Jianjun Liao

Photocatalytic Degradation of Methyl Orange Using a TiO2/Ti Mesh Electrode with 3D Nanotube Arrays

To further improve the photocatalytic techniques for water purification and wastewater treatment, we successfully prepared a new type of TiO(2)/Ti mesh photoelectrode, by anodization in ethylene glycol solution. The three-dimensional arrays of nanotubes formed on Ti mesh show a significant improvement in photocatalytic activity, compared to the nanotube arrays formed on foil. This can be demonstrated by about 22 and 38% enhancement in the degradation efficiency per mass and per area, respectively, when TiO(2)/Ti mesh electrode was used to photocatalyze methyl orange (MO). Furthermore, the effects of different parameters on MO photodegradation were investigated, such as different photoelectrode calcination temperature, the initial pH value of MO solution, and the present of hydrogen peroxide. The superior photocatalytic activity could be achieved by the TiO(2)/Ti mesh photoelectrode calcinated at 550 °C, due to the appearance of mixed crystal phases of anatase and rutile. In strong acidic or caustic conditions, such as pH 1 or 13, a high degradation efficiency can be both obtained. The presence of H(2)O(2) in photocatalytic reactions can promote photocatalytic degradation efficiencies. Moreover, the experimental results demonstrated the excellent stability and reliability of the TiO(2)/Ti mesh electrode.

Nitrogen-Doped TiO2 Nanotube Arrays with Enhanced Photoelectrochemical Property

N-doped TiO2 nanotube arrays were prepared by electrochemical anodization in glycerol electrolyte, followed by electrochemical deposition in NH4Cl solution. An orthogonal experiment was used to optimize the doping conditions. Electrolyte concentration, reaction voltage, and reaction time were the main factors to influence the N-doping effect which was the determinant of the visible range photoresponse. The optimal N-doping conditions were determined as follows: reaction voltage is 3 V, reaction time is 2 h, and electrolyte concentration is 0.5 M. The maximal photocurrent enhanced ratio was 30% under white-light irradiation. About 58% improvement of photocatalytic efficiency was achieved in the Rhodamine B degradation experiment by N doping. The kinetic constant of the N-doped TNT arrays sample was almost twice higher than that of the undoped sample. Further analysis by X-ray photoelectron spectroscopy supported that electrochemical deposition is a simple and efficient method for N doping into TiO2 nanotube arrays.

Electrochemically self-doped hierarchical TiO2 nanotube arrays for enhanced visible-light photoelectrochemical performance: an experimental and computational study

A two-step electrochemical anodization method was used to prepare typical hierarchical top-ring/bottom-tube TiO2 nanotube arrays (TNTAs). Ti3+ self-doping into TiO2 was achieved via electrochemical reduction at different negative potentials in the range from −1.0 V to −1.6 V. Compared with the pristine TNTAs, the TNTAs reduced at −1.4 V presented a dramatically enhanced photoelectrochemical performance, which showed a 2.4 times enhancement in photocurrent density under simulated AM 1.5G illumination and 2.3 times increase in visible-light photocurrent density. Approximately 100% improvement in photoelectrochemical catalytic efficiency was obtained in a phenol degradation experiment. First-principles calculations demonstrated that the new states induced by Ti3+ self-doping might act as a shallow donor level to promote the separation of photogenerated electron–hole pairs. Moreover, the light absorption improved by the hierarchical nanostructure and the excellent electron conductivity induced by Ti3+ doping also account for the enhancement in the photoelectrochemical performance. These results suggest a reasonable design of photoelectrodes for efficient photoelectrochemical applications in the future.

Effects of Surface Modification of Nanotube Arrays on the Performance of CdS Quantum-Dot-Sensitized Solar Cells

CdS-sensitized TiO2 nanotube arrays have been fabricated using the method of successive ionic layer adsorption and reaction and used as a photoanode for quantum-dot-sensitized solar cells. Before being coated with CdS, the surface of TiO2 nanotube arrays was treated with TiCl4, nitric acid (HNO3), potassium hydroxide (KOH), and methyltrimethoxysilane (MTMS), respectively, for the purpose of reducing the interface transfer resistance of quantum-dot-sensitized solar cells. The surfaces of the modified samples represented the characteristics of superhydrophilic and hydrophobic which directly affect the power conversion efficiency of the solar cells. The results showed that surface modification resulted in the reduction of the surface tension, which played a significant role in the connectivity of CdS and TiO2 nanotube arrays. In addition, the solar cells based on CdS/TiO2 electrode treated by HNO3 achieved a maximum power conversion efficiency of 0.17%, which was 42% higher than the reference sample without any modification.

Regulation of the Electroanalytical Performance of Ultrathin Titanium Dioxide Nanosheets toward Lead Ions by Non-Metal Doping

Three non-metallic elements, sulfur, fluorine, and iodine, were used to dope the ultrathin two-dimensional TiO2 nanosheets, which would regulate their electroanalytical properties toward heavy metal ions. Among these doped materials, fluorine-doped TiO2 nanosheets shows the highest electrochemical sensitivity and a superior detection limit toward Pb(II) when the doping concentration is 10%. When compared with the bare TiO2 nanosheets, the sensitivity increased by 102%, and the detection limit decreased by 36.4%. Through combining further electrochemical experiments and density-functional theory calculations, the enhanced electrochemical performance stemming from element doping was then investigated in detail. The theoretical calculation demonstrated that fluorine doping could greatly increase the adsorption energy of Pb(II) on the TiO2 nanosheets and enhance their loading capacity. Both cyclic voltammetric and electrical impedance spectroscopy analysis indicated the enhanced electron transfer rate on the electrode modified by fluorine-doped TiO2 nanosheets. Further measurement on the desorption performance showed the better stripping response of Pb(II) on the electrode with TiO2 nanosheets after fluorine doping, which suggests that fluorine doping is beneficial for Pb(II) diffuse onto the electrode surface for the reduction and stripping reaction. Therefore, the element doping of two-dimensional TiO2 nanosheets provides a facile method to extend the electronic materials toward detection of heavy metal ions in the environment.

Tuning Cd adsorption behaviours on graphene by introducing defects: a first-principles study

Abstract Adsorption of Cadmium (Cd) on pristine and defective graphenes, including Stone–Wales (SW) defect and single vacancy (SV) defect, was studied by first-principles calculations. It is found that Cd adatom is weakly adsorbed on the pristine and SW defective graphene, while SV defect shows a substantial increase in the bonding with Cd adatom. Analysis of electronic density-of-state indicates that the effect of SV defect on the adsorption process can be mainly ascribed to the hybridisation between C-2p and Cd-5s orbitals. The results of charge density changes due to the Cd adsorption show the substantial amount of electrons are transferred from Cd to graphene, and the magnetic moment of substrate is increased after the adsorption of Cd. These experimental results suggest that SV graphene could be a good sensor for the detection of heavy metal ions.

Synthesis and characterization of hierarchical structured TiO 2 nanotubes and their photocatalytic performance on methyl orange

Hierarchical structured TiO2 nanotubes were prepared by mechanical ball milling of highly ordered TiO2 nanotube arrays grown by electrochemical anodization of titanium foil. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, specific surface area analysis, UV-visible absorption spectroscopy, photocurrent measurement, photoluminescence spectra, electrochemical impedance spectra, and photocatalytic degradation test were applied to characterize the nanocomposites. Surface area increased as the milling time extended. After 5 h ball milling, TiO2 hierarchical nanotubes exhibited a corn-like shape and exhibited enhanced photoelectrochemical activity in comparison to commercial P25. The superior photocatalytic activity is suggested to be due to the combined advantages of high surface area of nanoparticles and rapid electron transfer as well as collection of the nanotubes in the hierarchical structure. The hierarchical structured TiO2 nanotubes could be applied into flexible applications on solar cells, sensors, and other photoelectrochemical devices.

Electrochemical and density functional theory investigation on the differential behaviors of core-ring structured NiCo 2 O 4 nanoplatelets toward heavy metal ions

In order to further improve the electroanalytical performance toward heavy metal ions, core-ring structured NiCo2O4 nanoplatelets were used to modify glass carbon electrode (GCE) for the determination of heavy metal ions in water. Owing to the high surface area of NiCo2O4 nanoplatelets, the Pb(II) sensitivity increased by a factor of 1.70, and the detection limit decreased by a factor of 2.64 as compared to solid NiCo2O4 nanoparticles modified GCE. Interestingly, NiCo2O4 nanoplatelets showed different sensitivities toward heavy metal ions with the same valence states, following the order Pb(II) > Cd(II) > Hg(II) > Cu(II). To better and scientifically understand the difference in sensitivity, adsorption and desorption abilities were integrated into account. Density functional theory calculations verified that the adsorption capability of NiCo2O4 toward Pb(II) was strongest among all heavy metal ions, thereby resulting in the largest sensitivity. Further desorption current measurements indicated the large desorption barrier of Cu(II) was another important factor leading to its lowest sensitivity. Finally, the applicability of the proposed method was demonstrated by the detection of heavy metal ions in real seawater.