray spectroscopy determine the size of the green adsorbents in the range of 20 nm and the presence of elements such as Fe, N, and Si determines the efficacy of the synthesised silica-coated AF-MnP. The AF-MnP-L1 shows the maximum adsorption capacity of 34.7 mg/g of sorbent calculated from the Langmuir isotherm model and the process follows pseudo-second-order kinetics. After treatment, the adsorbents can be easily separated from the solution in the presence of an external magnetic field and are reused for nine cycles after acid treatment with the minimal loss of adsorption efficiency.

Development of a magnetically separable co-immobilized laccase and versatile peroxidase system for the conversion of lignocellulosic biomass to vanillin.

Lignin obtained from renewable biomass is a potential feedstock for the synthesis of various value-added chemicals through efficient biocatalytic routes. The ligninolytic enzymes-assisted depolymerization of lignin to vanillin constitutes the most commercially attractive and promising approach in green chemistry as vanillin constitutes the second most prevalent flavoring agent. Thus, in the present work, immobilized laccase and versatile peroxidase, and further, a co-immobilized laccase and versatile peroxidase system on magnetic silica microspheres (MSMS) were developed to generate a robust biocatalytic system that mediates the depolymerization of lignin obtained from Casuarina equisetifolia biomass. The depolymerization of lignin by free and immobilized laccase showed a vanillin yield of 24.8% and 23%, respectively, at pH 4.0 in 6 h at 30°C against a vanillin yield of 20% and 21.7% with the free and immobilized versatile peroxidase, respectively, at pH 5.0°C and 50°C. Comparatively, the system with the co-immobilized laccase and versatile peroxidase exhibited a 1-fold and 1.2-fold higher vanillin yield than the free and immobilized laccase system, respectively. On comparing with the versatile peroxidase system, the co-immobilized biocatalytic system displayed 1.3-fold and 1.2-fold increased vanillin yield than the free and immobilized versatile peroxidase system, respectively, at a pH of 6.0 in 6 h at 30°C with an enzyme concentration of 1 U/ml. The reusability studies of the co-immobilized biocatalytic system exhibited that both the enzymes retained up to 40% of its activity till sixth cycle. Implications: The waste biomass of Casuarina equisetifolia is widely available around the coastal regions of India which does not have any agricultural or industrial applications. The present work exploits the lignocellulosic content of the Casuarina biomass to extract the lignin, which provides a renewable alternative for the production of the commercially high-valued compound, vanillin. This work also integrates a co-immobilized biocatalytic process comprising of laccase and versatile peroxidase leading to an environmentally benign enzymatic process for the depolymerization of lignin to vanillin.

Synergetic integration of laccase and versatile peroxidase with magnetic silica microspheres towards remediation of biorefinery wastewater.

In this study, a tailor-made biocatalyst consisting of a co-immobilized lignolytic enzyme cascade on multi-functionalized magnetic silica microspheres (MSMS) was developed. Physical adsorption was the most promising strategy for the synthesis of individual immobilized laccase (IL), immobilized versatile peroxidase (IP), as well as co-immobilized laccase (Lac) and versatile peroxidase (VP) with an enzyme activity recovery of about 79, 93, 27, and 27.5%, respectively. Similarly, the biocatalytic load of 116, 183, 23.6, and 31 U/g was obtained for IL, IP, and co-immobilized Lac and VP, respectively. The co-immobilized enzyme system exhibited better pH stability than the free and individual immobilized system by retaining more than 100% residual activity at pH 7.0 after a 150-h incubation; whereas, the thermal stability and kinetics of the co-immobilized biocatalyst were not much improved. IL and IP could be recycled for 10 cycles after which they retained 31 and 44% of their initial activities. Co-immobilized Lac and VP were reused for ten consecutive cycles at the end of which Lac activity was depleted, and 37% of VP activity was left. Free enzymes, IL, IP, co-immobilized Lac, and VP were applied to biorefinery wastewater (BRW) in a batch study to investigate the transformation of phenolic contaminants over a period of 5 days. The major classes of phenolic constituents in terms of their order of removal in a Lac-VP system was phenol >2-chlorophenol > trichlorophenol > dichlorophenol > cresols > dimethylphenol >2 methyl- 4, 6-dinitrophenol > 4-nitrophenol > tetrachlorophenols > pentachlorophenol. The free enzymes and individually immobilized enzymes resulted in 80% dephenolization in 5 days. By contrast, the co-immobilized biocatalyst provided rapid dephenolization yielding the same 80% removal within 24 h and 96% removal of phenols in 60 h after which the system stabilized, which is the major advantage of the co-immobilized biocatalyst. ᅟ Graphical abstract.

Review on nanoadsorbents: a solution for heavy metal removal from wastewater.

Elimination of heavy metals from contaminated streams is of prime concern due to their ability to cause toxic chaos with the metabolism of flora and fauna alike. Use of advanced nano-engineered technologies such as the innovative combination of surface chemistry, chemical engineering fundamentals and nanotechnology opens up particularly attractive horizons towards treatment of heavy metal contaminated water resources. The obtained product of surface engineered nanoadsorbent produced has successfully proven to show rapid adsorption rate and superior sorption efficiency towards the removal of a wide range of defiant heavy metal contaminants in wastewater. The use of these materials in water treatment results in markedly improved performance features like large surface area, good volumetric potential, extra shelf-lifetime, less mechanical stress, stability under operational conditions with excellent sorption behaviour, no secondary pollution, strong chelating capabilities and they are easy to recover and reuse. This review intends to serve as a one-stop-reference by bringing together all the recent research works on nanoparticles synthesis and its advantages as adsorbents in the treatment of heavy metal polluted wastewater that have so far been undertaken, thereby providing researchers with a deep insight and bridging the gap between past, present and future of the elegant nanosorbents.