Baibiao Huang

Ag@AgCl: A Highly Efficient and Stable Photocatalyst Active under Visible Light

Nanoparticles (NPs) of noble metals can strongly absorb visible light because of their plasmon resonance, which is greatly influenced by their morphology and size. The phenomenon of plasmon resonance gives rise to important applications such as colorimetric sensors, photovoltaic devices, photochromic devices, and photocatalysts. Noble metal NPs exhibit characteristic optical and physical properties that are substantially different from those of the corresponding bulk materials. In particular, silver NPs show efficient plasmon resonance in the visible region, which Awazu et al. recently utilized to develop a plasmonic photocatalyst. In their study, TiO2 was deposited on NPs consisting of a silver core covered with a silica (SiO2) shell to prevent oxidation of Ag by direct contact with TiO2. Under UV illumination, this plasmonic photocatalyst exhibits enhanced catalytic activity, which increases with decreasing thickness of the SiO2 shell. To enhance the activity of a plasmonic photocatalyst, it is desirable to deposit silver NPs directly onto the surface of an active dielectric substrate without a protective shell, because the near-field effect of the NPs will be more strongly felt by the substrate. Herein we show that such a photocatalyst can be obtained from silver chloride by exploiting its photosensitivity, and the resulting plasmonic photocatalyst is highly efficient and stable under visible-light illumination. Silver halides are photosensitive materials extensively used as source materials in photographic films. On absorbing a photon, a silver halide particle generates an electron and a hole, and subsequently the photogenerated electron combines with an Ag ion to form an Ag atom. Ultimately, a cluster of silver atoms is formed within a silver halide particle upon repeated absorption of photons. Due to this instability under sunlight, which provides the very basis for chemical photography, silver halides are seldom used as photocatalysts. Nevertheless, there have been reports that under UV/Vis illumination AgCl deposited on a conducting support photocatalyzes O2 production from water in the presence of a small excess of silver ions in solution, and that under UV illumination AgBr dispersed on a silica support photocatalyzes H2 production from CH3OH/H2O solution. [21] In their study on the AgBr/SiO2 photocatalyst, Kakuta et al. [21] observed that Ag species are formed on AgBr in the early stage of the reaction, and AgBr is not destroyed under successive UV illumination. As suggested by Kakuta et al., electron–hole separation may occur smoothly in the presence of Ag species, and the latter may catalyze H2 production from alcohol radicals formed by photo-induced holes. If so, silver NPs formed on silver halide particles might be expected to be a stable photocatalyst under visible-light illumination due to their plasmon resonance. This expectation led us to prepare a new photocatalyst active and stable under visible light, namely, AgCl particles with silver NPs formed on their surface, by first treating Ag2MoO4 with HCl to form AgCl powder and then reducing some Ag ions in the surface region of the AgCl particles to Ag species (for details, see the Experimental Section). For convenience, these are referred to as Ag@AgCl particles. The X-ray diffraction (XRD) pattern of the Ag@AgCl product clearly shows that the cubic phase of Ag with lattice constant a= 4.0861 A (JCPDS file: 65-2871) coexists with the cubic phase of AgCl with lattice constant a= 5.5491 A (JCPDS file: 31-1238; see Figure 1). Scanning electron microscopy (SEM) images of the Ag@AgCl product (Figure 2) reveal that silver NPs with diameters in the range of 20–150 nm are deposited on the surface of AgCl particles with diameters in the range of 0.2–1.3 mm. The UV/Vis diffuse-reflectance spectra of Ag@AgCl, AgCl, and N-doped TiO2 (used as reference photocatalyst) are compared in Figure 3. In contrast to AgCl and N-doped TiO2, Ag@AgCl has a strong adsorption in the visible region which is almost as strong as that in the UV region. This is attributed to the plasmon resonance of silver NPs deposited on AgCl particles. To evaluate the photooxidation capability of Ag@AgCl, we examined the decomposition of methylic orange (MO) dye in solution over the Ag@AgCl sample under visible-light irradiation as a function of time (Figure 4). For comparison, we also carried out decomposition of the MO dye in solution over the N-doped TiO2 reference photocatalyst under visible[*] P. Wang, Prof. Dr. B. Huang, X. Qin, Prof. X. Zhang, Dr. J. Wei State Key Lab of Crystal Materials Shandong University, Jinan 250100 (China) E-mail: bbhuang@sdu.edu.cn Homepage: http://www.icm.sdu.edu.cn/index.php

Highly Efficient Visible‐Light Plasmonic Photocatalyst Ag@AgBr

Visible improvements: Owing to the plasmon resonance of silver nanoparticles deposited on the surface of AgBr, the newly-prepared plasmonic photocatalyst Ag section signAgBr has a strong absorption in the visible region (see picture) and shows high efficiency in the photodegradation of organic pollutants under visible light.

Oxygen Vacancy Induced Band-Gap Narrowing and Enhanced Visible Light Photocatalytic Activity of ZnO

Oxygen vacancies in crystal have important impacts on the electronic properties of ZnO. With ZnO(2) as precursors, we introduce a high concentration of oxygen vacancies into ZnO successfully. The obtained ZnO exhibits a yellow color, and the absorption edge shifts to longer wavelength. Raman and XPS spectra reveal that the concentration of oxygen vacancies in the ZnO decreased when the samples are annealed at higher temperature in air. It is consistent with the theory calculation. The increasing of oxygen vacancies results in a narrowing bandgap and increases the visible light absorption of the ZnO. The narrowing bandgap can be confirmed by the enhancement of the photocurrent response when the ZnO was irradiated with visible light. The ZnO with oxygen vacancies are found to be efficient for photodecomposition of 2,4-dichlorophenol under visible light irradiation.

Facile in situ synthesis of visible-light plasmonic photocatalysts M@TiO2 (M = Au, Pt, Ag) and evaluation of their photocatalytic oxidation of benzene to phenol

We developed a facile in situ method of preparing noble-metal plasmonic photocatalysts M@TiO2 (M = Au, Pt, Ag). In this method, the UV irradiation of TiO2 powder dispersed in absolute ethanol generates some Ti3+ ions on the surface of TiO2 particles and these Ti3+ ions, upon addition of a noble-metal salt in the dark, reduce the metal cations to deposit metal nanoparticles on the TiO2 surface. This Ti3+-ion-assisted synthesis leads to a homogeneous loading of noble-metal nanoparticles on the surface of TiO2 particles, which allows photocatalytic reactions to take place under visible-light on the whole TiO2 surface. Among the three photocatalysts M@TiO2 (M = Au, Pt, Ag), Au@TiO2 exhibits a high yield (63%) and selectivity (91%) for the oxidation of benzene to phenol in aqueous phenol. For this photocatalytic reaction, our study suggests a mechanism in which the visible-light absorption by the Au nanoparticles causes electron transfer from the Au nanoparticles to the TiO2 particle, and the electron-depleted Au oxidizes phenoxy anions to form phenoxy radicals that oxidize benzene to phenol.

Synthesis of Highly Efficient Ag@AgCl Plasmonic Photocatalysts with Various Structures

By means of a simple ion-exchange process (using different precursors) and a light-induced chemical reduction reaction, highly efficient Ag@AgCl plasmonic photocatalysts with various self-assembled structures-including microrods, irregular balls, and hollow spheres-have been fabricated. All the obtained Ag@AgCl catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and UV-visible diffuse reflectance spectroscopy. The effect of the different morphologies on the properties of the photocatalysts was studied. The average content of elemental Ag in Ag@AgCl was found to be about 3.2 mol %. All the catalysts show strong absorption in the visible-light region. The obtained Ag@AgCl samples exhibit enhanced photocatalytic activity for the degradation of organic contaminants under visible-light irradiation. The stability of the plasmonic photocatalysts was also investigated in detail.

In situ ion exchange synthesis of the novel Ag/AgBr/BiOBr hybrid with highly efficient decontamination of pollutants

A novel Ag/AgBr/BiOBr hybrid was prepared by a rational in situ ion exchange reaction between BiOBr hierarchical microspheres and AgNO(3) in ethylene glycol followed by light reduction, which displayed superior visible light driven photocatalytic activities in sterilization of pathogenic organism and degradation of organic dye compared to N-doped P25.

Evidence of the Existence of Magnetism in Pristine VX2 Monolayers (X = S, Se) and Their Strain-Induced Tunable Magnetic Properties

First-principles calculations are performed to study the electronic and magnetic properties of VX(2) monolayers (X = S, Se). Our results unveil that VX(2) monolayers exhibit exciting ferromagnetic behavior, offering evidence of the existence of magnetic behavior in pristine 2D monolayers. Furthermore, interestingly, both the magnetic moments and strength of magnetic coupling increase rapidly with increasing isotropic strain from -5% to 5% for VX(2) monolayers. It is proposed that the strain-dependent magnetic moment is related to the strong ionic-covalent bonds, while both the ferromagnetism and the variation in strength of magnetic coupling with strain arise from the combined effects of both through-bond and through-space interactions. These findings suggest a new route to facilitate the design of nanoelectronic devices for complementing graphene.

Ag/AgBr/WO3·H2O: Visible-Light Photocatalyst for Bacteria Destruction

A new composite photocatalyst Ag/AgBr/WO(3).H(2)O was synthesized by reacting Ag(8)W(4)O(16) with HBr and then reducing some Ag(+) ions in the surface region of AgBr particles to Ag nanoparticles via the light-induced chemical reduction. Ag nanoparticles are formed from AgBr by the light-induced chemical reduction reaction. The Ag/AgBr particles are on the surface of WO(3).H(2)O and have irregular shapes with sizes varying between 63 and 442 nm. WO(3).H(2)O appears as flakes about 31 nm thick and 157-474 nm wide. The as-grown Ag/AgBr/WO(3).H(2)O sample shows strong absorption in the visible region because of the plasmon resonance of Ag nanoparticles in Ag/AgBr/WO(3).H(2)O. The ability of this compound to destroy E. coli and oxidize methylic orange under visible light was compared with those of other reference photocatalysts. Ag/AgBr/WO(3).H(2)O is a highly efficient photocatalyst under visible light. The Ag/AgBr/WO(3).H(2)O samples recovered from repeated photooxidation experiments are almost identical to the as-prepared samples, proving the stability of Ag/AgBr/WO(3).H(2)O sample.

One-Pot Template-Free Synthesis of Monodisperse Zinc Sulfide Hollow Spheres and Their Photocatalytic Properties

Monodisperse wurtzite ZnS hollow spheres with diameters of about 200 nm and shells composed of nanoparticles have been successfully synthesized in high yield by a one-pot template-free hydrothermal route. The reaction duration, reactant species, and reaction temperature have been shown to play important roles in the formation of ZnS hollow spheres. X-ray diffraction, scanning and transmission electron microscopy, nitrogen adsorption/desorption, UV/Vis diffuse reflectance spectroscopy, and photoluminescence were used to characterize the products. The results show that all the prepared nanospheres have hexagonal wurtzite structures and exhibit good size uniformity and regularity. A mechanism for the formation of the ZnS hollow spherical structure by localized Ostwald ripening has been proposed based on experimental observations. In addition, studies of the photocatalytic properties of the ZnS hollow spheres by exposure to UV irradiation have demonstrated that they have potential photocatalytic applications. Hydroxyl radicals (*OH) were not detected on the surface of UV-illuminated ZnS by the photoluminescence technique, which suggests that *OH is not the dominant photo-oxidant and a photogenerated hole could instead directly participate in the photocatalytic reaction. The prepared ZnS hollow spheres are also of great interest for use in flat displays, sensors, lasers, catalysis, separation technology, biomedical engineering, and nanotechnology.

An anion exchange approach to Bi2WO6 hollow microspheres with efficient visible light photocatalytic reduction of CO2 to methanol

An anion exchange strategy is explored to synthesize Bi(2)WO(6) hollow microspheres based on the microscale Kirkendall effect. The as-prepared Bi(2)WO(6) hollow microspheres display high CO(2) adsorption capacity and visible light photocatalytic conversion efficiency of CO(2) into methanol without the aid of any co-catalyst.