Sonochemical synthesis of lignin nanoparticles and their applications in poly (vinyl) alcohol composites.

Lignin is a common and abundant byproduct of the pulp and paper industry and is generally burned to produce steam. Opportunities exist to acquire greater value from lignin by leveraging the properties of this highly conjugated biomacromolecule for applications in UV absorption and polymer reinforcement. These applications can be commercialized by producing value-added lignin nanoparticles (LNPs) using a scalable sonochemical process. In the present research, monodisperse LNPs have been synthesized by subjecting aqueous dispersions of alkali lignin to acoustic irradiation. The resulting particle size distribution and colloidal stability, as determined by dynamic light scattering, transmission electron microscopy and zeta potential analysis, of LNPs can be adjusted by varying the solution pH and ultrasonication energy. As-synthesized LNPs with a mean diameter of 204 nm were incorporated into poly (vinyl) alcohol (PVA) to prepare thin and flexible nanocomposite films using a simple solvent casting method. The addition of 2.5 wt% LNP increased the material's Sun Protection Factor up to 26 compared to 0 for neat PVA, while maintaining light transmission above 75 % in the visible spectra. In addition, the tensile strength and elastic modulus of the PVA nanocomposites improved by 47 % and 36 %, respectively. The presence of LNP also enhanced the thermal stability of the materials. Significantly, the proposed sonochemical process may be generally applicable to the synthesis of a range of naturally-derived LNPs for a variety of value-added applications.

Dynamic Assembly of Strong and Conductive Carbon Nanotube/Nanocellulose Composite Filaments and Their Application in Resistive Liquid Sensing.

The continuous flow assembly of colloidal nanoparticles from aqueous suspensions into macroscopic materials in a field-assisted double flow focusing system offers an attractive way to bridge the outstanding nanoscale characteristics of renewable cellulose nanofibrils (CNFs) at scales most common to human technologies. By incorporating single-walled carbon nanotubes (SWNTs) during the fabrication process, high-performance functional filament nanocomposites were produced. CNFs and SWNTs were first dispersed in water without any external surfactants or binding agents, and the resulting nanocolloids were aligned by means of an alternating electric field combined with extensional sheath flows. The nanoscale orientational anisotropy was then locked by a liquid-gel transition during the materials assembly into macroscopic filaments, which greatly improved their mechanical, electrical, and liquid sensing properties. Significantly, these findings pave the way toward the environmentally friendly and scalable manufacturing of a variety of multifunctional fibers for diverse applications.

Simultaneous multiparameter whole blood hemostasis assessment using a carbon nanotube-paper composite capacitance sensor.

Rapid and accurate clinical assessment of hemostasis is essential for managing patients who undergo invasive procedures, experience hemorrhages, or receive antithrombotic therapies. Hemostasis encompasses an ensemble of interactions between the cellular and non-cellular blood components, but current devices assess only partial aspects of this complex process. In this work, we describe the development of a new approach to simultaneously evaluate coagulation function, platelet count or function, and hematocrit using a carbon nanotube-paper composite (CPC) capacitance sensor. CPC capacitance response to blood clotting at 1.3 MHz provided three sensing parameters with distinctive sensitivities towards multiple clotting elements. Whole blood-based hemostasis assessments were conducted to demonstrate the potential utility of the developed sensor for various hemostatic conditions, including pathological conditions, such as hemophilia and thrombocytopenia. Results showed good agreements when compared to a conventional thromboelastography. Overall, the presented CPC capacitance sensor is a promising new biomedical device for convenient non-contact whole-blood based comprehensive hemostasis evaluation.

Field-Assisted Alignment of Cellulose Nanofibrils in a Continuous Flow-Focusing System.

The continuous production of macroscale filaments of 17 µm in diameter comprising aligned TEMPO-oxidized cellulose nanofibrils (CNFs) is conducted using a field-assisted flow-focusing process. The effect of an AC external field on the material's structure becomes significant at a certain voltage, beyond which augmentations of the CNF orientation factor up to 16% are obtained. Results indicate that the electric field significantly contributes to improve the CNF ordering in the bulk, while the CNF alignment on the filament surface is only slightly affected by the applied voltage. X-ray diffraction shows that CNFs are densely packed anisotropically in the plane parallel to the filament axis without any preferential out of plane orientation. The improved nanoscale ordering combined with the tight CNF packing yields impressive enhancements in mechanical properties, with stiffness up to 25 GPa and more than 63% (up to 260 MPa), 46% (up to 2.8%), and 120% (up to 4.7 kJ/m3) increase in tensile strength, strain-to-failure, and toughness, respectively. This study demonstrates for the first time the control over the structural ordering of anisotropic nanoparticles in a dynamic system using an electric field, which can have important implications for the development of sustainable alternatives to synthetic textiles.

In situ immobilization of ultra-fine Ag NPs onto magnetic Ag@RF@Fe3O4 core-satellite nanocomposites for the rapid catalytic reduction of nitrophenols.

Novel magnetic Ag@RF@Fe3O4 core-satellite (MCS) nanocomposites were prepared through in situ photoreduction upon bridging Fe(III) and Ag+ via hydroxyl groups in resorcinol formaldehyde (RF) resin by virtue of the coordination effect. The catalytic activity of MCS nanocomposites was evaluated based on catalytic 4-nitrophenol (4-NP) reduction with NaBH4 as the reducing agent. It was noteworthy that the MCS-3 was beneficial to obtain a superior reaction rate constant of 2.27 min-1 and a TOF up to 72.7 h-1. Moreover, the MCS could be easily recovered by applying an external magnetic field and was reused for five times without significantly decrease in catalytic activity. Kinetic and thermodynamic study revealed that catalytic 4-NP reduction using MCS nanocatalysts obeyed the Langmuir-Hinshelwood mechanism and was controlled by the diffusion rate of substrates. Overall, the immobilization of ultra-fine Ag nanoparticles and the extremely negative potentials around MCS nanocomposites, which were effective for the diffusion of reactants, synergistically accelerated the catalytic reduction reactions.

Cellulose Nanofibril/Carbon Nanomaterial Hybrid Aerogels for Adsorption Removal of Cationic and Anionic Organic Dyes.

Advances in nanoscale science and engineering are providing new opportunities to develop promising adsorbents for environmental remediation. Here, hybrid aerogels are assembled from cellulose nanofibrils (CNFs) and carbon nanomaterials to remove cationic dye methylene blue (MB) and anionic dye Congo red (CR) in single and binary systems. Two classes of carbon nanomaterials, carbon nanotubes (CNTs) and graphene nanoplates (GnPs), are incorporated into CNFs with various amounts, respectively. The adsorption, mechanics and structure properties of the hybrid aerogels are investigated and compared among different combinations. The results demonstrate CNF-GnP 3:1 hybrid exhibits the best performance among all composites. Regarding a single dye system, both dye adsorptions follow a pseudo-second-order adsorption kinetic and monolayer Langmuir adsorption isotherm. The maximal adsorption capacities of CNF-GnP aerogels for MB and CR are 1178.5 mg g-1 and 585.3 mg g-1, respectively. CNF-GnP hybrid show a superior binary dye adsorption capacity than pristine CNF or GnP. Furthermore, nearly 80% of MB or CR can be desorbed from CNF-GNP using ethanol as the desorption agent, indicating the reusability of this hybrid material. Hence, the CNF-GnP aerogels show great promise as adsorption materials for wastewater treatment.

Lignin-Modified Carbon Nanotube/Graphene Hybrid Coating as Efficient Flame Retardant.

To reduce fire hazards and expand high-value applications of lignocellulosic materials, thin films comprising graphene nanoplatelets (GnPs) and multi-wall carbon nanotubes (CNTs) pre-adsorbed with alkali lignin were deposited by a Meyer rod process. Lightweight and highly flexible papers with increased gas impermeability were obtained by coating a protective layer of carbon nanomaterials in a randomly oriented and overlapped network structure. Assessment of the thermal and flammability properties of papers containing as low as 4 wt % carbon nanomaterials exhibited self-extinguishing behavior and yielded up to 83.5% and 87.7% reduction in weight loss and burning area, respectively, compared to the blank papers. The maximum burning temperature as measured by infrared pyrometry also decreased from 834 °C to 705 °C with the presence of flame retardants. Furthermore, papers coated with composites of GnPs and CNTs pre-adsorbed with lignin showed enhanced thermal stability and superior fire resistance than samples treated with either component alone. These outstanding flame-retardant properties can be attributed to the synergistic effects between GnPs, CNTs and lignin, enhancing physical barrier characteristics, formation of char and thermal management of the material. These results provide great opportunities for the development of efficient, cost-effective and environmentally sustainable flame retardants.

Removal of copper ions from aqueous solutions via adsorption on carbon nanocomposites.

The development of technologies for water purification is critical to meet the global challenges of insufficient water supply and inadequate sanitation. Among all wastewater treatments, adsorption is globally recognized as the most promising method because of its versatility and economic feasibility. Herein, the removal of copper ions (Cu(II)) from aqueous solutions through adsorption on free-standing hybrid papers comprised of a mixture between graphene and different types of carbon nanotubes (CNTs) was examined. Results indicate that the rate of adsorption and long-time capacity of the metal ions on the nanocomposites significantly exceeds that of activated carbon by a factor of 4. Moreover, the combination of graphene with CNTs endows an increase in the uptake of Cu(II) up to 50% compared to that of CNTs alone, with a maximum adsorption capacity higher than 250 mg·g(-1). The removal of Cu(II) from water is sensitive to solution pH, and the presence of oxygen functional groups on the adsorbent surface promotes higher adsorption rates and capacities than pristine materials. These hybrid nanostructures show great promise for environmental remediation efforts, wastewater treatments, and separation applications, and the results presented in this study have important implications for understanding the interactions of carbonaceous materials at environmental interfaces.

Free-standing carbon nanotube/graphene hybrid papers as next generation adsorbents.

The adsorption of a series of aromatic compounds from aqueous solution onto purified, free-standing single-walled carbon nanotube/graphene nanoplatelet hybrid papers is studied both experimentally and theoretically. Experimental data is obtained via changes in optical absorption spectra of the aqueous solutions and is used to extract all parameters required to implement a semi-empirical mass-transfer model. Agreement between experiment and theory is excellent and data from all compounds can be cast on a universal adsorption curve. Results indicate that the rate of adsorption and long-time capacity of many aromatic compounds on hybrid paper adsorbent significantly exceeds that of activated carbon by at least an order of magnitude. The combination of carbon nanotubes and graphene also promotes on the order of a 25% improvement in adsorption rates and capacities than either component alone. Hybrid nanocomposites show significant promise as adsorption materials used for environmental remediation efforts.