Functionalized Cellulose Nanocrystals Research Articles

Crosslinkable latex-based acrylic adhesives containing functionalized cellulose nanocrystals (fCNCs)

In this study, crosslinkable acrylic adhesives with functionalized cellulose nanocrystal (fCNCs) were prepared via in situ emulsion polymerization at 80 °C for 3h. The neat acrylic pressure sensitive adhesives (PSAs) without any nanoparticles were prepared using butyl acrylate (BA), 65 wt%, and methyl methacrylate (MMA), 35 wt%, and various amounts of 2-hydroxyethyl methacrylate (HEMA), 1, 3, 5, 7 wt% based on total BA and MMA monomers. For preparing fCNCs reinforced adhesives, the cellulose nanocrystals (CNCs) were functionalized using various concentrations of 3-methacryloxypropyl trimethoxy silane (MPS), 5, 20, 40 mM. The cellulose nanocrystals (CNCs), functionalized cellulose nanocrystals (fCNCs), and the prepared adhesives were characterized by Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The Adhesion performance of the adhesives was evaluated by lap shear and 180° peel tests. The results showed that increasing the HEMA content as crosslinking agent in the adhesive structure, enhanced its gel content, glass transition temperature (Tg), thermal stability, and adhesive performance, i.e. lap shear and peel strength. Finally, the adhesive containing 5 wt% HEMA was selected as the appropriate sample. Thereafter, the adhesives containing 5 wt% HEMA were synthesized in the presence of various amounts of fCNCs, i.e. 0.5, 1, 1.5 wt%. The Adhesion performance of the neat and reinforced adhesives indicated that increasing the fCNCs to the adhesive enhanced thermal stability, gel content, lap shear and peel strength. Additionally, the fCNCs prepared using higher concentration of MPS (40 mM) was more effective on the adhesion performance than the fCNCs prepared with the lower MPS contents, 5, 20 mM. The results showed that the adhesives prepared using 1 wt% and 1.5 wt% of fCNC40 (containing 40 mM MPS) exhibited better adhesion performance.

Functionalized cellulose nanocrystals extracted from date pits as agricultural waste for the efficient remediation of molybdenum from groundwater: Performance and mechanistic studies

The adsorption technique has proven to be an excellent option for treating contaminated water. This work was designed to investigate the efficient remediation of molybdenum (Mo(VI)) from groundwater by using a novel adsorbent composed of date pits (DP) modified by manganese oxide/cellulose nanocrystal (CNC) composite (MnO2/CNC@DP). The physicochemical properties of the adsorbent were examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope with energy-dispersive X-ray spectroscopy techniques (SEM/EDX), X-ray diffraction (XRD), and transmission electron microscopy (TEM) to study the functional group on the adsorbent surface, surface morphology and chemical composition, and the crystallinity behavior. The performance of prepared (MnO2/CNC@DP) toward Mo(VI) was studied using synthetic solutions and real groundwater samples. Also, the effect of pH, temperature, and initial Mo concentration on the adsorption process was investigated. Moreover, various adsorption isotherm models were calculated, and the thermodynamics of adsorption was studied. The recovery experiments for Mo(VI) saturated MnO2/CNC@DP were conducted by using acidic and alkaline solutions. At the optimum pH of 2, the adsorption capacity increased with increasing the initial concentration of Mo(VI), and Qmax was 30 mg/g at 35 °C. The removal of Mo(VI) from real groundwater was 88.42% The negative values of Gibbs energy (ΔG°) demonstrated that the adsorption is spontaneous, and the experimental data followed the Langmuir isotherm model. Moreover, Mo(VI) can be desorbed from the MnO2/CNC@DP surface by using 1.0M HCl. The proposed mechanisms for the adsorption of Mo(VI) by MnO2/CNC@DP were dominated by electrostatic attraction and inner-sphere complexation. As a result of the research, MnO2/CNC@DP is a promising adsorbent with a high potential for removing Mo(VI) from groundwater. Furthermore, This research provides new knowledge into the modification of date pits using different metal oxides/cellulose nanocrystal particles. Furthermore, the results suggest an excellent chance of employing the efficiently produced adsorbent MnO2/CNC@DP for sustainable groundwater treatment from additional contaminants.

Quantitative Determination of Metal Ion Adsorption on Cellulose Nanocrystals Surfaces.

Nanocellulose is a bio-based material that holds significant potential in the field of water purification. Of particular interest is their potential use as a key sorbent material for the removal of metal ions from solution. However, the structure of metal ions adsorbed onto cellulose surfaces is not well understood. The focus of this work is to determine quantitatively the three-dimensional distribution of metal ions of different valencies surrounding negatively charged carboxylate functionalized cellulose nanocrystals (CNCs) using anomalous small-angle X-ray scattering (ASAXS). These distributions can affect the water and ionic permeability in these materials. The data show that increasing the carboxylate density on the surface of the CNCs from 740 to 1100 mmol/kg changed the nature of the structure of the adsorbed ions from a monolayer into a multilayer structure. The monolayer was modeled as a Stern layer around the CNC nanoparticles, whereas the multilayer structure was modeled as a diffuse layer on top of the Stern layer around the nanoparticles. Within the Stern layer, the maximum ion density increases from 1680 to 4350 mmol of Rb+/(kg of CNC) with the increase in the carboxylate density on the surface of the nanoparticles. Additionally, the data show that CNCs can leverage multiple mechanisms, such as electrostatic attraction and the chaotropic effect, to adsorb ions of different valencies. By understanding the spatial organization of the adsorbed metal ions, the design of cellulose-based sorbents can be further optimized to improve the uptake capacity and selectivity in separation applications.

Transforming Wood into a High-Performance Engineering Material via Cellulose Nanocrystal Impregnation

Abstract The demand for wood in construction has led to shortages of strong wood types, causing a shift to costlier alternatives like concrete and nonbiodegradable materials, prompting the investigation of modifying softwoods for better engineering properties. This study investigates the optimization of a multistep impregnation process utilizing functionalized cellulose nanocrystals (f-CNCs) to enhance softwood properties. The process involves alkali delignification, ultrasonication, and vacuum pressure treatment to improve wood porosity and in turn improve CNC impregnation with uniform dispersion. Microstructural analyses through field emission scanning electron microscopy and atomic force microscopy (AFM) offer detailed insights into cell wall morphology and surface topography, whereas Fourier transform infrared spectroscopy highlights compositional shifts resulting from f-CNC impregnation. Mechanical testing demonstrates significant improvements for treated woods, particularly a 67 percent increase in modulus of elasticity for the 2 percent CNC-treated group compared with the control group; a 71 percent increase in modulus of rupture was observed for 2 percent CNC-, 3 percent NaOH-, and 2 percent acetic acid-treated group compared with the control sample. The sample delignified with 3 percent NaOH and impregnated by 2 percent f-CNC emerged as particularly effective. This research sets the stage for potential advancements in strengthening softwood using CNC, including a novel AFM method and alternative impregnation techniques like the Lowry method, inviting further exploration.

Multiple noncovalent interactions tailored crystallization and performance reinforcement mechanisms of Biopolyester Composites with functional Cellulose Nanocrystals

The slow crystallization and weak mechanical features of poly (butylene adipate-co-terephthalate) (PBAT) have become a severe industrial problem in food packaging. Inspired by principle of bionic structure, functional cellulose nanocrystals (CNC) modified with hexamethylene diisocyanate (HMDI) and toluene diisocyanate (TDI) can enhance the crystallization ability and mechanical properties of PBAT nanocomposites. Significantly, CNC-T (CNC modified by TDI) showed a stronger reinforced effect on PBAT properties than unmodified CNCs and CNC-H (CNC modified by HMDI) nanofillers due to hydrogen bonds, π-π interaction between PBAT matrix and CNC-T nanofillers with benzene ring structure. Thus, compared with pure PBAT, PBAT/5CNC-T composites displayed an enhancement of 34.5 % on the tensile strength and exhibited the most robust nucleation ability on PBAT crystallization than CNC and CNC-H. Meanwhile, the possible nucleation, crystallization, and performance reinforcement mechanisms of PBAT nanocomposites have been presented, which is very beneficial for designing robust PBAT nanocomposites with functional cellulose nanocrystals for potential green packaging.

Non-cytotoxic, highly functionalized cellulose nanocrystals with high crystallinity and thermal stability derived from a novel agromass of Elettaria cardamomum, using a soft and benign mild oxalic acid hydrolysis

Non-cytotoxic, highly crystalline, and functionalized, thermally stable cellulose nanocrystals are extracted from the stems of Elettaria cardamom, a novel underutilised agromass, by employing a neat green, mild oxalic acid hydrolysis. The protocol involves a chemo-mechanical strategy of coupling hydrolysis with steam explosion and homogenization. The obtained CNC showed a crystallinity index of 81.51 %, an aspect ratio of 17.80 ± 1.03 and a high degradation temperature of about 339.07 °C. The extraction procedure imparted a high negative surface functionalization with a zeta potential value of −34.244 ± 0.496 mV and a polydispersity of 16.5 %. The CNC had no antibacterial activity, according to non-cytotoxic experiments conducted on four bacterial strains. This supports the notion of “One Health” in the context of AMR by demonstrating the safety of antibiotic resistance due to consistent exposure upon environmental disposal. The as-extracted nanocellulose crystals can be a potential candidate for commercial application in wide and diversified disciplines like food packaging, anti-infective surfaces for medical devices, biosensors, bioelectronics etc.

Interfacial Compatibility of Core-Shell Cellulose Nanocrystals for Improving Dynamic Covalent Adaptable Networks' Fracture Resistance in Nanohybrid Vitrimer Composites.

The development of polymeric nanocomposites with dynamic covalent adaptable networks and biobased nanomaterials has been a promising approach toward sustainable advanced materials, enabling reprogramming and recycling capabilities. Herein, a core-shell nanohybrid of functionalized cellulose nanocrystals (CNCs) is explored to provide crucial interfacial compatibility for improving the covalent adaptable networks of epoxy-thiol vitrimers in fracture resistance. The poly(ε-caprolactone) (PCL) shells grafted from CNC surfaces can be cross-linked with the covalent adaptable networks via a hot-pressing transesterification process. According to the additive concentration and annealing temperature, the stress relaxation behavior of nanohybrid vitrimer composites can be effectively regulated by the core-shell PCL-grafted CNC (CNC-PCL) nanohybrids from a dispersed to cross-linked interaction. The addition of 15 wt % of the core-shell CNC-PCLs exhibits the reinforced improvement of nanohybrid vitrimer composites in the average Young's modulus of 2.5×, fracture stress of 5.4×, and fracture strain of 2.0×. The research findings might have profound implications for developing synergistic interfacial compatibility between dynamic vitrimer networks and functional nanoparticles for advanced polymeric nanocomposites.

Nanocomposite hydrogels flexible sensors with functional cellulose nanocrystals for monitoring human motion and lactate in sweat

Cellulose nanocrystals (CNCs) are envisioned as superior building blocks for the manufacture of green functional materials and show great potential in flexible electronics. However, the development of a new generation of sensors with the ability to monitor human motion and sweat composition in an integrated manner holds significant promise. In this manuscript, an executable strategy was provided to construct the flexible sensors both for human motion monitoring and sweat sensing detection. The biocompatible, stretchable and self-healing hydrogels were proposed by introducing CNCs modified by polydopamine (PDA) and gold nanoparticles (AuNPs) into the poly (vinyl alcohol) PVA network, which provided enhanced conductivity and mechanical strength. The prepared hydrogels strain sensors displayed a high gauge factor (GF = 0.99) and fast response (160 ms). In addition, taking lactate oxidase (LOx) as a model enzyme, the obtained sweat sensors exhibited a low detection limit (0.31 mM) and an excellent linear correlation (0.9987) in a range of 0.5– 30 mM. The multifunctional sensing strategy provides a new and convenient approach to enable the sensitive detection of multiple components in sweat, as well as small or large human motion monitoring in the near future.

Improvement of mechanical and thermal properties of polylactic acid electrospun films by incorporating L-Lactide functionalized cellulose nanocrystals

Despite being a promising biodegradable material, polylactic acid (PLA) still has several limitations mainly concerning its poor thermal resistance and brittleness. In addition, the high temperature during processing can lead to the deformation of PLA and thus reduce its performance of PLA. To overcome the above problems, L-Lactide functionalized cellulose nanocrystals enhanced PLA (PLA/CNC-g-PLA) were successfully prepared by electrospinning technology and the morphology, hydrophilic, thermal, and mechanical properties of the nanocomposite membranes with different ratios of CNC-g-PLA (1–10%) were characterized. The results demonstrated that the introduction of L-Lactide improved the interfacial compatibility between PLA and CNC. In addition, the mechanical properties and thermal stability of the composite fiber membranes were enhanced by improving the molecular chain orientation through electrospinning. The tensile strength and elongation at break of the composite fiber film increased by 2.4 and 8.2 times, and T0 and Tmax increased by 17 and 38 °C, respectively, when the addition of CNC-g-PLA was 5%. This promising nanocomposite with good properties is expected to be used in tissue engineering and food packaging applications.

Improving nanofiltration performance using modified cellulose nanocrystal-based TFN membranes

Heavy metal ions are one of the principal contaminants in industrial wastewater. Their removal in nanofiltration processes using thin-film nanocomposite (TFN) membranes is a promising treatment method. l-cysteine functionalized cellulose nanocrystals (CysCNCs) and acetylated CNCs (ACNCs) were synthesized via an iodine-catalyzed method. The successful modification of CNCs was confirmed using ATR-FTIR and 13C NMR spectroscopy. The modified CNCs were used in the synthesis of TFN membranes. Prior to interfacial polymerization, the CNCs were dispersed into the organic monomer solution (trimesoyl chloride in n-hexane) rather than in the aqueous monomer solution (piperazine), contrary to conventional practice.Membrane performance was assessed for thin film composite (TFC) and CNC, ACNC and CysCNC-TFN membranes. A simultaneous increase in water permeability/salt and heavy metal rejection of ACNC-TFNs and CysCNC-TFNs was observed. In heavy metal removal tests, the CysCNC-TFN0.2 membranes exhibited the highest water permeability (16 L/m2 h bar) compared to the ACNC-TFN0.1 membranes (14.5 L/m2 h bar), the CNC-TFN0.1 membranes (11.5 L/m2 h bar), and the TFC membranes (6 L/m2 h bar). The heavy metal rejections ranged from 89.2 to 98.4% for the copper ions and 87.0–95.2% for the lead ions, in the same order as for the water permeability results. Therefore, the water permeability/selectivity trade-off was overcome. The TFN membrane performance improvements were mainly attributed to both the nanoparticle functionality and their uniform distribution in the polyamide layer via their dispersion in the organic monomer solution.

A Gemini basic ionic liquid and functionalized cellulose nanocrystal-based mixed matrix membrane for CO2/N2 separation.

Owing to the adverse environmental impact, carbon capture and separation have gained tremendous interest throughout the globe. Herein, a CO2/N2 gas separative mixed matrix membrane containing amine functionalized cellulose nanocrystals and a Gemini basic ionic liquid has been developed, which exhibits the highest permeance of 21 033 GPU and moderate selectivity of 21.3.

Hair hydrolysate functionalized cellulose nanocrystal based chitosan membrane to harness power from wastewater fed MFCs

Chitosan (CS) is an environmentally benign polymer increasingly utilized to prepare low-cost proton exchange membranes (PEMs) for Microbial Fuel Cell (MFC) applications. In this work, hair hydrolysate functionalized CNCs have been utilized with CS matrix followed by cross-linking with epichlorohydrin to enhance the properties of neat chitosan for its application as Nafion-alternative membrane to harvest electricity from domestic wastewater fed MFC device for the first time. Characterizations reveals the structural interaction between the hair hydrolysate functionalized CNC and chitosan matrix resulting in higher antibacterial property with a low percentage of water uptake (60%) and swelling (26%) and higher ion conductivity (1.04 mS/cm). Maximum power density of 142.57 mW/m2 and maximum open circuit voltage of 769.58 mV is derived from real wastewater which is higher compared to previous literature. The results demonstrate the possibility of application of the new low-cost, sustainable PEM with enhanced properties for MFC and wastewater treatment in future.

Bio-Catalysis for the Functionalization of Cellulose Nanocrystals.

In this work, the chemical modification of cellulose nanocrystals (NCs) using an enzyme as a catalyst has been performed by a "grafting from" reaction, in order to covalently functionalize the external surface of NCs with both poly(L-lactic acid) (PLLA) and poly(ε-caprolactone) (PCL) by ring-opening polymerization. Firstly, cellulose nanocrystals were prepared from commercial cellulose microcrystals by acid hydrolysis and then functionalized by using Yarrowia lipolytica lipase immobilized on Lewatit resin as a catalyst. To confirm the success of the grafting reactions, 1H-NMR has been performed as well as FT-IR and Raman spectroscopy. Moreover, thermogravimetric analysis has been used to determine the amount of polymeric chains grafted onto the surface of cellulose nanocrystals. Furthermore, the crystalline nature of the polymeric chains grafted onto the cellulose surface has been studied by DSC, X-ray scattering, as well as SAXS analysis. To our knowledge, it is the first time that a biocatalyst approach has been used to obtain biopolymeric functionalized cellulose nanocrystals.

Functionalized Cellulose Nanocrystals as Active Reinforcements for Light-Actuated 3D-Printed Structures.

Conventional manufacturing techniques allow the production of photoresponsive cellulose nanocrystals (CNC)-based composites that can reversibly modify their optical, mechanical, or chemical properties upon light irradiation. However, such materials are often limited to 2D films or simple shapes and do not benefit from spatial tailoring of mechanical properties resulting from CNC alignment. Herein, we propose the direct ink writing (DIW) of 3D complex structures that combine CNC reinforcement effects with photoinduced responses. After grafting azobenzene photochromes onto the CNC surfaces, up to 15 wt % of modified nanoparticles can be introduced into a polyurethane acrylate matrix. The influence of CNC on rheological properties allows DIW of self-standing 3D structures presenting local shear-induced alignment of the active reinforcements. The printed composites, with longitudinal elastic modulus of 30 MPa, react to visible-light irradiation with 30-50% reversible softening and present a shape memory behavior. The phototunable energy absorption of 3D complex structures is demonstrated by harnessing both geometrical and photoresponsive effects, enabling dynamic mechanical responses to environmental stimuli. Functionalized CNC in 3D printable inks have the potential to allow the rapid prototyping of several devices with tailored mechanical properties, suitable for applications requiring dynamic responses to environmental changes.

Nanoarchitectonics of graphene oxide with functionalized cellulose nanocrystals achieving simultaneous dual connections and defect repair through catalytic graphitization for high thermal conductivity

Graphene, with an extremely high intrinsic thermal conductivity of 5300 W/mK, is of special interest to meet thermal requirements in future wearable and high-power electronic devices. Generally, microscopic graphene sheets can be built into a macroscopic material by using graphene oxide (GO) as the precursor. However, both the defects on the basal plane of GO sheets and the lack of connections at their boundaries induce massive scattering of phonons and a low thermal conductivity. Herein, we solve the problem through the nanoarchitectonics of GO with nano Fe3O4 functionalized cellulose nanocrystals (Fe–CNC). During the assembly process, Fe–CNC were compounded with GO homogeneously and formed a composite GO/Fe–CNC film with an aligned lamellar structure. A subsequent thermal reduction at 1500 °C resulted in the generation of Fe/Fe3C nanoparticles in the matrix of the reduced GO/Fe–CNC. During this process, the reduced GO (R-GO) sheets were dually connected by the Fe/Fe3C nanoparticles as well as the carbonized cellulose nanocrystals. Furthermore, the defects on the R-GO are repaired by Fe through a catalytic graphitization process. Thus, the scatterings of phonons at the adjacent sheet boundaries and on the basal plane of the R-GO sheets were reduced. A flexible and light weight composite film of reduced GO/Fe–CNC with a thermal conductivity of 1958.14 W/mK was obtained. The thermal conductivity is much higher than that of a pure R-GO film (388.72 W/mK) prepared under the same conditions. This assembly process achieved dual connections and defect repairs simultaneously and it provides an avenue for the design of graphene-based films with a high thermal conductivity.

Functionalized cellulose nanocrystal embedded into citrus pectin coating improves its barrier, antioxidant properties and potential application in food

Due to the hydrophilic of the pectin material, the coating has poor barrier properties and a negative preservation effect on fresh fruits. In this study, citrus pectin coating with improved barrier and antioxidant properties was prepared by embedding with functional cellulose nanocrystals (CNC). It was assessed that cellulose nanocrystals grafted with p-coumaric acid (CNC-P) were uniformly dispersed in the pectin matrix to improve coating barrier properties. The addition of 8 % CNC-P to the pectin coating led to a decrease in water vapor and oxygen permeability from the coating by 12.6 % and 22.3 %, respectively. Additionally, the grafted p-coumaric acid (PA) introduced antioxidant properties to the cellulose nanocrystals. The fresh-cut fruits preservation assay showed that the coating containing CNC-P exerted a stronger inhibition effect of the browning process within 8 h than other coatings. This study suggests that pectin coating embedded with CNC-P has the potential to be used in food packaging.

Sustainable preparation of surface functionalized cellulose nanocrystals and their application for Pickering emulsions

Herein, a highly efficient and sustainable approach, namely HCl-catalyzed para-toluene sulfonic acid/Formic acid (p-TsOH/FA) hydrolysis was reported to produce surface functionalized cellulose nanocrystals (CNCs). The optimized CNCs showed a high yield (79.6 %), high crystallinity (70.6 %) and high thermal stability (maximal weight loss temperature around 350 °C). In addition, the as-prepared CNCs possess excellent ability to stabilize oil-water due to the introduction of functional formyl groups, which could be promising stabilizers for Pickering emulsions (PEs). At a fixed oil-water ratio (2:8, v:v), the CNCs with the concentration of 0.5 wt% to 2.0 wt% could stabilize peanut oil to make PEs, and the emulsion droplets were <5 μm in diameter. In addition, the stability of the PEs at different temperature, pH, ionic strength, and long storage time were studied. The results indicated that the obtained CNCs could be sustainable and superior stabilizers for PEs.

Synthesis of urea-containing sodium alginate-g-poly(acrylic acid-co-acrylamide) superabsorbent-fertilizer hydrogel reinforced with carboxylated cellulose nanocrystals for efficient water and nitrogen utilization

A novel slow-release nitrogen fertilizer hydrogel nanocomposite was fabricated by in-situ free radical copolymerization between sodium alginate (SA), acrylic acid (AA), and acrylamide (AM) in an aqueous media using N, N’methylene bis-acrylamide (MBA) as a crosslinker, citric acid-functionalized cellulose nanocrystals (C-CNC) as a nanofiller and urea as a source of nitrogen. Several variables influencing the water absorbency of the fabricated hydrogels were studied and optimized. The optimized Hyd/C-CNC and Hyd/C-CNC/urea were fully characterized to determine their structure, thermal stability, and morphology. Swelling behavior in saline solutions such as (NaCl, CaCl2, and FeCl3) and at various pHs (2−12) as well as the swelling kinetics were investigated. The incorporation of functionalized cellulose nanocrystals into the hydrogel was very beneficial since it boosts the water absorbency from 260 ± 8 g/g for hydrogel without C-CNC to 316 ± 10 g/g for the hydrogel with 1.5 wt% of C-CNC. The soil experiment showed an enhanced soil water-retention capacity after the addition of 1 wt% of the Hyd/C-CNC polymer. The addition of urea confers to the Hyd/C-CNC material an enhanced water retention property and a slow-release nitrogen property. Under optimized conditions, the Hyd/C-CNC/urea had a total nitrogen amount of 13.66%, a high swelling degree (412 ± 4 g/g), and prolonged nitrogen release duration (20 days for complete N-release). Thus, the good water adsorption capacity, as well as the good slow-release fertilizer property, make this material a suitable water-saving material for agriculture applications.

Highly efficient removal of arsenic (III/V) from groundwater using nZVI functionalized cellulose nanocrystals fabricated via a bioinspired strategy

Utilizing nanoscale zero valent iron (nZVI) to purify groundwater contaminated by arsenic species [As(III/V)] is an efficient technology, but the fast and severe aggregation of nZVI limits its practical applications. Herein, nZVI was anchored onto the mussel-inspired polydopamine-coated cellulose nanocrystals (CNCs-PDA-nZVI) as an efficient material for As groundwater remediation. In this set, the introduction of nZVI was expected to significantly enhance the arsenic removal property, while cellulose nanocrystals (CNCs) endowed nZVI with ultrahigh dispersibility. The batch results showed that the maximum As adsorption capacities of CNCs-PDA-nZVI (i.e., 333.3 mg g−1 and 250.0 mg g−1 for As(III) and As(V), respectively) were ten times higher compared with those of pristine CNCs. The kinetics results revealed that chemical adsorption was dominant for As adsorption. The isotherms indicated that a homogeneous adsorption for As(III) and heterogenous adsorption for As(V) on the surface of CNCs-PDA-nZVI. The removal mechanisms for As by CNCs-PDA-nZVI included adsorption-oxidation, coprecipitation and inner-sphere complexation. Overall, the excellent arsenic removal efficiency makes CNCs-PDA-nZVI a promising material for the remediation of As polluted groundwater, and this in-situ anchoring strategy can be extended to overcome the aggregation bottleneck of other nanoparticles for various applications.

Experiment and molecular dynamics simulation of functionalized cellulose nanocrystals as reinforcement in cement composites

This study evaluated the potential effect of cellulose nanocrystal and coated polyethylene fiber on the mechanical properties of mortar. Two kinds of cellulose nanocrystals (CNC) directly as Nano-materials, and indirectly as film coated onto the polypropylene fibers were employed as cement-based reinforcement materials. The fluidity, flexural and compressive strength, and the microstructure of each specimen were measured. In the direct method, mortar mixed with the CNC containing carboxyl groups (CNC-C) showed superior properties compared to the CNC containing sulfo groups (CNC-S). The addition of CNC impacted the process of hydration and compactness of hydration products. The results of X-Ray polycrystalline diffractometer (XRD) and heat of hydration showed that CNC accelerated hydration process. Energy spectrum analysis (EDS) measured ratio of calcium to silicon (C/S) of calcium silicate hydrate (C-S-H) and proved that CNC-C increased the tightness of C-S-H while CNC-S decreased. The results of scanning electron microscopy (SEM) indicated that cellulose nanocrystals were interspersed in C-S-H, forming Nano-bridge and arresting Nano-crack. In the indirect method, the maximum increase in flexural strength of sample between all groups was the specimen that adding 0.3% (volume ratio of fiber to mortar) of CNC-C coated polypropylene fibers. The flexural and compressive strength of the mortar were increased by 22.81% and 10.65% compared to the control, respectively. The results of SEM indicated that coating enhanced bond of the fibers/matrix. Molecular dynamics simulation (MD) analyzed the binding energy, microstructure, dynamic characteristics and adsorption conformation between two CNCs and C-S-H at the molecular scale. MD presented clearly that the adsorption energy between CNC-S and C-S-H was much smaller than CNC-C and C-S-H. This was identical with CNC-C enhancing the mechanical properties of the mortar and CNC-S reducing the mechanical properties.