Shifu Chen

Visible light photocatalytic activity enhancement and mechanism of AgBr/Ag3PO4 hybrids for degradation of methyl orange

Novel AgBr/Ag(3)PO(4) hybrids were synthesized via an in situ anion-exchange method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive spectroscopy (EDS) and UV-vis diffuse reflectance spectroscopy (DRS). Under visible light (λ>420 nm), AgBr/Ag(3)PO(4) degraded methyl orange (MO) efficiently and displayed much higher photocatalytic activity than that of pure AgBr or Ag(3)PO(4). X-ray photoelectron spectroscopy (XPS) suggests that AgBr/Ag(3)PO(4) transformed to be Ag@AgBr/Ag(3)PO(4)@Ag system while remained good photocatalytic activity after 5 times of cycle experiments. In addition, the quenching effects of different scavengers proved that reactive OH and h(+) played the major role for the MO degradation. The photocatalytic activity enhancement of AgBr/Ag(3)PO(4) is closely related to the efficient separation of electron-hole pairs derived from the matching band potentials between AgBr and Ag(3)PO(4), as well as the good electron trapping role of Ag nanoparticles in situ formed on the surfaces of AgBr and Ag(3)PO(4) particles during the photocatalytic reaction.

In situ preparation of novel p-n junction photocatalyst BiOI/(BiO)2CO3 with enhanced visible light photocatalytic activity

Novel p-n junction photocatalysts BiOI/(BiO)2CO3 with different contents of BiOI were in situ synthesized by etching (BiO)2CO3 precursor with hydroiodic acid (HI) solution. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectrometry (FT-IR), energy-dispersive spectroscopy (EDS) and UV-vis diffuse reflectance spectroscopy (DRS) were employed to study the structures, morphologies and optical properties of the as-prepared samples. Under visible light (λ>420 nm), BiOI/(BiO)2CO3 hybrid displayed much higher photocatalytic activity than pure (BiO)2CO3 and BiOI for the degradation of methyl orange (MO). The increased photocatalytic activity of BiOI/(BiO)2CO3 could be attributed to the formation of the p-n junction between p-BiOI and n-(BiO)2CO3, which effectively suppresses the recombination of photoinduced electron-hole pairs. Moreover, the tests of radical scavengers confirmed that •O2- and h+ were the main reactive species for the degradation of MO.

Design of a direct Z-scheme photocatalyst: Preparation and characterization of Bi2O3/g-C3N4 with high visible light activity

A direct Z-scheme photocatalyst Bi2O3/g-C3N4 was prepared by ball milling and heat treatment methods. The photocatalyst was characterized by X-ray powder diffraction (XRD), UV-vis diffuse reflection spectroscopy (DRS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) surface areas, photoluminescence technique (PL), and electron spin resonance (ESR) technology. The photocatalytic activity was evaluated by degradation of methylene blue (MB) and rhodamine B (RhB). The results showed that Bi2O3/g-C3N4 exhibited a much higher photocatalytic activity than pure g-C3N4 under visible light illumination. The rate constants of MB and RhB degradation for Bi2O3(1.0wt.%)/g-C3N4 are about 3.4 and 5 times that of pure g-C3N4, respectively. The migration of photogenerated carriers adopts a Z-scheme mechanism. The photoexcited electrons in the CB of Bi2O3 and photogenerated holes in the VB of g-C3N4 are quickly combined, so the photoexcited electrons in the CB of g-C3N4 and holes in the VB of Bi2O3 participate in reduction and oxidation reactions, respectively. O2(-), OH and h(+) are the major reactive species for the Bi2O3/g-C3N4 photocatalytic system.

Photocatalytic activity of novel AgBr/WO3 composite photocatalyst under visible light irradiation for methyl orange degradation.

A novel AgBr/WO(3) composite photocatalyst was synthesized by loading AgBr on WO(3) substrate via deposition-precipitation method and characterized by XRD, SEM and DRS. The as-prepared AgBr/WO(3) was composed of monoclinic WO(3) substrate and face-centered cubic AgBr nanoparticles with crystalline sizes less than 56.8 nm. AgBr/WO(3) had absorption edge at about 470 nm in the visible light region. The optical AgBr content in AgBr/WO(3) was 0.30:1 (Ag/W) at the corresponding apparent rate, k(app), of 0.0160 min(-1) for MO degradation. The highest k(app) was 0.0216 min(-1) for 4 g/L catalyst. The OH acted as active species. Addition of H(2)O(2) within 0.020 mmol/L can efficiently trap electrons to generate more OH and further improved photocatalytic activity of AgBr/WO(3).

Electronic structure and optical properties of Ag3PO4 photocatalyst calculated by hybrid density functional method

The electronic structure and optical properties of Ag3PO4 were studied by hybrid density functional theory. The results indicated that the band gap is 2.43 eV, which agrees well with the experimental value of 2.45 eV. The conduction bands of Ag3PO4 are mainly attributable to Ag 5s and 5p states, while the valence bands are dominated by O 2p and Ag 4d states. The highest valence band edge potential was 2.67 V (vs. normal hydrogen electrode), which has enough driving force for photocatalytic water oxidation and pollutants degradation. The optical absorption spectrum showed that Ag3PO4 is a visible light response photocatalyst.

Ball milled h-BN: An efficient holes transfer promoter to enhance the photocatalytic performance of TiO2

High activity hexagonal-BN (h-BN)/TiO(2) composite photocatalysts were prepared by ball milling method. The structural and optical properties of the samples were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectra (DRS), and fluorescence emission spectra. The effect of the loading amount of h-BN and the ball milling time on the photocatalytic degradation of Rhodamine B (RhB) and methylene blue (MB) was investigated. The results indicated that the photocatalytic activity of TiO(2) could be improved substantially by coupling with a proper amount of milled h-BN. The optimal loading amount of h-BN was found to be 0.5 wt% and the milling time was 30 min. Under this condition, the photocatalytic removal efficiencies of TiO(2) for RhB and MB could be increased as high as 15 and 8 times. The role of the milling process and the mechanism for the enhancements was finally discussed in terms of creation of negatively charged h-BN surface and promotion the separation of photoinduced holes, respectively.

One-pot hydrothermal synthesis of BiPO4/BiVO4 with enhanced visible-light photocatalytic activities for methylene blue degradation

Novel composite BiPO4/BiVO4 photocatalysts with different amounts of BiPO4 were synthesized by a simple one-pot hydrothermal method at pH = 0.5. The obtained photocatalysts were systematically characterized using X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectroscopy (DRS). The photocatalytic activities of BiPO4/BiVO4 were evaluated by the degradation of methylene blue (MB), methyl orange (MO) and rhodamine B (RhB) under visible light (λ > 400 nm). The results showed that all of the BiPO4/BiVO4 composites exhibited much higher photocatalytic activities than pure BiVO4 and BiPO4. Among the composites, 10% BiPO4/BiVO4 could degrade 92.1% MB after 5 h illumination and possessed the best photocatalytic activity. Meanwhile, the k value of 10% BiPO4/BiVO4 was 0.503 h−1, which was twice that of pure BiVO4. The enhanced photocatalytic activity could be mainly ascribed to the suitable BiPO4/BiVO4 heterojunction interface which could effectively promote the separation of photoinduced electron–hole pairs. Moreover, the radical scavengers experiments demonstrated that ˙O2− and h+ were the main reactive species for MB degradation under visible light.

Charge deformation and orbital hybridization: intrinsic mechanisms on tunable chromaticity of Y3Al5O12:Ce3+ luminescence by doping Gd3+ for warm white LEDs

The deficiency of Y3Al5O12:Ce (YAG:Ce) luminescence in red component can be compensated by doping Gd3+, thus lead to it being widely used for packaging warm white light-emitting diode devices. This article presents a systematic study on the photoluminescence properties, crystal structures and electronic band structures of (Y1−xGdx)3Al5O12: Ce3+ using powerful experimental techniques of thermally stimulated luminescence, X-ray diffraction, X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS) and ultraviolet photoelectron spectra (UPS) of the valence band, assisted with theoretical calculations on the band structure, density of states (DOS), and charge deformation density (CDD). A new interpretation from the viewpoint of compression deformation of electron cloud in a rigid structure by combining orbital hybridization with solid-state energy band theory together is put forward to illustrate the intrinsic mechanisms that cause the emission spectral shift, thermal quenching, and luminescence intensity decrease of YAG: Ce upon substitution of Y3+ by Gd3+, which are out of the explanation of the classic configuration coordinate model. The results indicate that in a rigid structure, the charge deformation provides an efficient way to tune chromaticity, but the band gaps and crystal defects must be controlled by comprehensively accounting for luminescence thermal stability and efficiency.

Photocatalytic reforming of glycerol for H2 evolution on Pt/TiO2: fundamental understanding the effect of co-catalyst Pt and the Pt deposition route

To fundamentally understand the effects of deposited Pt and its deposition route on the photocatalytic reforming (PR) of glycerol for H2 evolution over Pt/TiO2, several 1 wt% Pt/P25 (PT) samples were prepared by photo-deposition (PD, glycerol as hole scavenger) and impregnation–reduction deposition routes (IRD, NaBH4 or H2/Ar as reductant) using H2PtCl6 as the precursor. The samples were characterized by XRD, UV-Vis DRS, TEM and XPS, and the PR activities were examined and compared under ambient conditions. The formation of photo-induced charge carriers (CCs) over PT was measured by a photoluminescence technique using terephthalic acid as a probe molecule. The results indicated that the reforming activity depends on both the nature of the light harvesting of P25 and the characteristics of the co-catalyst Pt, including its chemical state, size, and the interaction with P25; Pt particles serve as the active sites for H2 evolution. Uniform Pt particles could be selectively and intimately deposited on P25 in the Pt(0) state via an in situ PD process (PT-S), while by IRD routes, Pt particles were randomly loaded on P25 with the surface in Pt(0) and the bulk in Pt(II/IV) states. Unlike the Pt chemical state, the Pt sizes were less impacted by the deposition routes and were about 2 nm. Compared to P25, a low generation efficiency of CCs was observed on platinized samples due to the covering of the photo-active sites by Pt. Pt(0) exhibits higher light shielding effect than Pt(II/IV). Meanwhile, the separation of CCs was promoted by Schottky barriers formed at the Pt–TiO2 interface. Photo-induced electrons could be trapped by the barriers and the process was favored by well-contacted Pt(0) and obstructed by the bulk Pt(II/IV) component. The promotion effect of Pt(0) prevails over its adverse effect. Thus, PT-S exhibited the highest PR activity as it only possesses Pt(0), demonstrating the advantage of the PD process. A control test suggests Pt with this kind of feature can only be achieved in a dilute suspension by the PD route.

Efficient utilization of photogenerated electrons and holes for photocatalytic selective organic syntheses in one reaction system using a narrow band gap CdS photocatalyst

In this study, a nanoparticle structure of CdS with cubic phase (CdS-G) was prepared by a facile solid-state reaction at room temperature for the first time. CdS-G can be used as a highly active photocatalyst for selective oxidation of p-methoxybenzyl alcohol (pMBA) to p-methoxybenzaldehyde (pMBAD) and reduction of nitrobenzene (NB) to aniline (AL) in a coupled reaction system under green mild reaction conditions through visible light irradiation. Compared with the counterparts prepared by the conventional precipitation method (CdS-P) and hydrothermal method (CdS-H), the photocatalytic performance of CdS-G is greatly improved owing to the unique features of the nanostructure, the high surface area, pore volume, visible light absorption and photoelectric properties. The yield of pMBAD (AL) over CdS-G is about 1.6 (5.2) and 1.9 (20.8) times higher than that over CdS-P and CdS-H, respectively. The CdS-G sample exhibits excellent selectivity and stability because its valence band (VB) and conduction band (CB) positions matched well with the redox potentials of pMBA/pMBAD and NB/AL. Furthermore, the photogenerated holes and electrons can be efficiently and directly reacted with pMBA and NB, respectively. The photocatalytic selective oxidation and reduction reaction is a synergistic reaction via producing and consuming protons. The photogenerated holes and electrons could be utilized thoroughly to produce pMBAD and AL, respectively. The molar ratio of pMBA and NB was 3 : 1, and the yield of pMBAD and AL could be successfully achieved at a theoretical ratio of 1 : 1. This work highlights the promising scope for selective organic synthesis in one reaction system under mild conditions using photogenerated electrons and holes directly and simultaneously.