Shanqing Zhang

Anatase TiO2 microspheres with exposed mirror-like plane {001} facets for high performance dye-sensitized solar cells (DSSCs)

Anatase TiO(2) microspheres with exposed mirror-like plane {001} facets were successfully synthesized via a facile hydrothermal process. The photoanode composed of TiO(2) microsphere top layer shows an improved DSSCs efficiency owing to the superior light scattering effect of microspheres and excellent light reflecting ability of the mirror-like plane {001} facets.

Synthesis and characterisation of a polyacrylamide–polyacrylic acid copolymer hydrogel for environmental analysis of Cu and Cd

Abstract A polyacrylamide–polyacrylic acid copolymer hydrogel was prepared by the controlled hydrolysis of polyacrylamide in an alkaline solution of 10% sodium hydroxide. The structure and composition of the resulting copolymer hydrogel was approximately two acrylic acid units for every acrylamide unit. The capacity of the copolymer hydrogel to bind various metal ions was tested under a range of uptake conditions, with varying uptake time, pH and ionic strength. Ions such as Cu 2+ and Cd 2+ were bound more strongly to the copolymer hydrogel than the competing ions of Na + , K + , Ca 2+ and Mg 2+ , particularly at pH>5, largely due to the increased acidity of these transition metal ions. Metals bound to the copolymer hydrogel were efficiently (>94%) eluted in 2 M HNO 3 solution. The copolymer was found to have a p K a of ∼4.5 and had an equilibrium swelling ratio of 120 at pH>6 with an ionic strength equivalent to 0.01 M NaCl, and a swelling ratio of 265 at low ionic strengths. This material should be of use for the recovery and separation of Cu 2+ and Cd 2+ ions, and trace environmental analysis applications such as the diffusive gradients in thin films (DGT) technique.

A porous nitrogen and phosphorous dual doped graphene blocking layer for high performance Li–S batteries

Conductive confinement of sulfur and polysulfides via carbonaceous blocking layers can simultaneously address the issues of low conductivity, volume expansion of sulfur during the charge/discharge process and the polysulfide shuttling effect in lithium–sulfur (Li–S) batteries. Herein, a conductive and porous nitrogen and phosphorus dual doped graphene (p-NP-G) blocking layer is prepared via a thermal annealing and subsequent hydrothermal reaction route. The doping levels of N and P in p-NP-G as measured by X-ray photoelectron spectroscopy are ca. 4.38% and ca. 1.93%, respectively. The dual doped blocking layer exhibits higher conductivity than N or P single doped blocking layers. More importantly, density functional theory (DFT) calculations demonstrate that P atoms and –P–O groups in the p-NP-G layer offer stronger adsorption of polysulfides than the N species. The electrochemical evaluation results illustrate that the p-NP-G blocking layer can deliver superior initial capacity (1158.3 mA h g−1 at a current density of 1C), excellent rate capability (633.7 mA h g−1 at 2C), and satisfactory cycling stability (ca. 0.09% capacity decay per cycle), which are better than those of the N or P single doped graphene. This work suggests that this synergetic combination of conductive and adsorptive confinement strategies induced by the multi-heteroatom doping scheme is a promising approach for developing high performance Li–S batteries.

Facile synthesis of highly efficient one-dimensional plasmonic photocatalysts through Ag@Cu2O core-shell heteronanowires

A novel class of one-dimensional (1D) plasmonic Ag@Cu2O core-shell heteronanowires have been synthesized at room temperature for photocatalysis application. The morphology, size, crystal structure and composition of the products were investigated by XRD, SEM, TEM, XPS, and UV-vis instruments. It was found the reaction time and the amount of Ag nanowires play crucial roles in the formation of well-defined 1D Ag@Cu2O core-shell heteronanowires. The resultant 1D Ag@Cu2O NWs exhibit much higher photocatalytic activity toward degradation of organic contaminants than Ag@Cu2O core-shell nanoparticles or pure Cu2O nanospheres under solar light irradiation. The drastic enhancement in photocatalytic activity could be attributed to the surface plasmon resonance and the electron sink effect of the Ag NW cores, and the unique 1D core-shell nanostructure.

A Facile Vapor-Phase Hydrothermal Method for Direct Growth of Titanate Nanotubes on a Titanium Substrate via a Distinctive Nanosheet Roll-Up Mechanism

We present a facile vapor-phase hydrothermal approach for direct growth of vertically aligned titanate nanotubes on a titanium foil substrate. The resultant nanotubes display external diameters of 50-80 nm and walls with an average thickness of 10 nm that consist of more than 10 titanate layers. This is in strong contrast to the titanate nanotubes obtained from alkaline liquid-phase hydrothermal methods, which are generally smaller than 12 nm in external diameter and have walls consisting of less than five titanate layers. Importantly, the investigation confirmed that under vapor-phase hydrothermal conditions, the nanotubes were formed via a distinctive nanosheet roll-up mechanism that differs remarkably from those of conventional liquid-phase hydrothermal processes. For the first time, a coaxial circular cylinder crystal structure of the resultant nanotubes was confirmed.

Facile Fabrication of Anatase TiO2 Microspheres on Solid Substrates and Surface Crystal Facet Transformation from {001} to {101}

Anatase TiO(2) microspheres with controlled surface morphologies and exposed crystal facets were directly synthesized on metal titanium foil substrates by means of a facile, one-pot hydrothermal method without use of any templating reagent. The obtained products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelecron spectroscopy (XPS), and the focused ion beam (FIB) technique. The sizes of the resultant microspheres ranged from 1.1 to 2.1 μm. The transformation of anatase TiO(2) microspheres with exposed {001} facets surface to nanosheets surface with {101} facets was achieved by simply controlling the hydrothermal reaction time. The anatase TiO(2) microspheres with exposed square-shaped plane {001} facets were obtained by controlling the reaction time at 1 h. The prolonged reaction time transforms the anatase TiO(2) microspheres with exposed square-shaped plane {001} facets to eroded {001} facets then to a nanosheet surface with exposed {101} facets. With hydrothermal synthesis, the surface morphological structure and crystal facets formation are highly dependent on dissolution/deposition processes, which can be strongly influenced by attributes, such as pH of the reaction media, the total concentration of dissolved and suspended titanium species, and the concentration of fluoride in the reaction solution. The changes of these attributes during the hydrothermal process were therefore measured and used to illustrate the morphology and crystal-facet transformation processes of anatase TiO(2) microspheres. The surface morphologies and crystal-facet transformations during hydrothermal processes were found to be governed by the compositional changes of the reaction media, driven by dynamically shifted dissolution/deposition equilibria. The photocatalytic activities of the photoanodes made of anatase TiO(2) microspheres were evaluated. The experimental results demonstrated that the photocatalytic activity of anatase TiO(2) microspheres with exposed {001} facets was found to be 1.5 times higher than that of the anatase TiO(2) microspheres with exposed {101} facets.

Photoelectrochemical Characterization of Hydrogenated TiO2 Nanotubes as Photoanodes for Sensing Applications

In this work, hydrogenated TiO2 nanotubes (H-TNTs) electrodes were successfully fabricated via the anodization of a titanium sheet followed by a hydrogenation process. Oxygen vacancies were induced in the crystalline structure of TiO2 nanotubes (TNTs) as shallow donors that enhance the electronic conductivity of the TNTs. This improvement in the electronic conductivity and photoelectrocatalytic (PEC) performance was confirmed and evaluated by a photoelectrochemical characterization. Most importantly, the H-TNTs electrode was able to degrade potassium hydrogen phthalate (strong adsorbent) and glucose (weak adsorbent) indiscriminately. The corresponding photocurrents at the H-TNTs were 2-fold greater than that of the TNTs samples for the same concentrations of the organic compounds. This suggests that the H-TNTs electrode can be a promising sensor for the PEC determination of individual organic compounds or as an aggregative parameter of organic compounds (e.g., chemical oxygen demand).

Fabrication of Highly Ordered TiO2 Nanorod/Nanotube Adjacent Arrays for Photoelectrochemical Applications

This work reports a facile approach to fabricate a perpendicularly aligned and highly ordered TiO(2) nanorod/nanotube (NR/NT) adjacent film by directly anodizing a modified titanium foil. The titanium foil substrate was modified with a layer of crystalline TiO(2) film via a hydrothermal process in 0.05 M (NH(4))(2)S(2)O(8). The resultant NR/NT architecture consists of a highly ordered nanorod top layer that directly adjoins to a highly ordered nanotube array bottom layer. The thickness of the top nanorod layer was approximately 90 nm with average nanorod diameter of 22 nm after 20 min of anodization. The thickness of the bottom nanotube array layer was found to be ca. 250 nm after 20 min of anodization, having an average outer and inner tubular diameters of 120 and 80 nm, respectively. A broad implication of the method is that a simple modification to the substrate surface can lead to new forms of nanostructures. For as-anodized NR/NT samples, XRD analysis reveals that the nanorods are of anatase TiO(2) crystalline form while the nanotubes are amorphous. Anatase TiO(2) crystalline form of NR/NT film with high crystallinity can be obtained by thermally treating the as-anodized sample at 450 degrees C for 2 h in air. The resultant NR/NT film was used as a photoanode for photoactivity evaluation. Comparing with a nanotube array photoanode prepared by direct anodization of unmodified titanium foil, the NR/NT photoanode exhibits a unique feature of selective photocatalytic oxidation toward organics, which makes it very attractive to photocatalytic degradation of organic pollutants, sensing, and other applications.

Photoelectrochemical measurement of phthalic acid adsorption on porous TiO2 film electrodes

A new adsorption measurement method based on photoelectrochemical oxidation principles has been developed. The method can be used to directly quantify the amount of adsorbates at a TiO2 electrode surface in a sensitive and accurate manner. The adsorption of phthalic acid was studied as a test case. The relationship between the amount of adsorbate at the TiO2 surface and the concentration of phthalic acid in the solution was obtained. The adsorption of phthalic acid on TiO2 surface was shown to follow a Langmuir type adsorption model. For the first time, the adsorption equilibrium constant of an adsorbate at TiO2 surface has been photoelectrochemically measured. The adsorption equilibrium constant of phthalate on TiO2 porous film at pH 4.0, K=4.0×104 M−1, was obtained using our method, which was close to that obtained by conventional methods. The effect of solution pH on the amount of adsorbate at TiO2 surface was also investigated. The results indicate the adsorption of phthalic acid is mainly of chemical bonding nature.

Development of an electrochemical flow injection immunoassay (FIIA) for the real-time monitoring of biospecific interactions

Not only are sensors a revolution in analysis; they themselves are also experiencing a revolution brought about by parallel developments in sensor fabrication techniques and materials, polymer chemistry, signal processing methodologies, the increased use of biomolecular processes as a means of analyte detection, and the coupling of sensors to other techniques such as flow injection analysis. Many of these developments have been incorporated into the present study, which we are undertaking in the development of our immunosensor technology. The system described here utilises screen-printed electrodes which are low-cost, disposable devices that are simple to fabricate. Incorporated into our sensor is the electroactive polymer, polyaniline, which brings about mediatorless redox coupling between the electrode and biomolecular components attached to the polymer surface. This system also utilises enzyme-labelled antibodies as the biomolecular recognition component for the analysis of the test analyte, biotin. The system has also been integrated into a flow injection system. This has led to the monitoring of real-time antibody-antigen interactions using electrochemical methods and foreshadows the development of single-step immunosensors.