Herein, self-assembled three-dimensional reduced graphene oxide (RGO)-based hydrogels were synthesized and characterized in detail. A thorough investigation on the uptake of three widely used pharmaceutical drugs, viz. Naproxen (NPX), Ibuprofen (IBP) and Diclofenac (DFC) was carried out from aqueous solutions. To ensure the sustainability of developed hydrogel assembly, practically important parameters such as desorption, recyclability and applicability to real samples were also evaluated. Using the developed 3D hydrogels as adsorptive platforms, excellent decontamination for the above mentioned persistent pharmaceutical drugs was achieved in acidic pH with a removal efficiency in the range of 70-80%. These hydrogels showed fast adsorption kinetics and experimental findings were fitted to different kinetic models, such as pseudo-first order, pseudo-second order, intra-particle and the Elovich models in an attempt to better understand the adsorption kinetics. Furthermore, equilibrium adsorption data was fitted to the Langmuir and Freundlich models, where relatively higher R2 values obtained in case of former one suggested that monolayer adsorption played an important part in drug uptake. Thermodynamic aspects were also studied and negative ΔG0 values obtained indicated the spontaneous nature of adsorption process. The study was also extended to check practical utility of as-prepared hydrogels by spiking real aqueous samples with drug solution, where high % recoveries obtained for NPX, IBP and DFC were of particular importance with regard to prospective application in wastewater treatment systems. We advocate RGO-based hydrogels as environmentally benign, readily recoverable/recyclable material with excellent adsorption capacity for application in wastewater purification.
The utilization of renewable and functional group enriched nano-lignin as bio-additve in fabricating composite has become the focus of attention worldwide. Herein, lignin nanoparticles in the form of hollow spheres with the diameter of the order of 138 ± 39 nm were directly prepared from agro-industrial waste (palm kernel shell) using recyclable tetrahydrofuran in an acidified aqueous system without any chemical modification steps. We then fabricated a new chitosan/nano-lignin composite material as highly efficient sorbent, as demonstrated by efficient removal (~83%) of methylene blue (MB) dye under natural pH conditions. The adsorption process obeyed pseudo-second-order kinetics and adequate fitting of the adsorption data using Langmuir model suggested a monolayer adsorption with a maximum adsorption capacity of 74.07 mg g-1. Moreover, thermodynamic study of the system revealed spontaneous and endothermic nature of the sorption process. Further studies revealed that chitosan composite with nano-lignin showed better performance in dye decontamination compared to native chitosan and chitosan/bulk lignin composite. This could essentially be attributed to synergistic effects of size particularity (nano-effect) and incorporated functionalities due to lignin nanoparticles. Recyclability study performed in four repeated adsorption/regeneration cycles revealed recyclable nature of as-prepared composite, whilst adsorption experiments using spiked real water samples indicated recoveries as high as 89%. Based on this study, as-prepared bio-nanocomposite may thus be considered as an efficient and reusable adsorptive platform for the decontamination of water supplies.
Lignocellulosic biomass waste is a cheap, eco-friendly, and sustainable raw material for a wide array of applications. In the present study, an easy, fast, and economically feasible route has been proposed for the preparation of different zero-valent metal nanoparticles (ZV-MNPs) based on Cu, Co, Ag, and Ni NPs using empty fruit bunch (EFB) biomass residue as support material. The catalytic efficiency of ZV-MNPs/EFB catalyst was investigated against five model pollutants, such as methyl orange (MO), congo red (CR), methylene blue (MB), acridine orange (AO), and 4-nitrophenol (4-NP) using NaBH4 as a source of hydrogen and electron. Comparative study revealed that among as-prepared ZV-MNPs/EFB catalysts, Cu-NPs immobilized onto EFB (Cu/EFB) exhibited maximum catalytic efficiency towards pollutant abasement. Degradation reactions were highly efficient, and were completed within a short time (4 min) in case of MO, CR, and MB, whilst AO and 4-NP were reduced in less than 15 min. Kinetic investigation revealed that the degradation rate of model pollutants accorded with pseudo-first order model. Furthermore, supported catalysts were easily recovered after the completion of experiment by simply pulling the catalyst from reaction system. Recyclability tests performed on Cu/EFB revealed that more than 97% of the reduction was achieved in case of MO dye for four successive cycles of reuse. The as-prepared heterostructure showed multifunctional properties, such as enhanced uptake of contaminants, high catalytic efficiency, and easy recovery, hence, offers great prospects in wastewater purification.
In this work, facile fabrication of lignin nanoparticles (LNP)-based three-dimensional reduced graphene oxide hydrogel (rGO@LNP) has been demonstrated as a novel strategy for environmental applications. Herein, LNP were facilely synthesized from walnut shell waste through a direct chemical route. These LNP were incorporated into the continuous porous network of rGO network to fabricate rGO@LNP hydrogel. Characterization studies were carried out using various analytical techniques viz. scanning electron microscopy, Fourier transform IR spectroscopy, X-ray diffraction and thermogravimetric analysis. The efficiency of rGO@LNP hydrogel as adsorptive platform was evaluated by employing methylene blue and Pb2+ as model pollutants, whilst the effect of various experimental parameters was ascertained for optimal performance. Furthermore, Agar well diffusion method was used to check the antibacterial activities of the hydrogel using two bacterial pathogenic strains, i.e. Klebsiella pneumoniae (gram negative) and Enterococcus faecalis (gram positive). Results showed that after the inclusion of LNP into rGO hydrogel, there was a marked improvement in pollutant's uptake ability and compared to bare LNP and rGO, the composite hydrogel showed enhanced bactericidal effect. Overall, this approach is outstanding because of the synergy of functional properties of nano-lignin and rGO due to multi-interaction sites in the resulting hydrogel. The results presented herein support the application of rGO@LNP as innovative water filter material for scavenging broad spectrum pollutants and bactericidal properties.