Aluminum-Crosslinked Nanocellulose Scaffolds for Fluoride Removal.

Anionic carboxylated cellulose nanofibers (CNF) are effective media to remove cationic contaminants from water. In this study, sustainable cationic CNF-based adsorbents capable of removing anionic contaminants were demonstrated using a simple approach. Specifically, the zero-waste nitro-oxidization process was used to produce carboxylated CNF (NOCNF), which was subsequently converted into a cationic scaffold by crosslinking with aluminum ions. The system, termed Al-CNF, is found to be effective for the removal of fluoride ions from water. Using the Langmuir isotherm model, the fluoride adsorption study indicates that Al-CNF has a maximum adsorption capacity of 43.3 mg/g, which is significantly higher than that of alumina-based adsorbents such as activated alumina (16.3 mg/g). The selectivity of fluoride adsorption in the presence of other anionic species (nitrate or sulfate) by Al-CNF at different pH values was also evaluated. The results indicate that Al-CNF can maintain a relatively high selectivity towards the adsorption of fluoride. Finally, the sequential applicability of using spent Al-CNF after the fluoride adsorption to further remove cationic contaminant such as Basic Red 2 dye was demonstrated. The low cost and relatively high adsorption capacity of Al-CNF make it suitable for practical applications in fluoride removal from water.

Cellulose Sulfate Nanofibers for Enhanced Ammonium Removal.

In this study, a sulfonation approach using chlorosulfonic acid (CSA) to prepare cellulose sulfate nanofibers (CSNFs) from raw jute fibers is demonstrated. Both elemental sulfur content and zeta potential in the CSNFs are found to increase with increasing CSA content used. However, the corresponding crystallinity in the CSNFs decreases with the increasing amount of CSA used due to degradation of cellulose chains under harsh acidic conditions. The ammonium adsorption results from the CSNFs with varying degrees of sulfonation were analyzed using the Langmuir isotherm model, and the analysis showed a very high maximum ammonium adsorption capacity (41.1 mg/g) under neutral pH, comparable to the best value from a synthetic hydrogel in the literature. The high ammonium adsorption capacity of the CSNFs was found to be maintained in a broad acidic range (pH = 2.5 to 6.5).

Sustainable Plant-Based Biopolymer Membranes for PEM Fuel Cells.

Carboxycellulose nanofibers (CNFs) promise to be a sustainable and inexpensive alternative material for polymer electrolyte membranes compared to the expensive commercial Nafion membrane. However, its practical applications have been limited by its relatively low performance and reduced mechanical properties under typical operating conditions. In this study, carboxycellulose nanofibers were derived from wood pulp by TEMPO oxidation of the hydroxyl group present on the C6 position of the cellulose chain. Then, citric acid cross-linked CNF membranes were prepared by a solvent casting method to enhance performance. Results from FT-IR spectroscopy, 13C NMR spectroscopy, and XRD reveal a chemical cross-link between the citric acid and CNF, and the optimal fuel cell performance was obtained by cross-linking 70 mL of 0.20 wt % CNF suspension with 300 µL of 1.0 M citric acid solution. The membrane electrode assemblies (MEAs), operated in an oxygen atmosphere, exhibited the maximum power density of 27.7 mW cm-2 and the maximum current density of 111.8 mA cm-2 at 80 °C and 100% relative humidity (RH) for the citric acid cross-linked CNF membrane with 0.1 mg cm-2 Pt loading on the anode and cathode, which is approximately 30 times and 22 times better, respectively, than the uncross-linked CNF film. A minimum activation energy of 0.27 eV is achieved with the best-performing citric acid cross-linked CNF membrane, and a proton conductivity of 9.4 mS cm-1 is obtained at 80 °C. The surface morphology of carboxycellulose nanofibers and corresponding membranes were characterized by FIB/SEM, SEM/EDX, TEM, and AFM techniques. The effect of citric acid on the mechanical properties of the membrane was assessed by tensile strength DMA.

Effective Thallium(I) Removal by Nanocellulose Bioadsorbent Prepared by Nitro-Oxidation of Sorghum Stalks.

Thallium(I) (Tl(I)) pollution has become a pressing environmental issue due to its harmful effect on human health and aquatic life. Effective technology to remove Tl(I) ions from drinking water can offer immediate societal benefits especially in the developing countries. In this study, a bio-adsorbent system based on nitro-oxidized nanocellulose (NOCNF) extracted from sorghum stalks was shown to be a highly effective Tl(I) removal medium. The nitro-oxidation process (NOP) is an energy-efficient, zero-waste approach that can extract nanocellulose from any lignocellulosic feedstock, where the effluent can be neutralized directly into a fertilizer without the need for post-treatment. The demonstrated NOCNF adsorbent exhibited high Tl(I) removal efficiency (>90% at concentration < 500 ppm) and high maximum removal capacity (Qm = 1898 mg/g using the Langmuir model). The Tl(I) adsorption mechanism by NOCNF was investigated by thorough characterization of NOCNF-Tl floc samples using spectroscopic (FTIR), diffraction (WAXD), microscopic (SEM, TEM, and AFM) and zeta-potential techniques. The results indicate that adsorption occurs mainly due to electrostatic attraction between cationic Tl(I) ions and anionic carboxylate groups on NOCNF, where the adsorbed Tl(I) sites become nuclei for the growth of thallium oxide nanocrystals at high Tl(I) concentrations. The mineralization process enhances the Tl(I) removal efficiency, and the mechanism is consistent with the isotherm data analysis using the Freundlich model.

Nanocellulose for Sustainable Water Purification.

Nanocelluloses (NC) are nature-based sustainable biomaterials, which not only possess cellulosic properties but also have the important hallmarks of nanomaterials, such as large surface area, versatile reactive sites or functionalities, and scaffolding stability to host inorganic nanoparticles. This class of nanomaterials offers new opportunities for a broad spectrum of applications for clean water production that were once thought impractical. This Review covers substantial discussions based on evaluative judgments of the recent literature and technical advancements in the fields of coagulation/flocculation, adsorption, photocatalysis, and membrane filtration for water decontamination through proper understanding of fundamental knowledge of NC, such as purity, crystallinity, surface chemistry and charge, suspension rheology, morphology, mechanical properties, and film stability. To supplement these, discussions on low-cost and scalable NC extraction, new characterizations including solution small-angle X-ray scattering evaluation, and structure-property relationships of NC are also reviewed. Identifying knowledge gaps and drawing perspectives could generate guidance to overcome uncertainties associated with the adaptation of NC-enabled water purification technologies. Furthermore, the topics of simultaneous removal of multipollutants disposal and proper handling of post/spent NC are discussed. We believe NC-enabled remediation nanomaterials can be integrated into a broad range of water treatments, greatly improving the cost-effectiveness and sustainability of water purification.

Study the Use of Activated Carbon and Bone Char on the Performance of Gravity Sand-Bag Water Filter.

In this study, granulated activated charcoal (GAC) and bio charcoal (BC) is used as a filler in P3 biosand bag filter to study their filtration performance against a range of fluoride impurities from 1-1400 mg/L. A set of experiments are done to analyze the filtration efficiency of the sandbag filter against fluoride impurities after incorporating different amounts (e.g., 0.2, 2 kg) and a combination of GAC and BC. A combination of filler GAC and BC (1 kg each) have exhibited excellent results with 100% fluoride removal efficiency against 5 mg/L fluoride impurities for an entire experimental time of 165 min. It is because of the synergetic effect of adsorption caused by the high surface area (739 m2/g) of GAC and hydroxyapatite groups in BC. The data from remediation experiments using individual GAC and BC are fitted into the Langmuir and Freundlich Isotherm Models to check their adsorption mechanism and determine GAC and BC's maximum adsorption capacity (Qm). The remediation data for both GAC and BC have shown the better fitting to the Langmuir Isotherm Model with a high R2 value of 0.994 and 0.970, respectively, showing the excellent conformity with monolayer adsorption. While the GAC and BC have presented negative Kf values of -1.08 and -0.72, respectively, for Freundlich Model, showing the non-conformity to multilayer adsorption. The Qm values obtained from Langmuir Model for GAC is 6.23 mg/g, and for BC, it is 9.13 mg/g. The pH study on adsorption efficiency of individual GAC and BC against 5 mg/L of fluoride impurities indicates the decrease in removal efficiency with an increase in pH from 3 to 9. For example, BC has shown removal efficiency of 99.8% at pH 3 and 99.5% at pH 9, while GAC has exhibited removal efficiency of 96.1% at pH 3 and 95.9% at pH 9. Importantly, this study presents the significance of the synergetic application of GAC and BC in the filters, where GAC and BC are different in their origin, functionalities, and surface characteristics.

Reinforcement of Natural Rubber Latex Using Jute Carboxycellulose Nanofibers Extracted Using Nitro-Oxidation Method.

Synthetic rubber produced from nonrenewable fossil fuel requires high energy costs and is dependent on the presumed unstable petroleum price. Natural rubber latex (NRL) is one of the major alternative sustainable rubber sources since it is derived from the plant 'Hevea brasiliensis'. Our study focuses on integrating sustainably processed carboxycellulose nanofibers from untreated jute biomass into NRL to enhance the mechanical strength of the material for various applications. The carboxycellulose nanofibers (NOCNF) having carboxyl content of 0.94 mmol/g was prepared and integrated into its nonionic form (-COONa) for its higher dispersion in water to increase the interfacial interaction between NRL and NOCNF. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) analyses of NOCNF showed the average dimensions of nanofibers were length (L) = 524 ± 203 nm, diameter (D) 7 ± 2 nm and thickness 2.9 nm. Furthermore, fourier transform infra-red spectrometry (FTIR) analysis of NOCNF depicted the presence of carboxyl group. However, the dynamic light scattering (DLS) measurement of NRL demonstrated an effective diameter in the range of 643 nm with polydispersity of 0.005. Tensile mechanical strengths were tested to observe the enhancement effects at various concentrations of NOCNF in the NRL. Mechanical properties of NRL/NOCNF films were determined by tensile testing, where the results showed an increasing trend of enhancement. With the increasing NOCNF concentration, the film modulus was found to increase quite substantially, but the elongation-to-break ratio decreased drastically. The presence of NOCNF changed the NRL film from elastic to brittle. However, at the NOCNF overlap concentration (0.2 wt. %), the film modulus seemed to be the highest.

Arsenic(III) Removal by Nanostructured Dialdehyde Cellulose-Cysteine Microscale and Nanoscale Fibers.

Arsenite (As(III)) contamination in drinking water has become a worldwide problem in recent years, which leads to development of various As(III) remediation approaches. In this study, two biomass-based nanostructured materials, microscale dialdehyde cellulose-cysteine (MDAC-cys) and nanoscale dialdehyde cellulose-cysteine (NDAC-cys) fibers, have been prepared from wood pulp. Their As(III) removal efficiencies and mechanism were determined by combined adsorption, atomic fluorescence spectrometry, microscopy (scanning electron microscopy, transmission electron microscopy, and atomic force microscopy), and spectroscopy (Fourier transform infrared, 13C CPMAS NMR) methods. The adsorption results of these materials could be well described by the Freundlich isotherm model, where the maximum adsorption capacities estimated by the Langmuir isotherm model were 344.82 mg/g for MDAC-cys and 357.14 mg/g for NDAC-cys, respectively. Both MDAC-cys and NDAC-cys materials were further characterized by X-ray diffraction and thermogravimetric analysis, where the results indicated that the thiol groups (the S content in MDAC-cys was 12.70 and NDAC-cys was 17.15%) on cysteine were primarily responsible for the adsorption process. The nanostructured MDAC-cys system appeared to be more suitable for practical applications because of its high cost-effectiveness.

A study of TiO2 nanocrystal growth and environmental remediation capability of TiO2/CNC nanocomposites.

Nanocellulose, which can be derived from any cellulosic biomass, has emerged as an appealing nanoscale scaffold to develop inorganic-organic nanocomposites for a wide range of applications. In this study, titanium dioxide (TiO2) nanocrystals were synthesized in the cellulose nanocrystal (CNC) scaffold using a simple approach, i.e., hydrolysis of a titanium oxysulfate precursor in a CNC suspension at low temperature. The resulting TiO2 nanoparticles exhibited a narrow size range between 3 and 5 nm, uniformly distributed on and strongly adhered to the CNC surface. The structure of the resulting nanocomposite was evaluated by transmission electron microscopy (TEM) and X-ray diffraction (XRD) methods. The growth mechanism of TiO2 nanocrystals in the CNC scaffold was also investigated by solution small-angle X-ray scattering (SAXS), where the results suggested the mineralization process could be described by the Lifshitz-Slyozov-Wagner theory for Ostwald ripening. The demonstrated TiO2/CNC nanocomposite system exhibited excellent performance in dye degradation and antibacterial activity, suitable for a wide range of environmental remediation applications.

A Simple Approach to Prepare Carboxycellulose Nanofibers from Untreated Biomass.

A simple approach was developed to prepare carboxycellulose nanofibers directly from untreated biomass using nitric acid or nitric acid-sodium nitrite mixtures. Experiments indicated that this approach greatly reduced the need for multichemicals, and offered significant benefits in lowering the consumption of water and electric energy, when compared with conventional multiple-step processes at bench scale (e.g., TEMPO oxidation). Additionally, the effluent produced by this approach could be efficaciously neutralized using base to produce nitrogen-rich salts as fertilizers. TEM measurements of resulting nanofibers from different biomasses, possessed dimensions in the range of 190-370 and 4-5 nm, having PDI = 0.29-0.38. These nanofibers exhibited lower crystallinity than untreated jute fibers as determined by TEM diffraction, WAXD and 13C CPMAS NMR (e.g., WAXD crystallinity index was ∼35% for nanofibers vs 62% for jute). Nanofibers with low crystallinity were found to be effective for removal of heavy metal ions for drinking water purification.

Shape and size engineered cellulosic nanomaterials as broad spectrum anti-microbial compounds.

Oxidized celluloses have been used for decades as antimicrobial wound gauzes and surgical cotton. We now report the successful synthesis of a next generation narrow size range (25-35nm) spherical shaped nanoparticles of 2,3,6-tricarboxycellulose based on cellulose I structural features, for applications as new antimicrobial materials. This study adds to our previous study of 6-carboxycellulose. A wide range of bacteria such as Escherichia coli, Staphloccocus aureus, Bacillus subtilis and Mycobacterium tuberculosis (non-pathogenic as well as pathogenic strains) were affected by these polymers in in vitro studies. Activity against Mycobacteria were noted at high concentrations (MIC99 values 250-1000µg/ml, as compared to anti-TB drug Isoniazid 0.3µg/ml). However, the broad spectrum activity of oxidized celluloses and their nanoparticles against a wide range of bacteria, including Mycobacteria, show that these materials are promising new biocompatible and biodegradable drug delivery vehicles wherein they can play the dual role of being a drug encapsulant as well as a broad spectrum anti-microbial and anti-TB drug.

Supramolecular transitions in native cellulose-I during progressive oxidation reaction leading to quasi-spherical nanoparticles of 6-carboxycellulose.

Cellulose-I swells considerably in phosphoric acid, and converts to amorphous cellulose via a cellulose-II transition state. Controlled oxidation of cellulose-I to 6-carboxycellulose (6 CC) using HNO3-H3PO4-NaNO2 oxidation system led to the selective production of 6 CC's of varying carboxyl contents (1.7-22%) as well as various shapes and sizes (macro-sized fibrils of several micron length and/or spherical nanoparticles of 25-35 nm), depending on the reaction conditions. 6 CC's having less than 14% carboxyl content were largely in cellulose-II form (WAXRD values in-between cellulose I and cellulose II), whereas at 14-22% the 6 CC's were largely amorphous; only trace crystallinity was observed at 19% and 22% carboxyl 6 CC. Spherical nanoparticles retained a high degree of crystallinity having cellulose-I structure, whereas the macro-sized fibrils were largely converted to cellulose-II structure. Analysis by WAXRD as well as by CP-MAS (13)C NMR studies gave similar conclusions. Reduced molecular weight with progressive oxidation, including presence of oligomers, was also evident from an increase in the reducing-end carbon peak at ∼ 92 ppm. For high oxidation levels (>14%) the NMR 92-96 ppm peaks disappeared on extracting with dilute alkali, due to soluble oligomers being removed.

Thermal stability of cellulose and their nanoparticles: effect of incremental increases in carboxyl and aldehyde groups.

Oxidized cellulose containing carboxyl and aldehyde functional groups represent an important class of cellulose derivatives. In this study effect of incrementally increasing COOH and CHO groups at C2, C3, and C6 positions of cellulose and nanocellulose has been investigated, with a view to understanding their effect on thermal treatment of cellulose. The results show that 2,3-dialdehyde cellulose (DAC) is the most thermally stable oxidized product of cellulose while the most unstable derivatives contain carboxyl group at the C6 position (6CC). Carboxymethylcellulose (CMC), with carboxymethyl group on C6 position, is more stable than 6CC. Multi-functionalized celluloses 2,3,6-tricarboxycellulose and 6-carboxy-2,3-dialdehyde, have the same level of thermal stability as 6CC, showing that the presence of carboxyl at the C6 is a key destabilizing factor in the thermal stability of oxidized cellulose products. More the number of reducing end groups on the polymer chain, lower the thermal stability of the cellulose, as proved by comparing the TGA/DTG of monomeric analogs dextrose, cellobiose and glucuronic acid with the oxidized celluloses. The thermal stability trend observed for oxidized celluloses was DAC>DCC>nanoparticles>dextrose>glucuronic acid, caused by extent of reducing ends and COOH groups.

Functionalized celluloses and their nanoparticles: morphology, thermal properties, and solubility studies.

Agricultural residues derived cellulose was used to synthesize a new series of carboxy functionalized cellulosic nanoparticles (quasi-spherical shaped, 13.2-21.5% carboxyl content) and macro-sized 6-carboxycelluloses (long-fibril shaped, 1.7-22% carboxyl content). The DP (50-70) and yield (upto 46%) of nanoparticles were manipulated by controlling the reaction temperature and time. TGA/DTG thermographs of the carboxycelluloses gave thermostability data and co-related well with the residual crystalline, amorphous, and anhydroglucuronic acid content. The particle shape and size had no effect on the thermal stability. Some derivatives were fully or partially soluble in aqueous alkali and non-aqueous solvents, which can lead to increased versatility of these polymers.

Functional nanoparticles obtained from cellulose: engineering the shape and size of 6-carboxycellulose.

Agricultural residue derived cellulose and cotton cellulose were used to synthesize quasi-spherical nanoparticles of 6-carboxycellulose having diameter 25-35 nm. This provides a new range of functionalized nanostructured celluloses with increased versatility and applications. The nanoparticles were efficient in stabilizing carbon nanotube dispersions and were effective anti-microbial agents against E. coli.