Xinyong Li

PHOTOCATALYTIC ACTIVITY OF WOX-TIO2 UNDER VISIBLE LIGHT IRRADIATION

Abstract With an attempt to extend light absorption of the TiO2-based photocatalysts toward the visible light range and eliminate the rapid recombination of excited electrons/holes during photoreaction, new photocatalyst (WOx-TiO2) powder was prepared by a sol–gel method. The photooxidation efficiency of WOx-TiO2 catalyst was also evaluated by conducting a set of experiments to photodegrade methylene blue (MB) in aqueous solution. The photocatalytic activity of WOx-TiO2 was examined by X-ray diffraction (XRD), UV–VIS absorption spectra, X-ray photoelectron emission spectroscopy (XPS), photoluminescence spectra (PL), surface photovoltage spectra (SPS) and electron-field-induced surface photovoltage spectra (EFISPS). The experiments demonstrated that the MB in aqueous solution was successfully photodegraded using WOx-TiO2 under visible light irradiation. It was found that an optimal WOx dosage of 3% in WOx-TiO2 achieved the highest rate of MB photodegradation in this experimental condition. It has been confirmed that WOx-TiO2 could be excited by visible light (E

Controllable synthesis of ZnO nanoflowers and their morphology-dependent photocatalytic activities

Different surface morphologies of TiO2 films were prepared through hydrothermal synthesis method on transparent fluorine-doped tin oxide (FTO) substrates by changing reaction temperatures. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and X-ray photoelectron spectrometer (XPS). As the hydrothermal temperatures increases, the surface morphologies of the TiO2 changes from nanorods (150 °C) to nanobuds (180 °C), and finally to nanoflowers (210 °C). Evolution of these structures are accompanied by great variations of optical properties and photocatalytic activities including a narrowing of band gap from 3.01 to 2.97 eV, increase of UV–visible absorption intensity and specific surface area, and photocatalytic degradation efficiencies from 88.18 to 95.56%. Under ultraviolet light (UV light) irradiation, the TiO2 nanoflowers exhibit significantly activity (95.56%) in degradation of methyl orange (MO) compared to commercial P25 (76.15%). The outstanding photocatalytic activity of the TiO2 nanoflowers can be attributed to the synergetic effect of much larger specific surface area, the larger content of oxygen vacancy, and higher intensity of absorption. These findings help to grow unique TiO2 films with desired structure and activities for photocatalyst applications.

Role of Hydroxyl Radicals and Mechanism of Escherichia coli Inactivation on Ag/AgBr/TiO2 Nanotube Array Electrode under Visible Light Irradiation

A ternary Ag/AgBr/TiO(2) nanotube array electrode with enhanced visible-light activity was synthesized by a two-step approach including electrochemical process of anodization and an in situ photoassisted deposition strategy. The dramatically enhanced photoelectrocatalytic activity of the composite electrode was evaluated via the inactivation of Escherichia coli under visible light irradiation (λ>420 nm), whose performance of complete sterilization was much superior to other reference photocatalysts. PL, ESR, and radicals trapping studies revealed hydroxyl radicals were involved as the main active oxygen species in the photoelectrocatalytic reaction. The process of the damage of the cell wall and the cell membrane was directly observed by ESEM, TEM, and FTIR, as well as further confirmed by determination of potassium ion leakage from the killed bacteria. The present results pointed to oxidative attack from the exterior to the interior of the Escherichia coli by OH(•), O(2)(•-), holes and Br(0), causing the cell to die as the primary mechanism of photoelectrocatalytic inactivation.

Electrochemically assisted photocatalytic degradation of 4-chlorophenol by ZnFe2O4-modified TiO2 nanotube array electrode under visible light irradiation.

A well-aligned ZnFe(2)O(4)/TiO(2) composite nanotube array (ZnFe(2)O(4)/TiO(2)-NTs) electrode with visible-light activity was successfully prepared using a two-step electrochemical process of anodization and a novel cathodic electrodeposition method followed by annealing. The ZnFe(2)O(4) nanoparticles were highly dispersed inside the TiO(2)-NTs but minimized at the tube entrances. The structure and optical properties of the TiO(2) nanotubes and the derived composites have been well characterized. The composites displayed a strong photo response in the visible region and low recombination rate of the electron-hole pairs. In addition, the synthesized ZnFe(2)O(4)/TiO(2)-NTs electrode showed much higher photocurrent density in the visible region than pure TiO(2)-NTs electrode. The dramatically enhanced electrochemically assisted photocatalytic activity of the composite electrode was evaluated in the decomposition of 4-chlorophenol and dichloroacetate under visible light irradiation (420 nm < lambda < 600 nm). The improved photoelectrocatalytic (PEC) activity is derived from the synergetic effect between ZnFe(2)O(4) and TiO(2), which promoted the migration efficiency of photogenerated carriers at the interface of the composite and enhanced the efficiency of photon harvesting in the visible region. The degradation of 4-chlorophenol was monitored by measuring Cl(-) concentrations and analyzing reaction intermediates by high-performance liquid chromatography-mass spectroscopy (HPLC-MS).

A general, one-step and template-free synthesis of sphere-like zinc ferrite nanostructures with enhanced photocatalytic activity for dye degradation

Spinel zinc ferrite nanospheres with diameters of about 212 nm were synthesized in high yield via a general, one-step and template-free solvothermal route. The prepared nanospheres had cubic spinel structure and exhibited good size uniformity and regularity. The absorption edge of ZnFe(2)O(4) nanospheres shifted to a higher energy in the UV-Vis absorption spectrum compared with that of ZnFe(2)O(4) nanoparticles. The ZnFe(2)O(4) nanospheres exhibited remarkably high surface photovoltage response in the UV and visible region, suggesting the enhanced separation ability of photogenerated electrons and holes. The dramatically enhanced photocatalytic activity of the ZnFe(2)O(4) nanospheres was evaluated in the decomposition of rhodamine B under Xe lamp irradiation. Hydroxyl radicals on the surface of photoilluminated ZnFe(2)O(4) nanospheres were detected by the photoluminescence technique, which suggested that hydroxyl radicals played an important role in the photocatalytic reaction. This study provided new insight into the design and preparation of functional nanomaterials with sphere structure in high yield, and the as-grown architectures demonstrated an excellent ability to remove organic pollutants in wastewater.

Fabrication of Cu2O/TiO2 nanotube heterojunction arrays and investigation of its photoelectrochemical behavior

Cu2O/TiO2 nanotube heterojunction arrays have been prepared by photoreduction depositing Cu2O nanoparticles on TiO2 nanotube arrays. The heterojunction arrays show uniformly distributed Cu2O nanoparticles, and high crystallinity of anatase and cubic from the TiO2 and Cu2O, respectively. The asymmetry of the current-voltage plot for the material reveals that a heterojunction has been formed between TiO2 and Cu2O. Enhanced charge separation efficiency and improved photoconversion capability are confirmed by electrochemical impedance spectroscopy and photocurrent measurement.

Fabrication of Ag/Ag3PO4/TiO2 heterostructure photoelectrodes for efficient decomposition of 2-chlorophenol under visible light irradiation

TiO2 nanotube arrays were decorated with Ag/Ag3PO4 nanoparticles through a sequential chemical bath deposition and followed by partial reduction of Ag+ ions in the Ag3PO4 nanoparticles to Ag0 under UV irradiation. The structure and optical properties of the Ag/Ag3PO4/TiO2 nanotube electrode were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflectance spectroscopy, photoluminescence (PL) spectroscopy and electrochemical techniques. The photoelectrocatalytic (PEC) activity of the composite electrode was evaluated by the decomposition of 2-chlorophenol under visible light irradiation (λ > 420 nm). Clusters of Ag/Ag3PO4 nanoparticles were successfully formed on the surface of the TiO2 nanotubes (NTs) causing no damage to the ordered structure of the nanotubes. The PL intensity of Ag/Ag3PO4/TiO2 NTs was much lower than that of TiO2 nanotubes. The p-type Ag3PO4 and Ag nanoparticles deposited on the TiO2 NTs could promote the transfer of photo-generated electrons, which inhibited the recombination of electrons and holes effectively, leading to a significant increase in the photocurrent density. Moreover, the Ag/Ag3PO4/TiO2 heterostructure photoelectrodes showed much higher PEC activity than the pure TiO2 NTs for the degradation of 2-CP aqueous solution under visible light irradiation. The enhanced PEC activity could be attributed to the visible-light photocatalytic activity of Ag3PO4 and the heterostructure between Ag3PO4 and TiO2. The electron spin resonance (ESR) spin-trap study further demonstrated that ˙OH could be generated on the Ag/Ag3PO4/TiO2 NTs under visible light irradiation.

Synthesis and Photoinduced Charge-Transfer Properties of a ZnFe2O4-Sensitized TiO2 Nanotube Array Electrode

TiO2 nanotube arrays sensitized with ZnFe2O4 nano-crystals were successfully fabricated by a two-step process of anodization and a vacuum-assistant impregnation method followed by annealing. The sample was studied by an environmental scanning electron microscope, a transmission electron microscope, energy-dispersive X-ray analysis, and X-ray diffraction to characterize its morphology and chemical composition. Ultraviolet-visible (UV-vis) absorption spectra and a photoelectrochemical measurement approved that the ZnFe2O4 sensitization enhanced the probability of photoinduced charge separation and extended the range of the photoresponse of TiO2 nanotube arrays from the UV to visible region. In addition, the behaviors of photoinduced charge transfer in a TiO2 nanotube array electrode before and after sensitization by ZnFe2O4 nanocrystals were comparatively studied. The photoluminescence of the TiO2 nanotube array electrode became suppressed, and the surface photovoltage responses on the spectrum were significantly enhanced after the introduction of ZnFe2O4 nanocrystals. The transfer dynamics of the photoinduced charges were observed directly by a transient photovoltage measurement, which revealed a fast charge separation at the interface between ZnFe2O4 nanocrystals and TiO2 nanotubes upon light excitation.

Synthesis and photocatalytic oxidation properties of iron doped titanium dioxide nanosemiconductor particles

The structure, physical characteristics and selective photocatalytic oxidation properties of quantum confined nanosize iron doped TiO2 (Q-TiO2/Fe3+) particles were studied by TG-DSC, XRD, DRS, EPR and Selective Oxidation Photocatalytic Measurements. It is shown that the solubility of iron in the obtained Q-TiO2/Fe3+ nanoparticles is 1.0 atom% and the iron doping level has a great influence on the transformation of anatase to rutile (A-R). The quantum confined effect was observed for Q-TiO2/Fe3+ nanoparticles. All of the samples have EPR Bulk-Fe3+ and Surf-Fe3+ signals, which are located in the bulk and surface of TiO2 nanoparticles respectively. Quantitative EPR results indicate that the relative EPR intensity of these paramagnetic centers shows regular change with varying corresponding iron modification level. In situ EPR indicates that the photo-generated charge carrier (h+, e−) could be trapped by different Fe3+ sites simultaneously, i.e., trapping of h+ is due to Surf-Fe3+ sites at g = 4.30, whereas that of e− is attributed to Bulk-Fe3+ sites at g = 1.99. Selective photocatalytic oxidation of cyclohexane into cyclohexanol with higher selectivity has been obtained by molecular oxygen activation over Q-TiO2/Fe3+ nanoparticles under mild conditions. It is thought that the optical surface state of Q-TiO2/Fe3+ nanoparticles play a key role in the selective photocatalytic oxidations.

BiFeO3/TiO2 Nanotube Arrays Composite Electrode: Construction, Characterization, and Enhanced Photoelectrochemical Properties

This work aims at the exploration of nanostructured ferroelectric-material-modified semiconductor electrodes for enhanced photo-induced activity. A well-aligned BiFeO3/TiO2-nanotubes (NTs) array with visible-light activity was successfully synthesized on a titanium sheet by combining anodization and an ultrasonic-immersion method followed by annealing. The structural and optical properties of the TiO2-NTs and the composite BiFeO3/TiO2-NTs were comparatively characterized. The composite BiFeO3/TiO2-NTs grown on a Ti sheet and used as an electrode exhibited a stronger absorption in the visible region and a much higher photoconversion efficiency than the pure TiO2-NTs/Ti electrode. Electrochemical impedance investigation attested to a significant improvement of the interfacial electron-transfer kinetics with enhanced separation of electron-hole pairs. The as-prepared composite electrode showed a high efficiency for photoelectrocatalytic degradation towards rhodamine B under visible-light irradiation (λ > 400 nm). The enhanced photoelectrocatalytic activity of the composite electrode could be attributed to the synergistic effect between the lowered electron-hole recombination rate by the applied bias and the wider spectral response promoted by the BiFeO3 component.