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Rice husks are an agricultural residue of great annual production and have a high cellulose content. In this study, we have prepared highly charged carboxyl cellulose nanofibers (CNFs) from rice husks using the TEMPO-oxidation method and the extracted CNFs were evaluated as an adsorbent for the removal of lead(II) and lanthanum(III) (Pb(II) and La(III)) ions from contaminated water. Three different forms of nanocellulose adsorbents were prepared: suspension, freeze-dried, and nanocomposite containing magnetic nanoparticles, where their adsorption performance was tested against the removal of the two chosen heavy metal ions. The maximum adsorption capacity of rice husk based CNFs was found to be the highest in the nanocellulose suspension, i.e., 193.2 mg g−1 for Pb(II) and 100.7 mg g−1 for La(III). The separation of the used adsorbent in the suspension was further facilitated by the gelation of the CNFs and metal cations, where the resulting floc could be removed by gravity-driven filtration. The absorption mechanism of the investigated CNF system is mainly due to electrostatic interactions between negatively charged carboxylate groups and multivalent metal ions. It was found that 90% lanthanum content in the form of lanthanum oxychloride (determined by X-ray powder diffraction) could be obtained by incinerating the CNF/LaCl3 gel. This study demonstrates a viable and sustainable solution to upcycle agricultural residues into remediation nanomaterials for the removal and recovery of toxic heavy metal ions from contaminated water.

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.

Raw wood was subjected to sequential oxidation to produce 2,3,6-tricarboxycellulose (TCC) nanofibers with a high surficial charge of 1.14 mmol/g in the form of carboxylate groups. Three oxidation steps, including nitro-oxidation, periodate, and sodium chlorite oxidation, were successfully applied to generate TCC nanofibers from raw wood. The morphology of extracted TCC nanofibers measured using TEM and AFM indicated the average length, width, and thickness were in the range of 750 ± 110, 4.5 ± 1.8, and 1.23 nm, respectively. Due to high negative surficial charges on TCC, it was studied for its absorption capabilities against Pb2+ ions. The remediation results indicated that a low concentration of TCC nanofibers (0.02 wt%) was able to remove a wide range of Pb2+ ion impurities from 5–250 ppm with an efficiency between 709–99%, whereby the maximum adsorption capacity (Qm) was 1569 mg/g with R2 0.69531 calculated from Langmuir fitting. It was observed that the high adsorption capacity of TCC nanofibers was due to the collective effect of adsorption and precipitation confirmed by the FTIR and SEM/EDS analysis. The high carboxylate content and fiber morphology of TCC has enabled it as an excellent substrate to remove Pb2+ ions impurities.

Understanding the morphology and flow behavior of cellulose nanofibers (CNFs) dispersed in organic solvents can improve the process of fabricating new cellulose-based nanocomposites. In this study,...

Two different chemical methods, TEMPO-oxidation and nitro-oxidation, were used to extract carboxyl cellulose nanofibers (CNFs) from non-wood biomass sources (i.e., jute, soft and hard spinifex grasses). The combined TEMPO-oxidation and homogenization approach was very efficient to produce CNFs from the cellulose component of biomass; however, the nitro-oxidation method was also found to be effective to extract CNFs directly from raw biomass even without mechanical treatment. The effect of these two methods on the resulting cross-section dimensions of CNFs was investigated by solution small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The UV-Vis spectroscopic data from 0.1 wt% TEMPO-oxidized nanofiber (TOCNF) and nitro-oxidized nanofiber (NOCNF) suspensions showed that TOCNF had the highest transparency (> 95%) because of better dispersion, resulted from the highest carboxylate content (1.2 mmol/g). The consistent scattering and microscopic results indicated that TOCNFs from jute and spinifex grasses possessed rectangular cross-sections, while NOCNFs exhibited near square cross-sections. This study revealed that different oxidation methods can result in different degrees of biomass exfoliation and different CNF morphology.

Regenerated microfibrillated cellulose (R-MFC) fibers were prepared successfully by a combined dissolution and regeneration approach using phosphoric acid/ethanol treatment on jute cellulose. The prepared R-MFC fibers possessed high surface area (10.74 m2/g), good aspect ratio (L/D = 30), and excellent thermal stability (Tmax = 352 °C). In addition, the fibers exhibited 3.84 wt % of phosphate groups (PO42–) with a ζ-potential of −8.4 mV and low crystallinity index (CI) of 47.5%. These R-MFC fibers were in the cellulose II polymorph, confirmed by 13C CPMAS NMR and WAXD measurements, and they were effective to anchor the growth of ZnO nanocrystals. WAXD and TEM examinations on the imbedded ZnO nanocrystals indicated that they possessed the hexagonal wurtzite crystal structure and could assemble into a flower-like morphology in the R-MFC scaffold. A R-MFC composite containing 41 wt % of ZnO nanocrystals was found to be very efficient to remove arsenic (As(V)) ions from water with the maximum capacity of 4,42...

Green and sustainable cellulose nanocrystals-TiO2 nanocomposite was prepared for environmental applications using a facile method comprised of thermal degradation of aqueous titanium precursors., 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.

Proton exchange membranes (PEMs), such as Nafion, are still one of the reasons for the high cost of PEMFCs. Among the alternatives, cellulose, a low cost and biodegradable material, has been considered in the form of its derivatives, such as cellulose acetate, bacterial cellulose or nanocellulose, as the PEM in fuel cells. However, its use involves more chemical synthesis steps. Here, we use low-cost 1.5-micron cellulose filter paper as the scaffold and prepare membranes for PEMFCs by simply impregnating it with a 10% Nafion solution or immersing it in resorcinol bis(diphenyl phosphate) (RDP). The prepared membranes are primarily composed of cellulose, with a cellulose to Nafion or RDP ratio of 2 : 1 or 1 : 1. The membrane electrode assemblies (MEAs) incorporating the as-prepared membranes exhibit a maximum output power of 23 mW cm−2 at 80 °C for the cellulose/Nafion membrane or 10 mW cm−2 at 60 °C for the cellulose/RDP membrane with only 0.1 mg cm−2 Pt loading on the anode and cathode, when operated in air. The stability results of the membranes after 100 hours of continuous operation indicate a loss of only 10% in power for the cellulose/Nafion membrane and 20% for the cellulose/RDP membrane. It is revealed by FTIR spectroscopy that both the Nafion polymer and RDP were hydrogen bonded to the cellulose fibers, facilitating proton conduction and stabilizing them against further dissolution.

The objective of this paper is to establish the significance of the mycoremediation of contaminants such as Cd2+ to achieve sustainable and eco-friendly remediation methods. Industries such as electroplating, paint, leather tanning, etc. release an enormous amount of Cd2+ in wastewater, which can drastically affect our flora and fauna. Herein, we report on the in vitro bioadsorption of Cd2+ ions using fungal isolates obtained from different contaminated industrial sites. The detailed studies revealed that two fungal species, i.e., Trichoderma fasciculatum and Trichoderma longibrachiatum, were found to be most effective against the removal of Cd2+ when screened for Cd2+ tolerance on potato dextrose agar (PDA) in different concentrations. Detailed adsorption studies were conducted by exploring various experimental factors such as incubation time, temperature, pH, inoculum size, and Cd2+ salt concentrations. Based on optimum experimental conditions, T. fasciculatum exhibited approximately 67.10% removal, while T. longibrachiatum shows 76.25% removal of Cd2+ ions at pH 5.0, 120 h incubation time, at 30&deg, C. The inoculum sizes for T. fasciculatum and T. longibrachiatum were 2.5% and 2.0%, respectively. Finally, the morphological changes due to Cd2+ accumulation were examined using scanning electron microscopy (SEM). Further, Fourier transform infrared spectroscopy (FTIR) spectroscopy reveals the presence of various functional groups (-CH, &ndash, C=O, NH and &ndash, OH), which seem to be responsible for the efficient binding of Cd2+ ions over the fungal surfaces.

High aspect ratio carboxycellulose nanofibers (NOCNF), having typical length over 1000 nm, width ∼4.6 nm, thickness ∼1.3 nm, and carboxylate content of 0.42 mmol/g, were extracted from jute fibers using a modified nitro-oxidation method. The extracted nanofiber was found to possess crystallinity of 69% (measured by wide-angle X-ray diffraction, WAXD), relatively higher than that of raw jute fibers (crystallinity ∼61%). Gelation of NOCNF in aqueous suspensions was observed due to the high aspect ratio of the fiber even at a relatively low concentration. Rheological studies on the NOCNF suspensions at different concentrations (0.01–1 wt %) revealed the shear-thinning behavior with increasing shear rate. The corresponding viscoelastic moduli (G′ and G′′) results indicated that the NOCNF suspension at concentration between 0.1 and 0.2 wt % possessed a liquid–gel transition. The rheological data near the gelation point could be fitted by the Winter–Chambon model, where the results confirmed the formation of a ...

Mechanistic behavior and flow properties of cellulose nanofibers (CNFs) in aqueous systems can be described by the crowding factor and the concept of contact points, which are functions of the aspect ratio and concentration of CNF in the suspension. In this study, CNFs with a range of aspect ratio and surface charge density (380–1360 μmol/g) were used to demonstrate this methodology. It was shown that the critical networking point of the CNF suspension, determined by rheological measurements, was consistent with the gel crowding factor, which was 16. Correlated to the crowding factor, both viscosity and modulus of the systems were found to decrease by increasing the charge density of CNF, which also affected the flocculation behavior. Interestingly, an anomalous rheological behavior was observed near the overlap concentration (0.05 wt %) of CNF, at which the crowding factor was below the gel crowding factor, and the storage modulus (G′) decreased dramatically at a given frequency threshold. This behavior ...

Carboxycellulose nanofibers were extracted from untreated jute using a simple nitro-oxidation method based on nitric acid/sodium nitrite. The characteristics of nitro-oxidized carboxycellulose nanofibers (NOCNF) with low crystallinity (35%), high carboxylate content (1.15 mmol/g) and high surface charge (− 70 mV) made them an excellent substrate for Pb(II) ion removal from water. For example, a low concentration of NOCNF suspension (0.23 wt%) could remove a wide range of Pb(II) ions ranging from 50 to 5000 ppm in a short time-interval ( 1000 ppm). Evidence of nanoscale lead hydroxide crystallization, induced by the lead(II)-NOCNF aggregated scaffold, was confirmed by FTIR, UV–visible spectroscopy, SEM/EDS, WAXD and TEM measurements.

Nanocelluloses, in the form of carboxycellulose nanofibers, with low crystallinity (CI ∼ 50%), high surface charge (−68 mV), and hydrophilicity (static contact angle 38°), were prepared from an untreated (raw) Australian spinifex grass using a nitro-oxidation method employing nitric acid and sodium nitrite. The resulting nanofibers (NOCNF) were found to be an effective medium to remove Cd2+ ions (cadmium(II)) from water. For example, a low concentration of NOCNF suspension (0.20 wt %) could remove Cd2+ ions over a large concentration range (50–5000 ppm) in a relatively short time period (≤5 min). The results showed that at low Cd2+ concentrations (below 500 ppm), the remediation mechanism was dominated by interactions between carboxylate groups on the NOCNF surface and Cd2+ ions, which also acted as a cross-linking agent to gel the NOCNF suspension. At high Cd2+ concentrations (above 1000 ppm), the remediation mechanism was dominated by the mineralization process of forming Cd(OH)2 nanocrystals, which was...

Carboxycellulose nanofibers (NOCNF) were extracted from untreated jute fibers using a simple nitro-oxidation method, employing nitric acid and sodium nitrite. The resulting NOCNF possessed high surface charge (−70 mV) and large carboxylate content (1.15 mmol/g), allowing them to be used as an effective medium to remove UO22+ ions from water. The UO22+ (or U(VI)) removal mechanism was found to include two stages: the initial stage of ionic adsorption on the NOCNF surface following by the later stage of uranyl hydroxide mineralization, as evidenced by the Fourier transform infrared, scanning electron microscopy with energy dispersive spectroscopy capabilities, transmission electron miscroscopy, and wide-angle X-ray diffraction results. Using the Langmuir isotherm model, the extracted NOCNF exhibited a very high maximum adsorption capacity (1470 mg/g), about several times higher than the most efficient adsorbent reported (poly(acrylic acid) hydrogel). It was also found that the remediation of UO22+ ions by N...

Carboxylated cellulose nanofibers (CNFs), having an average width of 7 nm and thickness of 1.5 nm, were produced by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation method. The fiber cross-sectional dimensions were determined using small-angle X-ray scattering (SAXS), transmission electron microscopy and atomic force microscopy techniques, where the rheological properties under different concentration and ionic strength were also investigated. The formation of hydrogel was evidenced by increasing the CNF concentration or ionic strength of the solvent (water), while the gel structure in ion-induced CNF hydrogels was found to be relatively inhomogeneous. The gelation behavior was closely related to the segmental aggregation of charged CNF, which could be quantitatively characterized by the correlation length (ξ) from the low-angle scattering profile and the scattering invariant (Q) in SAXS.

One step green synthesis of silver nanoparticles (AgNPs) from silver nitrate (AgNO3) using Leucaena leucocephala seeds extract as the reducing agent at room temperature was performed. The bioreduced NPs were characterized by UV-vis spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), scanning electron microscopy (SEM) coupled with energy dispersive spectrophotometry, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA) techniques. Qualitative information of major components in the seed extract was obtained through its phytochemical screening. The phytochemical data of L. leucocephala revealed the presence of terpenes, flavonoids, coumarins and sterols. The reaction was optimized for AgNO3, extract concentration and time duration for the reaction. The obtained NPs showed a characteristic UV peak of AgNPs at 420 nm. TEM and SEM images showed the spherical shaped NPs over which the extract coating was very prominent. The binding of L. leucocephala seeds extract onto NPs was tested using FTIR and TGA. The antifungal activity of the as-synthesized NPs against two fungal species, namely Phlebiopsis gigantea and Echinodontium taxodii, was studied. The antimicrobial effect of the as-synthesized NPs was ascertained against Escherichia coli and Staphylococcus aureus. The antioxidant potential of the AgNPs was tested with 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging. Also, the sensitivity of the NPs towards Fe3+ ions was tested in aqueous media.

In this paper, we report the simple synthesis, detailed characterization, and total wastewater cleanup by adsorption using bare and surfactant-functionalized cerium oxide (CeO2) nanoparticles. The synthesis of CeO2 nanoparticles was performed by a facile aqueous solution process and characterized by a diverse range of techniques, which confirmed that the nanoparticles are well-crystalline, possessing good structural and optical properties. The competence of the prepared nanoparticles was further explored to determine the dye removal efficiency. The developed nanoparticles have also provided chlorine-free disinfection of water. The observed results revealed that the synthesized nanoparticles efficiently lower the pollutant concentrations, reduced turbidity, and exhibited significant reductions in total dissolved solids, chemical and biochemical oxygen demands, and pathogenic load. Interestingly, the surfactant-functionalized nanoparticles revealed that they possess the ability to remove approximately 99% o...

Proton-exchange membrane fuel cells (PEMFCs) are considered to be one of the most promising clean technologies to mitigate climate change, air pollution, and energy crisis. Although PEMFCs have been intensively investigated over the past five decades, the relatively low current density, high cost, and poor durability remain as obstacles to full commercialization. In this study, we present the development and the application of a porosity-tunable carbon aerogel (CA) as an alternative to the carbon support in the PEMFC to overcome its technical barriers. CA demonstrates highly tunable mesopore volume and surface area. The N2 isotherm with non-localized density functional theory analysis shows the optimized CA had extremely high mesopore volume, which was 4.26 times larger than the traditional carbon support (i.e., Vulcan XC-72R). Transmission electron microscopy shows a better catalyst (i.e., platinum nanoparticles) distribution on the CA support. This even distribution of platinum nanoparticles significantly enhances the catalyst utilization of the electrodes in our cyclic voltammetry analysis. It also contributes up to a 713% higher specific power density in our fuel cell testing. The standard accelerated stress tests exhibit that CA has excellent durability compared with the conventional carbon support. Thus, the mesoporous CA provides an efficient and durable alternative to existing carbon material as a catalyst support in PEMFCs.

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...

Poly(lactic acid) (PLA) foams, with the combination of shish-kebab and spherulite nanoporous structure in skin and core layer respectively, was prepared using a novel technique comprising loop oscillating push–pull molding (LOPPM) and supercritical carbon dioxide low-temperature foaming process (SC−CO2LTFP). The foams present superior impact toughness which is 6-fold higher than that of neat PLA, and no significant decrease was observed for the storage modulus. Moreover, SC−CO2LTFP at soaking temperature ranging from 110 to 150 °C were performed to determine the evolution of pore morphology. The ultratough and supermoduli are unprecedented for PLA, and are in great need for broader applications.

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.