Zhanhu Guo

One-Pot Synthesis of Magnetic Graphene Nanocomposites Decorated with Core@Double-shell Nanoparticles for Fast Chromium Removal

A facile thermodecomposition process to synthesize magnetic graphene nanocomposites (MGNCs) is reported. High-resolution transmission electron microscopy and energy filtered elemental mapping revealed a core@double-shell structure of the nanoparticles with crystalline iron as the core, iron oxide as the inner shell and amorphous Si-S-O compound as the outer shell. The MGNCs demonstrate an extremely fast Cr(VI) removal from the wastewater with a high removal efficiency and with an almost complete removal of Cr(VI) within 5 min. The adsorption kinetics follows the pseudo-second-order model and the novel MGNC adsorbent exhibits better Cr(VI) removal efficiency in solutions with low pH. The large saturation magnetization (96.3 emu/g) of the synthesized nanoparticles allows fast separation of the MGNCs from liquid suspension. By using a permanent magnet, the recycling process of both the MGNC adsorbents and the adsorbed Cr(VI) is more energetically and economically sustainable. The significantly reduced treatment time required to remove the Cr(VI) and the applicability in treating the solutions with low pH make MGNCs promising for the efficient removal of heavy metals from the wastewater.

Advanced titania nanostructures and composites for lithium ion battery

Owing to the increasing demand of energy and shifting to the renewable energy resources, lithium ion batteries (LIBs) have been considered as the most promising alternative and green technology for energy storage applied in hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and other electric utilities. Owing to its environmental benignity, availability, and stable structure, titanium dioxide (TiO2) is one of the most attractive anode materials of LIBs with high capability, long cycling life, high safety, and low cost. However, the poor electrical conductivity and low diffusion coefficient of Li-ions in TiO2 hamper the advancement of TiO2 as anode materials of LIBs. Therefore, intensive research study has been focused on designing the nanostructures of TiO2 and its composites to reduce the diffusion length of Li-ion insertion/extraction and improve the electrical conductivity of the electrode materials. In this article, the development of TiO2 and its composites in nano-scales including fabrication, characterization of TiO2 nanomaterials, TiO2/carbon composite, and TiO2/metal oxide composites to improve their properties (capacity, cycling performance, and energy density) for LIBs are reviewed. Meanwhile, the mechanisms for influences of the structure, surface morphology, and additives to TiO2 composites on the related properties of TiO2 and TiO2 composites to LIBs are discussed. The new directions of research on this field are proposed.

Surface functionalized alumina nanoparticle filled polymeric nanocomposites with enhanced mechanical properties

Alumina nanoparticles were successfully functionalized with a bi-functional coupling agent, (3-methacryloxypropyl)trimethoxysilane (MPS), through a facile neutral solvent method. MPS was found to be covalently bound with the nanoparticles. The linked MPS was polymerized with a vinyl-ester resin monomer through a free radical polymerization. Atomic force microscope phase images showed a uniform distribution of nanoparticles. Microtensile test results revealed the Youngs modulus and strength increasing with particle loading. Microscopic examinations revealed the presence of large plastic deformations at the micron scale in the nanocomposites in agreement with the observed strengthening effect of functionalized nanoparticles. Thermo-gravimetric analysis (TGA) did not show any significant change in the thermal degradation of the nanocomposite as compared with the neat resin. The polymer matrix effectively protected the alumina nanoparticles from dissolution in basic and acidic solutions.

In situ stabilized carbon nanofiber (CNF) reinforced epoxy nanocomposites

Carbon nanofibers (CNFs) suspended epoxy resin nanocomposites and the corresponding polymer nanocomposites are fabricated. The surface of CNFs is introduced a functional amine terminated groups via silanization, which in situ react with epoxy monomers. This in situ reaction favors the CNFs dispersion and improves the interfacial interaction between CNFs and monomers. Effects of particle loading, surface treatment and operating temperatures of rheological tests on the complex viscosity, storage modulus and loss modulus are systematically studied. Unique rheological phenomena “a decreased viscosity with a better dispersion” are observed and explained in terms of the improved filler dispersion quality. Meanwhile, significant increase in the tensile property and storage modulus is observed and related to the better dispersion and the introduced strong interfacial interaction as revealed by SEM imaging. Finally, electrical conductivity is investigated and an unusual deficiency of surface treatment to improve the electrical conductivity is explained by an insulating coating layer.

Electrically conductive thermoplastic elastomer nanocomposites at ultralow graphene loading levels for strain sensor applications

An electrically conductive ultralow percolation threshold of 0.1 wt% graphene was observed in the thermoplastic polyurethane (TPU) nanocomposites. The homogeneously dispersed graphene effectively enhanced the mechanical properties of TPU significantly at a low graphene loading of 0.2 wt%. These nanocomposites were subjected to cyclic loading to investigate the influences of graphene loading, strain amplitude and strain rate on the strain sensing performances. The two dimensional graphene and the flexible TPU matrix were found to endow these nanocomposites with a wide range of strain sensitivity (gauge factor ranging from 0.78 for TPU with 0.6 wt% graphene at the strain rate of 0.1 min−1 to 17.7 for TPU with 0.2 wt% graphene at the strain rate of 0.3 min−1) and good sensing stability for different strain patterns. In addition, these nanocomposites demonstrated good recoverability and reproducibility after stabilization by cyclic loading. An analytical model based on tunneling theory was used to simulate the resistance response to strain under different strain rates. The change in the number of conductive pathways and tunneling distance under strain was responsible for the observed resistance-strain behaviors. This study provides guidelines for the fabrication of graphene based polymer strain sensors.

Lightweight conductive graphene/thermoplastic polyurethane foams with ultrahigh compressibility for piezoresistive sensing

Lightweight conductive porous graphene/thermoplastic polyurethane (TPU) foams with ultrahigh compressibility were successfully fabricated by using the thermal induced phase separation (TISP) technique. The density and porosity of the foams were calculated to be about 0.11 g cm−3 and 90% owing to the porous structure. Compared with pure TPU foams, the addition of graphene could effectively increase the thickness of the cell wall and hinder the formation of small holes, leading to a robust porous structure with excellent compression property. Meanwhile, the cell walls with small holes and a dendritic structure were observed due to the flexibility of graphene, endowing the foam with special positive piezoresistive behaviors and peculiar response patterns with a deflection point during the cyclic compression. This could effectively enhance the identifiability of external compression strain when used as piezoresistive sensors. In addition, larger compression sensitivity was achieved at a higher compression rate. Due to high porosity and good elasticity of TPU, the conductive foams demonstrated good compressibility and stable piezoresistive sensing signals at a strain of up to 90%. During the cyclic piezoresistive sensing test under different compression strains, the conductive foam exhibited good recoverability and reproducibility after the stabilization of cyclic loading. All these suggest that the fabricated conductive foam possesses great potential to be used as lightweight, flexible, highly sensitive, and stable piezoresistive sensors.

An overview of the engineered graphene nanostructures and nanocomposites

This critical review focuses on the property analysis of graphene and graphene nanocomposites (GNCs) and their demonstrated superior performances in energy storage and conversion, electrochemical- and bio-sensing, environmental remediation and flame retardant application and atomic thickness membrane separation. The performances of graphene and GNCs are strongly dependent on their chemical component, synthetic method, nanoscale morphology, and assembling structure of the hybrids. The current progress in supercapacitor energy storage density, solar cell power conversion efficiency, thermoelectric energy conversion efficiency, electrochemical sensing capability, biosensor sensitivity, heavy metal adsorption capacity and efficiency, photocatalytic degradation rate of organic dye, flame retardant polymer nanocomposites, graphene and porous graphene membranes is discussed with detailed examples through extensive analysis of the literature.

Nanoparticle Dispersion and Aggregation in Polymer Nanocomposites: Insights from Molecular Dynamics Simulation

It is a great challenge to fully understand the microscopic dispersion and aggregation of nanoparticles (NPs) in polymer nanocomposites (PNCs) through experimental techniques. Here, coarse-grained molecular dynamics is adopted to study the dispersion and aggregation mechanisms of spherical NPs in polymer melts. By tuning the polymer-filler interaction in a wide range at both low and high filler loadings, we qualitatively sketch the phase behavior of the PNCs and structural spatial organization of the fillers mediated by the polymers, which emphasize that a homogeneous filler dispersion exists just at the intermediate interfacial interaction, in contrast with traditional viewpoints. The conclusion is in good agreement with the theoretically predicted results from Schweizer et al. Besides, to mimick the experimental coarsening process of NPs in polymer matrixes (ACS Nano 2008, 2, 1305), by grafting polymer chains on the filler surface, we obtain a good filler dispersion with a large interparticle distance. Considering the PNC system without the presence of chemical bonding between the NPs and the grafted polymer chains, the resulting good dispersion state is further used to investigate the effects of the temperature, polymer-filler interaction, and filler size on the filler aggregation process. It is found that the coarsening or aggregation process of the NPs is sensitive to the temperature, and the aggregation extent reaches the minimum in the case of moderate polymer-filler interaction, because in this case a good dispersion is obtained. That is to say, once the filler achieves a good dispersion in a polymer matrix, the properties of the PNCs will be improved significantly, because the coarsening process of the NPs will be delayed and the aging of the PNCs will be slowed.

Magnetic polyaniline nanocomposites toward toxic hexavalent chromium removal

The removal of toxic hexavalent chromium (Cr(VI)) from polluted water by magnetic polyaniline (PANI) polymer nanocomposites (PNCs) was investigated. The PNCs were synthesized using a facile surface initiated polymerization (SIP) method and demonstrated unique capability to remove Cr(VI) from polluted solutions with a wide pH range. Complete Cr(VI) removal from a 20.0 mL neutral solution with an initial Cr(VI) concentration of 1.0–3.0 mg L−1 was observed after a 5 min treatment period with a PNC load of 10 mg. The PNC dose of 0.6 g L−1 was found to be sufficient for complete Cr(VI) removal from 20.0 mL of 9.0 mg L−1 Cr(VI) solution. The saturation magnetization was observed to have no obvious decrease after treatment with Cr(VI) solution, and these PNCs could be easily recovered using a permanent magnet and recycled. The Cr(VI) removal kinetics were determined to follow pseudo-first-order behavior with calculated room temperature pseudo-first-order rate constants of 0.185, 0.095 and 0.156 min−1 for the solutions with pH values of 1.0, 7.0 and 11.0, respectively. The Cr(VI) removal mechanism was investigated by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and energy-filter transmission electron microscopy (EFTEM). The results showed that PANI was partially oxidized after treatment with Cr(VI) solution, with Cr(VI) being reduced to Cr(III). The EFTEM observation indicated that the adsorbed Cr(III) had penetrated into the interior of the PNCs instead of simply adsorbing on the PNC surface. This synthesized material was found to be easily regenerated by 1.0 mol L−1p-toluene sulfonic acid (PTSA) or 1.0 mol L−1 hydrochloric acid (HCl) and efficiently reused for further Cr(VI) removal.

Carbon nanostructure-derived polyaniline metacomposites: electrical, dielectric, and giant magnetoresistive properties.

Polyaniline (PANI) nanocomposites incorporating different loadings of graphene and various other carbon nanostructures including carbon nanotubes (CNTs) and carbon nanofibers (CNFs) have been synthesized using a surface-initiated polymerization (SIP) method. Transmission electron microscopy (TEM) results indicate that the graphene has been exfoliated into a few layers (typically one, two, and three layers) during polymerization and has been uniformly dispersed in the PANI matrix. The graphene layer dispersion degree is quantified by a free-path spacing measurement (FPSM) method based on the TEM microstructures. The SIP method also demonstrates its feasibility for coating PANI on one-dimensional (1D) CNFs and CNTs without introducing additional surface functional groups. The effects of graphene size, loading level, and surface functionality on the electrical conductivity and dielectric permittivity of their corresponding nanocomposites have been systematically studied. The temperature-dependent conductivity behavior revealed a quasi-3D variable range hopping (VRH) electron transport mechanism for all the nanocomposites. Giant magnetoresistance (GMR) at room temperature is observed in pure PANI, which can be enhanced by the incorporation of a high loading of graphene (5%) due to the π-π stacking-induced efficient electron transport at the PANI/graphene interface. More interestingly, negative permittivity is found in each composite which can be easily tuned by adjusting the filler loading, morphology, and surface functionality.