Preparation and properties of cellulose/silver nanoparticle composites with in situ-generated silver nanoparticles using Ocimum sanctum leaf extract

In the present work, silver nanoparticles were in situ-generated in cellulose matrix using Ocimum sanctum leaf extract as a reducing agent. Regenerated wet cellulose films were first immersed in O. sanctum leaf extract and then it was allowed to diffuse into the films. The leaf extract–diffused wet films were dipped in different concentrated aq.AgNO₃ solutions. The leaf extract inside the wet films reduced AgNO₃ into nanosilver. The dry composite films were black in color. Some of the nanoparticles were also formed outside the film in the solution. The nanoparticles were viewed by transmission electron microscopy and scanning electronic microscopy techniques. The composite films showed good antibacterial activity. The cellulose, matrix, and the composite films were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis techniques. The tensile properties of the composite films were higher than those of the matrix. These biodegradable films can be used for packaging and medical purposes.     

Electrochemically regenerative visible light-induced reactivity of α-Fe2O3 films with Ag(core)–AgCl(shell) microcrystal composites

Ag(core)–AgCl(shell) microcrystal composites (Ag@AgCl) have been formed on an α-Fe₂O₃ film-coated SnO₂ electrode by a 2 step method consisting of the electrochemical reduction of Ag⁺ ions and the subsequent electrochemical oxidation. The synergy of α-Fe₂O₃ and Ag@AgCl gave rise to a high visible light-induced reactivity (λ_ex > 420 nm) for the oxidation of 2-naphthol (2-NAP) used as a model water pollutant in the presence and absence of oxygen. These findings were attributable to the function of Ag@AgCl composites as an excellent charge-separation promoter and built-in acceptor.     

Cellulose–silica composite aerogels from “one-pot” synthesis

Cellulose–silica composite aerogels were prepared via “one-pot” process: aqueous solutions of cellulose–8 wt% NaOH and sodium silicate were mixed, coagulated and dried with supercritical CO₂. The system was studied both in the fluid and solid (dry) states. Cellulose and sodium silicate solutions were mixed at different temperatures and concentrations; mixture properties were monitored using dynamic rheology. The gelation time of the mixture was strongly reduced as compared to that of cellulose–NaOH solutions; we interpret this phenomenon as cellulose self-aggregation inducing partial coagulation due to competition for the solvent with sodium silicate. The gelled cellulose/sodium silicate samples were placed in aqueous acid solution which completed cellulose coagulation and led to in situ formation of sub-micronic silica particles trapped in a porous cellulose matrix. After drying with supercritical CO₂, an organic–inorganic aerogel composite was formed. The densities obtained were in the range of 0.10–0.25 g/cm³ and the specific surface area was between 100 and 200 m²/g. The silica phase was shown to have a reinforcing effect on the cellulose aerogel, increasing its Young’s modulus.     

Ag nanoparticle-embedded one-dimensional β-CD/PVP composite nanofibers prepared via electrospinning for use in antibacterial material

Ag nanoparticle-embedded one-dimensional β-CD (β-cyclodextrin)/PVP composite nanofibers were prepared using a one-step electrospinning technique. Ag nanoparticles were obtained in the AgNO₃/β-CD/DMF solution, in which silver nitrate been introduced as the precursor, DMF as solvent, β-CD as reducing and capping agent. After electrospinning of the composite solution at room temperature, the β-CD/PVP nanofibers containing Ag nanoparticles were obtained. The electrospun composite solution containning Ag nsnopsrticles were confirmed by UV-visible absorption spectra; the resulting composite nanofibers were characterized by scanning electron microscopy , transmission electron microscopy, and X-ray diffraction. Ag-β-CD/PVP nanofiber exhibits good antibacterial property for Escherichia coli and Staphylococcus aureus. Consequently, we propose that these Ag nanoparticle-embedded 1D-nanostructures prepared via electrospinning may be used as antibacterial material.     

Formulation and characterization of in situ generated copper nanoparticles reinforced cellulose composite films for potential antimicrobial applications

Cellulose was dissolved in aq.(LiOH + urea) solution pre-cooled to –12.5°C and the wet films were prepared using ethyl alcohol coagulation bath. The gel cellulose films were dipped in 10 wt.% Cassia alata leaf extract solution and allowed the extract to diffuse into them. The leaf extract infused wet cellulose films were dipped in different concentrated aq. copper sulphate solutions and allowed for in situ generation of copper nanoparticles (CuNPs) inside the matrix. The morphological, structural, antibacterial, thermal, and tensile properties of dried cellulose/CuNP composite films were carried out. The presence of CuNPs was established by EDX spectra and X-ray diffraction. The composite films displayed higher thermal stability than the matrix due to the presence of CuNPs. Cellulose/CuNP composite films possessed better tensile strength than the matrix. The composite films showed good antibacterial activity against E.coli bacteria. We conclude that good antibacterial activity and better tensile properties of the cellulose/CuNP composite films make them suitable for antibacterial wrapping and medical purposes.     

High strength cellulose composite films reinforced with clay for applications as antibacterial materials

High strength cellulose composite films with antibacterial activities were prepared by dispersing montmorillonites (MMT) into cellulose solution in LiOH/urea aqueous solvent followed by regeneration in ethanol coagulation bath, and then by soaking in 5 wt% hexadecylpyridine bromide ethanol solutions to induce the antibacterial action. The cellulose/MMT composite films were characterized by field emission scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, FTIR, UV-spectra, wide angle X-ray diffraction and mechanical test. The results revealed that MMT was dispersed well in the cellulose matrix to form layer structure with a thickness of approximately 3 nm. The mechanical properties of the cellulose/MMT composite films were significantly improved to achieve 132 MP for tensile strength as a result of the MMT delamination. The hexadecylpyridine bromide was fixed well in the cellulose/MMT matrix through cation exchange, leading to the excellent antibacterial activities against Staphylococcus aureus and Escherichia coli, which is important in their practical applications.     

Moisture and solvent responsive cellulose/SiO<Subscript>2</Subscript> nanocomposite materials

Water responsive SiO₂/cellulose nanocomposite hydrogels and films were constructed, for the first time, by dispersing SiO₂ nanoparticles into cellulose solution in LiOH/urea solvent, and then by crosslinking with epichlorohydrin or regeneration in coagulation bath, respectively. The cellulose nanocomposite materials were characterized by Field emission scanning electron microscopy, FTIR, dynamic rheology, wide angle X-ray diffraction and mechanical test. The SiO₂/cellulose nanocomposites at wet state or in water displayed unique behaviors, showing higher light transmittance than those before contacting with water. The results revealed that strong hydrogen-bonding interaction among water, cellulose and SiO₂ led the good dispersion of SiO₂ nanoparticles in the cellulose matrix. The incorporation of SiO₂ nanoparticles improved the transmittance and mechanical strength of the cellulose hydrogels, and also enhanced the mechanical strength of the films. Especially, the cellulose/SiO₂ nanocomposite films were milky at dry state, and changed to transparent after being soaked in water, different from the cellulose film without the SiO₂ nanoparticles. In our findings, SiO₂ and cellulose with water could form strong hydrogen bonding to create a homogenous network structure. The cellulose/SiO₂ composite as a smart material exhibited moisture and solvent responsiveness, showing potential applications in moisture detection.     

Structure and properties of regenerated cellulose/tourmaline nanocrystal composite films

Nanocomposite films were successfully prepared from cellulose and tourmaline nanocrystals with mean diameters of 70 nm in a 1.5 M NaOH/0.65 M thiourea aqueous solution by coagulation with 5 wt % CaCl₂ and then a 3 wt % HCl aqueous solution for 2 min. The structure and properties of the composite films were characterized by X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and tensile testing. The results indicated that the tourmaline nanocrystals were dispersed in a cellulose matrix, maintaining the original structure of the nanocrystals in the composite films. The loss peaks (tan δ) in the DMA spectra and the decomposition temperatures in the DSC curves of the composite films were significantly shifted toward low temperatures, suggesting that the nanocrystals broke the partial intermolecular hydrogen bonds of cellulose, and this led to a reduction in the thermal stability. However, the nanocomposite films exhibited a homogeneous structure and dispersion of the nanocrystals. When the tourmaline content was in the range of 4–8 wt %, the composite films possessed good tensile strength (92–107 MPa) and exhibited obvious antibacterial action against Staphylococcus aureus. This work provides a potential way of preparing functional composite films or fibers from cellulose and nanoinorganic particles with NaOH/thiourea aqueous solutions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 367–373, 2004     

Controlled growth of ZnO nanorod templates and TiO<Subscript>2</Subscript> nanotube arrays by using porous TiO<Subscript>2</Subscript> film as mask

Silver nanoparticles well dispersed in a spherical Poly(vinylpyrollidone)(PVP) matrix were simply prepared by spray pyrolysis of aqueous solutions of AgNO₃ and PVP without any reducing agent. Highly monodisperse silver particles were obtained above the initial mass ratio of PVP/AgNO₃ ∼ 1 and in a certain narrow temperature range. Below the critical mass ratio the silver particles grew to larger ones polydispersely. As the ratio increased above it, they became smaller maintaining their monodispersity. The use of PVP considerably decreased the reduction temperature of the silver nitrate from 450 °C to 250 °C under the same pyrolysis conditions, due to its reducing nature. As the pyrolysis temperature increased above the decomposition temperature of PVP, the silver particles in the matrix grew to merge to a single particle while their crystallite size did not increase as much. The spherical assemblies of the silver nanoparticles were hardly disengaged even after severe washing off the matrix materials. The mechanism of the nanoparticle growth was also discussed.     

Entanglement properties of cellulose and amylose in an ionic liquid

Concentrated solutions of cellulose and amylose were prepared with an ionic liquid 1‐butyl‐3‐methylimidazolium chloride (BmimCl), which was chosen as a good solvent for these polysaccharides. Dynamic viscoelasticity of the concentrated solutions was examined to obtain the molecular weight between entanglements, M_e. The value of M_e in the molten state (M_e,melt), a material constant that reflecting the entanglement properties, was determined for cellulose and amylose by extrapolating M_e to the “melt.” A marked difference in M_e,melt was found: 3.2 × 10³ for cellulose and 2.5 × 10⁴ for amylose. The value of M_e,melt for cellulose, which is composed of β‐(1,4) bonding of D ‐glucose units, is very close to those for polysaccharides with a random‐coil conformation such as agarose and gellan in BmimCl. The much larger M_e,melt for amylose can be attributed to the helical nature of the amylose chain, α‐(1,4)‐linked D ‐glucose units. The effect of concentration on the zero‐shear viscosity for the solutions of cellulose and amylose was also examined. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Construction of inorganic nanoparticles by micro-nano-porous structure of cellulose matrix

In our previous work, the CdS nanoparticles/cellulose films exhibited significantly high photocatalytic H₂ production efficiency under visible light irradiation than the ordinary CdS photocatalyst. In present paper, the CdS nanoparticles were synthesized in situ in pores of the regenerated cellulose substrate and the porous structure of cellulose, formation of the CdS nanoparticles and interactions between CdS and cellulose matrix in the composite films were investigated deeply. The experimental results indicated that the micro-nano-porous structure of the cellulose matrix could be used easily to create inorganic nanoparticles, which supplied not only cavities for the formation of nanoparticles, but also a shell (semi-stiff cellulose molecules support the pore wall) to protect their nano-structure. When the cellulose films with porous structure at wet state were immersed into inorganic ions solution, the ions interacted immediately with the –OH groups of cellulose, and then transformed into inorganic composite via another treatment, finally inorganic nanoparticles formed during the dry. The pore size of the cellulose matrix decreased from 180 nm (at wet state) to about 18 nm (at dry state), leading to the formation of nanoparticles. The results revealed that the CdS nanoparticles with a mean particle diameter about 6 nm were dispersed well, and were immobilized tightly in the cellulose matrix, resulting in a portable photocatalyst with high efficiency for photocatalytic for H₂ evolution. This is simple and “green” pathway to prepare the organic–inorganic hybrid materials.     

A novel catalyst based on electrospun silver-doped silica fibers with ribbon morphology

Mesoporous silica nanofibers and Ag-doped composite nanoribbons were synthesized by a facile combination of an electrospinning technique and the sol–gel method. Tetraethyl orthosilicate, polyvinylpyrrolidone (PVP), triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide), copolymer Pluronic P123, and silver nitrate (AgNO₃) were the components of sol for the production of Ag-doped hybrid silica ribbons. Heat removal of structure-directing agent P123 in the hybrid fibers at high temperatures resulted in a mesoporous morphology, and the degradation of PVP caused AgNO₃ to convert into silver in the form of nanoparticles. The size and content of the particles in the hybrid ribbons could be controlled by the concentration of AgNO₃ and thermal treatment conditions. Scanning electron microscopy, N₂ adsorption–desorption isotherm, transmission electron microscopy, X-ray diffraction, and UV–Vis spectroscopy were used to characterize the composite ribbons. The catalytic activity of the ribbons was evaluated by reduction of methylene blue dye and found to be better than in previous studies.     

Preparation of Disperse Silver Particles by Chemical Reduction

Mastery over the microscopic shape and size of a nanoparticle enables accurate control of its properties for some strict application. The mechanism of shape-controlled synthesis was discussed by investigating the formation of silver nanospheres prepared by chemical reduction method using Ag(NH₃)₂⁺ as metal source, ascorbic acid as reducing agent and polyvinylpyrrolidone (K-30) as dispersant. The effects of temperature, PVP/AgNO₃ mass ratio, pH value and the interaction between PVP and silver on the shape and particle size were studied by XRD and SEM. The results show that the morphology of silver particles could transform from branched to spherical and the particle size gradually decrease with the increase of PVP/AgNO₃ mass ratio. The particles size can also be significantly influenced by pH value and temperature. The key point for preparing high dispersity spherical silver powder is that the growth rate of each plane of the particle must be uniform and synchronous. Silver powders with spherical particles with mean size of 0.2 μm were synthesized under the optimum conditions (PVP/AgNO₃ mass ratio 0.6, pH 7, reaction temperature of 40°C).     

Facile preparation and characterization of anatase TiO2/nanocellulose composite for photocatalytic degradation of methyl orange

Anatase TiO₂/nanocellulose composite was prepared for the first time via a one-step method at a relatively low temperature by using cellulose nanofibers as carrier and tetrabutyl titanate as titanium precursor. The morphology, structure and element composition of the composite were characterized by SEM, EDS, TEM, XRD, XPS and UV–vis DRS. The specific surface area and thermal stability of the composite were investigated by N₂ adsorption–desorption and thermogravimetric analysis, respectively, and the band gaps of the prepared photocatalysts were calculated based on the UV–vis DRS results. In addition, the prepared composite was used for the photocatalytic degradation of methyl orange (aqueous solution, 40 mg L⁻¹). It was found that the composite had a good morphology and anatase crystal structure, and Ti-O-C bond was formed between TiO₂ and nanocellulose. The specific surface area of composite was increased and the thermal stability was decreased compared with the cellulose nanofiber. Moreover, the degradation rate of methyl orange was achieved as 99.72% within 30 min, and no obvious activity loss was observed after five cycles. This work might give some insights into the design of efficient photocatalysts for the treatment of organic dye wastewater.     

Spectroscopic and Discharge Studies on Graphene Oxide Doped PVA/PVP Blend Nanocomposite Polymer Films

Graphene oxide (GO) nanoparticles were synthesized by modified Hummers method. The synthesized GO nanoparticles were incorporated in polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend polymers for the preparation of nanocomposite polymer films by solution cast technique. Different characterizations such as XRD, UV–Vis and FTIR were carried-out on to the prepared nanocomposite polymer films. The thermal analysis of the films was studied by DSC. The morphology of PVA/PVP:GO polymer films confirms GO was exfoliated within the PVA/PVP matrix and also reveals the heterogeneous phase of nanocomposite polymer electrolyte systems. From the conductivity studies the highest conductivity of PVA/PVP: GO (0.45: 0.3) was found to be 8.05 × 10^–4 S/cm at room temperature. Solid state battery has been fabricated with the configuration of Mg⁺/(PVA/PVP:GO)/(I₂ + C + electrolyte) and its cell parameters were calculated for a constant load of 100 kΩ.     

Aligned electrospun cellulose fibers reinforced epoxy resin composite films with high visible light transmittance

Uniaxially oriented cellulose nanofibers were fabricated by electrospinning on a rotating cylinder collector. The fiber angular standard deviation (a parameter of fiber orientation) of the mats was varied from 65.6 to 26.2^o by adjusting the rotational speed of the collector. Optically transparent epoxy resin composite films reinforced with the electrospun cellulose nanofibrous mats were then prepared by the solution impregnation method. The fiber content in the composite films was in the range of 5–30 wt%. Scanning electron microscopy studies showed that epoxy resin infiltrated and completely filled the pores in the mats. Indistinct epoxy/fiber interfaces, epoxy beads adhering on the fiber surfaces, and torn fiber remnants were found on the fractured composite film surfaces, indicating that the epoxy resin and cellulose fibers formed good interfacial adherence through hydrogen-bonding interaction. In the visible light range, the light transmittance was 88–92% for composite films with fiber loadings of 16–32 wt%. Compared to the composite films reinforced with 20 wt% randomly oriented fibers, the mechanical strength and Young’s modulus of the composite films reinforced with same amount of aligned fibers increased by 71 and 61%, respectively. Dynamical mechanical analysis showed that the storage moduli of the composite films were greatly reinforced in the temperature above the glass transition temperature of the epoxy resin matrix.     

In situ synthesis of plate-like Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles in porous cellulose films with obvious magnetic anisotropy

Nanocomposite cellulose films with obvious magnetic anisotropy have been prepared by in situ synthesis of plate-like Fe₂O₃ nanoparticles in the cellulose matrix. The influence of the concentrations of FeCl₂ and FeCl₃ solutions on the morphology and particle size of the synthesized Fe₂O₃ nanoparticles as well as on the properties of the composite films has been investigated. The Fe₂O₃ nanoparticles synthesized in the cellulose matrix was γ-Fe₂O₃, and its morphology was plate-like with size about 48 nm and thickness about 9 nm, which was totally different from those reported works. The concentration of FeCl₂ and FeCl₃ solution has little influence on the particle size and morphology of the Fe₂O₃ nanoparticles, while the content of Fe₂O₃ nanoparticles increased with the increase of the concentration of the precursor solution, indicating that porous structured cellulose matrix could modulate the growth of inorganic nanoparticles. The unique morphology of the Fe₂O₃ nanoparticles endowed the composite films with obvious magnetic anisotropy, which would expand the applications of the cellulose based nanomaterials.     

Ag@AgCl修饰的锐钛矿相TiO2纳米管的制备及其光催化性能

首先采用水热合成法和双氧水处理制备了具有锐钛矿相的TiO2纳米管,然后通过沉淀和光化学反应将Ag@AgCl纳米粒子负载于其上,从而制得TiO2纳米管负载的表面等离子体光催化剂.结果表明,经Ag@AgCl纳米粒子修饰后,锐钛矿相TiO2纳米管因表面等离子共振效应而对可见光具有明显的响应,光生电子-空穴对更容易分离,因而T...     

Antimicrobial cotton fibres prepared by in situ synthesis of AgCl into a silica matrix

Functional antimicrobial cotton fibres were prepared in a novel two-step procedure utilising the pad-dry-cure method to apply an inorganic–organic hybrid sol–gel precursor (reactive binder, RB) followed by the in situ synthesis of AgCl particles on the RB-treated fibres. The morphology and surface composition of the modified cotton fibres were investigated by scanning electron microscopy imaging and X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy spectral analyses. The bulk concentration of Ag on the cotton fibres was determined by inductively coupled plasma mass spectroscopy, and the antimicrobial activity against the bacteria Escherichia coli and Staphylococcus aureus was estimated according to the ISO 20645:2004 (E) and AATCC 100-1999 methods. The results showed that this application process yields the following important benefits: (1) the presence of the RB silica matrix increased the fibres’ capacity for adsorbing AgCl particles compared with the same fibres without RB; (2) the in situ synthesis enabled a simple and environmentally friendly preparation of AgCl particles from AgNO₃ and their embedment into the fibres; (3) the AgCl particles were bound to the RB silica matrix by physical forces, which allowed for their controlled release from the fibres; (4) the capacity of the RB-modified cotton samples to hold embedded AgCl particles was sufficient to provide a 100 % bacterial reduction even after 10 repeated washing cycles; and (5) the chemical modification of the cotton fibres did not significantly change their whiteness, wettability or softness.     

Enhanced deconstruction and dissolution of lignocellulosic biomass in ionic liquid at high water content by lithium chloride

Fabricating an aqueous ionic liquid (IL) for deconstruction and dissolution of lignocellulose is attractive because addition of water could reduce the cost and viscosity of the solvent and improve the biomass processing, but the solvating power of the IL is usually depressed in the presence of water. In the present study, an aqueous IL consisting of 1-butyl-3-methylimidazolium chloride (BmimCl), water, and lithium chloride was fabricated for efficient deconstruction and dissolution of lignocellulose (bamboo). The dissolution of cell wall components (cellulose, lignin, and hemicelluloses) in the aqueous IL was investigated. The results indicated that the presence of water significantly reduced the solvating power of BmimCl; For example, 11.5 % water decreased the dissolution of bamboo in BmimCl from ~97 to ~53 %. Dissolution of cellulose and lignin was specifically depressed. However, addition of lithium chloride was able to improve the tolerance of BmimCl to water and enhance the deconstruction and dissolution of biomass in BmimCl with high water content. It was found that approximately 80 % bamboo could be dissolved in solvent consisting of 45 wt% BmimCl and 55 wt% LiCl·2H₂O (25 wt% overall water content in the solvent). In particular, lignin and hemicelluloses were selectively dissolved by 96 and 92 %, respectively. The undissolved residue was predominantly composed of cellulose (~86 %) with a small amount of lignin (<5 %). BmimCl-LiCl-H₂O is a promising and effective solvent system with low cost and viscosity for biomass processing.