Biopolymer-based beads for the adsorptive removal of organic pollutants from wastewater: Current state and future perspectives.

Among biopolymer-based adsorbents, composites in the form of beads have shown promising results in terms of high adsorption capacity and ease of separation from the effluents. This review addresses the potential of biopolymer-based beads to remediate wastewaters polluted with emerging organic contaminants, for instance dyes, active pharmaceutical ingredients, pesticides, phenols, oils, polyaromatic hydrocarbons, and polychlorinated biphenyls. High adsorption capacities up to 2541.76 mg g-1 for dyes, 392 mg g-1 for pesticides and phenols, 1890.3 mg g-1 for pharmaceuticals, and 537 g g-1 for oils and organic solvents have been reported. The review also attempted to convey to its readers the significance of wastewater treatment through adsorption by providing an overview on decontamination technologies of organic water contaminants. Various preparation methods of biopolymer-based gel beads and adsorption mechanisms involved in the process of decontamination have been summarized and analyzed. Therefore, we believe there is an urge to discuss the current state of the application of biopolymer-based gel beads for the adsorption of organic pollutants from wastewater and future perspectives in this regard since it is imperative to treat wastewater before releasing into freshwater bodies.

A comprehensive review on processing, characteristics, and applications of cellulose nanofibrils/graphene hybrid-based nanocomposites: Toward a synergy between two-star nanomaterials.

Nanostructured materials are fascinating since they are promising for intensely enhancing materials' performance, and they can offer multifunctional features. Creating such high-performance nanocomposites via effective and mild approaches is an inevitable requirement for sustainable materials engineering. Nanocomposites, which combine two-star nanomaterials, namely, cellulose nanofibrils (CNFs) and graphene derivatives (GNMs), have recently revealed interesting physicochemical properties and excellent performance. Despite numerous studies on the production and application of such systems, there is still a lack of concise information on their practical uses. In this review, recent progress in the production, modification, properties, and emerging uses of CNFs/GNMs hybrid-based nanocomposites in various fields such as flexible energy harvesting and storage, sensors, adsorbents, packaging, and thermal management, among others, are comprehensively examined and described based on recent investigations. Nevertheless, numerous challenges and gaps need to be addressed to successfully introduce such nanomaterials in large-scale industrial applications. This review will certainly help readers understand the design approaches and potential applications of CNFs/GNMs hybrid-based nanocomposites for which new research directions in this emerging topic are discussed.

Oil palm frond-derived cellulose nanocrystals: Effect of pretreatment and elucidating its reinforcing potential in hydrogel beads.

Herein, cellulose nanocrystals were synthesized from oil palm fronds (CNC-OPF) involving two pretreatment approaches, viz. autohydrolysis and soda pulping. The pretreatments were applied individually to OPF fibers to assess their influence on CNCs' physicochemical and thermal properties. CNC-OPF samples were assessed using complementary characterization techniques, which confirmed their purity and characteristics. CP/MAS 13C NMR and TEM studies revealed that autohydrolysis pretreatment yielded CNCs with effective hemicellulose and extractives removal compared to that of soda pulping. XRD analysis demonstrated that autohydrolysis-treated CNC-OPF contained a much higher crystallinity index compared to soda pulping treatment. BET measurement disclosed a relatively higher surface area and wider pore diameter of autohydrolysis-treated CNC-OPF. Autohydrolysis-treated CNCs were applied as a reinforcement filler in alginate-based hydrogel beads for the removal of 4-chlorophenol from water, which attained a qmax of 19.168 mg g-1. BET analysis revealed the less porous nature of CNC-ALG hydrogel beads which could have contributed to hydrogel beads' relatively lower adsorption capacity. The point of zero charge of CNC-ALG hydrogel beads was 4.82, suggesting their applicability only within a short solution pH range. This study directs future studies to unveil the possibilities of functionalizing CNCs in order to enhance the adsorption performance of CNC-immobilized hydrogel beads towards 4-chlorophenol and other organic contaminants.

Structural characterization of modified coconut husk lignin via steam explosion pretreatment as a renewable phenol substitutes.

The effects of steam explosion (SE) pretreatment on the structural properties of lignin isolated from coconut husk (CH) biomass via soda pulping were investigated in this work. The isolated SE lignin was classified as dilute acid impregnation SE lignin (ASEL), water impregnation SE lignin (WSEL), and 2-naphthol impregnation SE lignin (NSEL). The various types of functional groups isolated from SE lignin were characterized and compared using a variety of complementary analyses: FTIR spectroscopy, NMR spectroscopy, GPC chromatography, HPAEC-PAD chromatography and thermal analyses. It was revealed that ASEL has the highest solid recovery with 55.89 % yield as well as the highest sugars content compared to WSEL (45.66 % yield) and NSEL (49.37 % yield). Besides, all isolated SE lignin contain a significant quantity of non-condensed G-type and S-type units but less amount of H-type units as supported by previous research. The SE lignin produced lignin with higher molecular weight (Mw ASEL: 72725 g mol-1 > Mw WSEL: 13112 g mol-1 > Mw NSEL: 6891 g mol-1) seems to influence the success of the synthesis reaction of phenolic resins. Because of the large variances in the physicochemical properties of SE lignin polymers, their structural properties were increased toward numerous alternative techniques in lignin-based applications.

Conversion of archeological iron rust employing coconut husk lignin.

Rust powder collected from an archeological iron was evaluated by complementary analyses such as FTIR, XRD, XRF, and SEM/EDX. The analyses revealed that lepidocrocite (L) was the major component in the archeological iron. Coconut husk (CH) can be classified as a type of lignocellulosic biomass of renewable resources that are widely available, especially in coastal areas. In this research, the isolated lignin extracted from CH is being studied as a potential alternative for environmentally friendly applications. The isolated lignin from soda and organosolv pulping went through several analyses such as FTIR, NMR (13C and 2D-HSQC), and TGA analyses. The analyses showed that lignin isolated via soda pulping has superior antioxidant capabilities due to its greater phenolic-OH content compared to lignin isolated from organosolv pulping. The effects of lignin concentrations, pH, and reaction time were utilized in rust conversion studies of an archeological iron. 5 wt% of soda lignin (SL) was revealed as the ideal condition in this rust conversion study with a value of 84.21 %. The treated rust powder with 5 wt% of SL was then further gone through several complementary analyses, which revealed that the treated rust had nearly transformed into an amorphous state.

Simultaneous naphthalene degradation and electricity production in a biowaste-powered microbial fuel cell.

Naphthalene is a very common and hazardous environmental pollutant, and its biodegradation has received serious attention. As demonstrated in this study, naphthalene-contaminated wastewater can be biodegraded using a microbial fuel cell (MFC). Furthermore, the potential of MFC for electricity generation appears to be a promising technology to meet energy demands other than those produced from fossil fuels. Nowadays, efforts are being made to improve the overall performance of MFC by integrating biowaste materials for anode fabrication. In this study, palm kernel shell waste was used to produce palm kernel shell-derived graphene oxide (PKS-GO) and palm kernel shell-derived reduced graphene oxide (PKS-rGO), which were then fabricated into anode electrodes to improve the system's electron mobilization and transport. The MFC configuration with the PKS-rGO anode demonstrated greater energy production potential, with a maximum power density of 35.11 mW/m2 and a current density of 101.76 mA/m2, compared to the PKS-GO anode, which achieved a maximum power density of 17.85 mW/m2 and a current density of 72.56 mA/m2. Furthermore, there is simultaneous naphthalene biodegradation with energy production, where the biodegradation efficiency of naphthalene with PKS-rGO and PKS-GO is 85.5%, and 79.7%, respectively. In addition, the specific capacitance determined from the cyclic voltammetry curve revealed a value for PKS-rGO of 2.23 × 10-4 F/g, which is also higher than the value for PKS-GO (1.57 × 10-4 F/g) on the last day of operation. Anodic microbial analysis shows that electrogens thrive in the MFC process. Finally, a comparison with previous literature and the future prospects of the study are also presented.

Improved p-chlorophenol adsorption onto copper-modified cellulose nanocrystal-based hydrogel spheres.

The present study intended to develop efficient hydrogel spheres in treating simulated wastewater contaminated with p-chlorophenol. Herein, copper-modified nanocellulose was grafted onto alginate to produce eco-friendly hydrogel spheres to utilize as a viable biosorbent. Fabricated spheres were characterized through scanning electron microscopy, thermogravimetry, surface area measurement, point of zero charge and zeta potential analyses. The adsorption of p-chlorophenol was optimized by altering various experimental conditions. Pseudo second order kinetics and Langmuir adsorption isotherm best described the adsorption of p-chlorophenol onto copper-modified cellulose nanocrystal-based spheres. The maximum adsorption capacity was 66.67 mg g-1 with a reusability up to five regeneration cycles. The thermodynamic study directed that p-chlorophenol adsorption was exothermic, spontaneous, and reversible within the analyzed temperature range. Weber-Morris model revealed that intraparticle diffusion was not the singular rate-controlling step in the adsorption process. Hence, copper-modified nanocellulose spheres could be employed as a sustainable and effective biosorbent for p-chlorophenol adsorption from wastewater.

Importance of carbon structure for nitrogen and sulfur co-doping to promote superior ciprofloxacin removal via peroxymonosulfate activation.

Herein, five N, S-co-doped carbocatalysts were prepared from different carbonaceous precursors, namely sawdust (SD), biochar (BC), carbon-nanotubes (CNTs), graphite (GP), and graphene oxide (GO) and compared. Generally, as the graphitization degree increased, the extent of N and S doping decreased, graphitic N configuration is preferred, and S configuration is unaltered. As peroxymonosulfate (PMS) activator for ciprofloxacin (CIP) removal, the catalytic performance was in order: NS-CNTs (0.037 min-1) > NS-BC (0.032 min-1) > NS-rGO (0.024 min-1) > NS-SD (0.010 min-1) > NS-GP (0.006 min-1), with the carbonaceous properties, rather than the heteroatoms content and textural properties, being the major factor affecting the catalytic performance. NS-CNTs was found to have the supreme catalytic activity due to its remarkable conductivity (3.38 S m-1) and defective sites (ID/IG = 1.28) with high anti-interference effect against organic and inorganic matter and varying water matrixes. The PMS activation pathway was dominated by singlet oxygen (1O2) generation and electron transfer regime between CIP and PMS activated complexes. The CIP degradation intermediates were identified, and a degradation pathway is proposed. Overall, this study provides a better understanding of the importance of selecting a suitable carbonaceous platform for heteroatoms doping to produce superior PMS activator for antibiotics decontamination.

Cellulose nanofibrils-graphene hybrids: recent advances in fabrication, properties, and applications.

With the fast-developing social economy and the acceleration of industrialization, seeking effective renewable, sustainable, and environmentally friendly resources that show promising properties is an urgent task and a crucial means to achieve sustainable progress in the face of the growing depletion of non-renewable resources and the deterioration of environmental issues. Cellulose nanofibrils (CNFs) are natural polymeric nanomaterials with excellent biocompatibility, biodegradability, good mechanical features, high strength, low density, high specific surface area, and tunable chemistry. Their combination with other nanomaterials, such as graphene derivatives (GNMs), has been demonstrated to be effective since they produce hybrids with outstanding physicochemical properties, tailorable functionality, and high performance. In this review, recent advances in the preparation, modification, and emerging application of CNFs/GNMs hybrids are described and discussed using the latest studies. First, the concise background of nanocellulose and graphene derivatives is provided, followed by the interfacial interactions between CNFs and GNMs. The different hybrids exhibit great promise in separation, adsorption, optics, flexible electronics, energy storage, thermal management, barrier and packaging, and electromagnetic shielding. The main challenges that inhibit the applicability of these hybrids are finally highlighted, and some perspectives for future research directions are provided.

A recent advancement on preparation, characterization and application of nanolignin.

Each year, 50 to 70 million tonnes of lignin are produced worldwide as by-products from pulp industries and biorefineries through numerous processes. Nevertheless, about 98% of lignin is directly burnt to produce steam to generate energy for the pulp mills and only a handful of isolated lignin is used as a raw material for the chemical conversion and for the preparation of various substances as well as modification of lignin into nanomaterials. Thus, thanks to its complex structure, the conversion of lignin to nanolignin, attracting growing attention and generating considerable interest in the scientific community. The objective of this review is to provide a complete understanding and knowledge of the synthesis methods and functionalization of various lignin nanoparticles (LNP). The characterization of LNP such as structural, thermal, molecular weight properties together with macromolecule and quantification assessments are also reviewed. In particular, emerging applications in different areas such as UV barriers, antimicrobials, drug administration, agriculture, anticorrosives, the environment, wood protection, enzymatic immobilization and others were highlighted. In addition, future perspectives and challenges related to the development of LNP are discussed.

Microwave-assisted catalysis of water-glycerol solutions for hydrogen production over NiO/zeolite catalyst.

In this study, glycerol as an abundant green feedstock was used as a hydrogen source to investigate the reaction of water-glycerol solution decomposition by microwave-assisted catalytic to produce hydrogen over NiO/zeolite catalyst. The catalyst was prepared by inception wetness and then characterized through X-ray diffraction (XRD), scanning electron microscopy (SEM), Energy diffraction X-ray (EDX), and transmission electron microscope (TEM) measurements. The conversion process of glycerol into hydrogen was performed in a fixed-bed microwave-assisted reactor. Effect of microwave power, NiO content, and feed flow rate (FFR) on glycerol conversion and hydrogen selectivity were studied. The results of XRD and EDX measurement showed that NiO crystalline exists on the catalyst sample. The particle size of NiO/zeolite was determined in the range of 30-300 nm, and the particle was found well dispersed on the zeolite surface as confirmed by TEM. Furthermore, the maximum conversion rate can achieve about 96.67 %, while the highest hydrogen production was found up to 73.5 % with the condition of 20% of NiO as an active site on natural zeolite. It was found that the NiO content of 20% gave the best glycerol conversion at the microwave power of 600 W and FFR 0.5 ml/min. Microwave-assisted catalytic irradiation of glycerol appears to be a promising candidate for the production of H2 from an aqueous glycerol solution.

Graphene and zeolite as adsorbents in bar-micro-solid phase extraction of pharmaceutical compounds of diverse polarities.

A bar micro-solid phase (bar µ-SPE) extraction method using either graphene or zeolite or their mixtures as an adsorbent, coupled with high-performance liquid chromatography (using a C1 column) was developed for the simultaneous determination of pharmaceutical compounds (metformin (MET), buformin (BUF), phenformin (PHEN) and propranolol (PROP)) of diverse polarity (log P from -1.82 to 3.10). Parameters influencing the extraction, such as conditioning solvents, pH of the sample, sample volume, amount of adsorbent, stirring rate, time of extraction, type and volume of desorption solvent and time of desorption were investigated. Under the optimized conditions, the extraction method using graphene (extraction efficiency, % EE, ∼6-15%) resulted in the least amount of extracted drugs. However, the use of zeolite and zeolite/graphene mixtures improves the % EE significantly, i.e. 30% for PHEN and 42% for PROP using zeolite; 22% for MET and 18% for BUF using the adsorbent mixture. Under similar conditions, enrichment factors for these drugs range from 11-15. The validated method was performed for the determination of the drugs that were spiked to urine samples. Good recoveries ranging from 72.8 to 116% were achieved.

Preparation and characterization of nanosized lignin from oil palm (Elaeis guineensis) biomass as a novel emulsifying agent.

A study was carried out to determine the effectiveness of lignin, extracted from oil palm (Elaeis guineensis) biomass as water-in-oil (W/O) emulsifying agent. To achieve this goal, soda lignin (SL) was extracted via soda pulping process and a series of nanosized soda lignin (NSL) were prepared using homogenizer at three different speed i.e. 10,400 rpm (NSL 10), 11,400 rpm (NSL 11) and 12,400 rpm (NSL 12) for one hour. All prepared samples were characterized by FT-IR, UV-Vis spectroscopy, thermogravimetric analysis (TGA), zeta potential analyser, Transmission Electron Microscope (TEM) and Extreme High Resolution Field Emission Scanning Electron Microscope (XHR-FESEM). The result of FTIR showed that there is no prominent change occurred in spectra of all samples while a good stability was reflected by TGA curves. The percentage of creaming index and visual observations of all samples demonstrated that NSL 12 and dosage 2 g (out of 1 g, 1.5 g and 2 g) were found to be the best among all samples. Furthermore, the results of IFT indicate that NSL 12 was proven to be more stable than the commercial product. Therefore, NSL 12 is selected for toxicological studies and was found safe in both, in vitro and in vivo studies.

Current advancement on the isolation, characterization and application of lignin.

The most critical issues faced by the world nowadays is to provide the sustainability of consumption for energy and natural resources. Lignin is said to be one of the alternative new discoveries best-suited lignocellulosic biomass due to its low cost, sufficient availability and environmentally safe. The valuable properties exhibited by lignin can give broader applications usage such as in composite materials, wood industries, polymer composite industries, pharmaceutical and corrosion inhibitor industries. Many biomass wastes resources, isolation processes and treatments are undergoing development in order to enhance the producing new lignin-based materials on an industrial scale. Therefore, this review discussed on the current knowledge on the structure and chemistry of isolation of lignin from different sources using various common methods, its characterization, properties and its applications.

Nanocellulose: From Fundamentals to Advanced Applications.

Over the past few years, nanocellulose (NC), cellulose in the form of nanostructures, has been proved to be one of the most prominent green materials of modern times. NC materials have gained growing interests owing to their attractive and excellent characteristics such as abundance, high aspect ratio, better mechanical properties, renewability, and biocompatibility. The abundant hydroxyl functional groups allow a wide range of functionalizations via chemical reactions, leading to developing various materials with tunable features. In this review, recent advances in the preparation, modification, and emerging application of nanocellulose, especially cellulose nanocrystals (CNCs), are described and discussed based on the analysis of the latest investigations (particularly for the reports of the past 3 years). We start with a concise background of cellulose, its structural organization as well as the nomenclature of cellulose nanomaterials for beginners in this field. Then, different experimental procedures for the production of nanocelluloses, their properties, and functionalization approaches were elaborated. Furthermore, a number of recent and emerging uses of nanocellulose in nanocomposites, Pickering emulsifiers, wood adhesives, wastewater treatment, as well as in new evolving biomedical applications are presented. Finally, the challenges and opportunities of NC-based emerging materials are discussed.

Preparation and characterizations of oil palm fronds cellulose nanocrystal (OPF-CNC) as reinforcing filler in epoxy-Zn rich coating for mild steel corrosion protection.

Oil palm frond (OPF) is one of largest contributions to the biomass waste from oil palm plantation. In this work, OPF has been successfully utilized to prepare cellulose nanocrystal (OPF-CNC) by acid hydrolysis. OPF was initially treated with autohydrolysis treatment. The obtained OPF-CNC was characterized via complementary analyses. The produced OPF-CNC showed a high crystallinity index value (60%) and high BET surface area (26.10 m2 g-1) as compared to α-cellulose (crystallinity index: 54% and BET surface area:7.14 m2g-1). The surface analyses via scanning electron microscope (SEM) and transmission electron microscopy (TEM) demonstrated that the OPF-CNC has a smooth surface with a needle-like shape, where the average length and diameter are 95.09 nm and 6.81 nm, respectively. The corrosion analyses via electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PD) illustrate that the coated mild steel with the inclusion of 0.5 wt% OPF-CNC has managed to sharply reduce the corrosion (99%). The coated mild steel with the inclusion of 0.5 wt% OPF-CNC showed the highest hydrophobicity (100.5 ± 0.7°) and has lowest amount of O via water contact angle and energy dispersive X-ray spectroscopy (EDX) analyses respectively, indicating lowest corrosion rate.

Effect of extraction methods on the molecular structure and thermal stability of kenaf (Hibiscus cannabinus core) biomass as an alternative bio-filler for rubber composites.

Lignin from kenaf (Hibiscus cannabinus) core was investigated as an alternative filler for rubber. Three types of extraction methods were used to isolate lignin from kenaf, namely kraft, soda and organosolv process. The particle size, surface area, functionalities changes, molecular weight and thermal properties of the lignin were characterized. The results showed that Kraft lignin (KL) has the smallest particle size (40.41 µm) compared to soda lignin (SL) (63.85 µm) and organosolv lignin (OL) (66.85 µm). This is in good agreement with the BET surface area of 9.52 m2/g, 1.25 m2/g and 2.40 m2/g respectively. However, the smaller surface area of SL compared to OL is due to the smaller pore size and pore volume of SL. KL also showed high hydroxyl content with corresponding high thermal stability as confirmed by NMR and TGA. The thermal stability of the lignin correlates well with the molecular weight (MW). From the overall characteristics, it can be concluded that KL, SL and OL can be used as an alternative filler in rubber compounds to substitute common fillers like silica and carbon.

One-step synthesis of chitosan-polyethyleneimine with calcium chloride as effective adsorbent for Acid Red 88 removal.

Chitosan-polyethyleneimine with calcium chloride as ionic cross-linker (CsPC) was synthesized as a new kind of adsorbent using a simple, green and cost-effective technique. The adsorption properties of the adsorbent for Acid Red 88 (AR88) dye, as a model analyte, were investigated in a batch system as the function of solution pH (pH 3-12), initial AR88 concentration (50-500 mg L-1), contact time (0-24 h), and temperature (30-50 °C). Results showed that the adsorption process obeyed the pseudo-first order kinetic model and the adsorption rate was governed by both intra-particle and liquid-film mechanism. Equilibrium data were well correlated with the Freundlich isotherm model, with the calculated maximum adsorption capacity (qm) of 1000 mg g-1 at 30 °C. The findings underlined CsPC to be an effective and efficient adsorbent, which can be easily synthesized via one-step process with promising prospects for the removal of AR88 or any other similar dyes from the aqueous solutions.

Reinforced lignin-phenol-glyoxal (LPG) wood adhesives from coconut husk.

Lignin was extracted from coconut husk via alkaline pulping, either Kraft or soda. The isolated lignin samples were classified as hydroxy-benzaldehyde, vanillin, and syringaldehyde type according to Fourier-transform Infrared Spectroscopy, 1H and 13C Nuclear Magnetic Resonance (NMR) spectra. Soda lignin (SL) showed higher thermal stability and glass transition temperature (Tg) than Kraft lignin (KL) as proven by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. The soda-lignin-phenol-glyoxal (SLPG) resins with the optimum percentage of lignin substitution at 30% showed improved solid content and gel time in comparison to 30% of Kraft-lignin-phenol-glyoxal (KLPG) and phenol-glyoxal (PG) resin. The good mechanical properties in SLPG is due to the higher amount of molecular weight as well as higher phenolic and G-type unit in lignin that improve the properties of 30% SLPG adhesive. Moreover, the addition of layered double hydroxides (LDH) as reinforced filler up to 15%-30% SLPG adhesive blend shows a great performance (especially mechanical properties) as compared to 30% SLPG adhesive alone.