Shiwei Lin

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.

Fabrication of carbon-coated NiO supported on graphene for high performance supercapacitors

In this work, carbon-coated NiO nanoparticles supported on graphene (NiO@C/graphene) have been synthesized by integrating an atomic layer deposition (ALD) technique with a simple acetylene decomposition method. Transmission electron microscopy, X-ray diffraction analysis, X-ray photoelectron spectroscopy and Raman results demonstrated that uniform carbon films were coated onto the surfaces of NiO nanoparticles supported on graphene. The electrochemical properties of the NiO@C/graphene were then investigated. The results showed that the special design enabled synergistic effects from graphene and the carbon layer to improve the electrochemical capacitive properties of NiO. As a supercapacitor electrode, the 400-NiO@C/graphene exhibits an initial specific capacitance of 408 F g−1 (1838 F g−1 for NiO) at 1 A g−1 and 68% is retained at 50 A g−1. After 2000 charge–discharge cycles, the specific capacitance improves the initial value of ∼28% at a high current density of 10 A g−1, suggesting a great potential for high performance supercapacitors.

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.

Photoelectrochemical Performance of Quantum dot-Sensitized TiO2 Nanotube Arrays: a Study of Surface Modification by Atomic Layer Deposition Coating

Although CdS and PbS quantum dot-sensitized TiO2 nanotube arrays (TNTAs/QDs) show photocatalytic activity in the visible-light region, the low internal quantum efficiency and the slow interfacial hole transfer rate limit their applications. This work modified the surface of the TNTAs/QDs photoelectrodes with metal-oxide overlayers by atomic layer deposition (ALD), such as coating Al2O3, TiO2, and ZnO. The ALD deposition of all these overlayers can apparently enhance the photoelectrochemical performance of the TNTAs/QDs. Under simulated solar illumination, the maximum photocurrent densities of the TNTAs/QDs with 10xa0cycles ZnO, 25xa0cycles TiO2, and 30xa0cycles Al2O3 overlayers are 5.0, 4.3, and 5.6xa0mA/cm2 at 1.0xa0V (vs. SCE), respectively. The photoelectrode with Al2O3 overlayer coating presents the superior performance, whose photocurrent density is 37 times and 1.6 times higher than those of the TNTAs and TNTAs/QDs, respectively. Systematic examination of the effects of various metal-oxide overlayers on the photoelectrochemical performance indicates that the enhancement by TiO2 and ZnO overcoatings can only ascribed to the decrease of the interfacial charge transfer impedance, besides which Al2O3 coating can passivate the surface states and facilitate the charge transfer kinetics. These results could be helpful to develop high-performance photoelectrodes in the photoelectrochemical applications.

A miniature photoelectrochemical sensor based on organic electrochemical transistor for sensitive determination of chemical oxygen demand in wastewaters.

A three-electrode configuration is often required in the conventional photoelectrochemical measurements. Nevertheless, one common drawback is the reference electrode and the counter electrode used in the measurements, which has been proved to be an impediment for the miniaturization. In this study, a simple, cost-effective and miniature photoelectrochemical sensor based on high sensitive organic electrochemical transistor (OECT) is developed and used for the determination of chemical oxygen demand (COD) in wastewaters. The devices show detection limit down to 0.01xa0mg/L COD, which is two orders of magnitude better than that of the conventional photoelectrochemical method. The excellent sensing performance can be contributed to the novel sensing mechanism of OECT devices. That is, the devices are sensitive to the potential changes induced by the photoelectrochemical reaction on TiO2 nanotube arrays gate electrodes. Real sample analyses are also carried out. The results demonstrate that the measured COD values using the OECT devices and the standard dichromate methods are in a good agreement. Since the proposed sensor is constructed on a miniature transistor, it is expected that the device shows a promising application on the integrated COD monitoring platform.

Phase Modulation of (1T‐2H)‐MoSe2/TiC‐C Shell/Core Arrays via Nitrogen Doping for Highly Efficient Hydrogen Evolution Reaction

Tailoring molybdenum selenide electrocatalysts with tunable phase and morphology is of great importance for advancement of hydrogen evolution reaction (HER). In this work, phase- and morphology-modulated N-doped MoSe2 /TiC-C shell/core arrays through a facile hydrothermal and postannealing treatment strategy are reported. Highly conductive TiC-C nanorod arrays serve as the backbone for MoSe2 nanosheets to form high-quality MoSe2 /TiC-C shell/core arrays. Impressively, continuous phase modulation of MoSe2 is realized on the MoSe2 /TiC-C arrays. Except for the pure 1T-MoSe2 and 2H-MoSe2 , mixed (1T-2H)-MoSe2 nanosheets are achieved in the N-MoSe2 by N doping and demonstrated by spherical aberration electron microscope. Plausible mechanism of phase transformation and different doping sites of N atom are proposed via theoretical calculation. The much smaller energy barrier, longer Huf8ffSe bond length, and diminished bandgap endow N-MoSe2 /TiC-C arrays with substantially superior HER performance compared to 1T and 2H phase counterparts. Impressively, the designed N-MoSe2 /TiC-C arrays exhibit a low overpotential of 137 mV at a large current density of 100 mA cm-2 , and a small Tafel slope of 32 mV dec-1 . Our results pave the way to unravel the enhancement mechanism of HER on 2D transition metal dichalcogenides by N doping.

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.

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.

Two-Dimensional Nanomaterials for Gas Sensing Applications: The Role of Theoretical Calculations

Two-dimensional (2D) nanomaterials have attracted a large amount of attention regarding gas sensing applications, because of their high surface-to-volume ratio and unique chemical or physical gas adsorption capabilities. As an important research method, theoretical calculations have been massively applied in predicting the potentially excellent gas sensing properties of these 2D nanomaterials. In this review, we discuss the contributions of theoretical calculations in the study of the gas sensing properties of 2D nanomaterials. Firstly, we elaborate on the gas sensing mechanisms of 2D layered nanomaterials, such as the traditional charge transfer mechanism, and a standard for distinguishing between physical and chemical adsorption, from the perspective of theoretical calculations. Then, we describe how to conduct a theoretical analysis to explain or predict the gas sensing properties of 2D nanomaterials. Thirdly, we discuss three important methods that have been applied in order to improve the gas sensing properties, that is, defect functionalization (vacancy, edge, grain boundary, and doping), heterojunctions, and electric fields. Among these strategies, theoretical calculations play a very important role in explaining the mechanisms underlying the enhanced gas sensing properties. Finally, we summarize both the advantages and limitations of the theoretical calculations, and present perspectives for further research on the 2D nanomaterials-based gas sensors.

Tailoring Bandgap of Perovskite BaTiO3 by Transition Metals Co-Doping for Visible-Light Photoelectrical Applications: A First-Principles Study

The physical and chemical properties of V-M″ and Nb-M″ (M″ is 3d or 4d transition metal) co-doped BaTiO3 were studied by first-principles calculation based on density functional theory. Our calculation results show that V-M″ co-doping is more favorable than Nb-M″ co-doping in terms of narrowing the bandgap and increasing the visible-light absorption. In pure BaTiO3, the bandgap depends on the energy levels of the Ti 3d and O 2p states. The appropriate co-doping can effectively manipulate the bandgap by introducing new energy levels interacting with those of the pure BaTiO3. The optimal co-doping effect comes from the V-Cr co-doping system, which not only has smaller impurity formation energy, but also significantly reduces the bandgap. Detailed analysis of the density of states, band structure, and charge-density distribution in the doping systems demonstrates the synergistic effect induced by the V and Cr co-doping. The results can provide not only useful insights into the understanding of the bandgap engineering by element doping, but also beneficial guidance to the experimental study of BaTiO3 for visible-light photoelectrical applications.