Impact of synthesis methods on nanosized silver modified titania photocatalysts

This work reports the synthesis and studies on photocatalytic activity of a material based on titanium oxide doped with silver. Two kinds of Ag-deposited TiO₂ were synthesized via soft chemical reduction (SCR) and photodeposition (PD) methods. The structure, composition and chemical properties of the obtained products were investigated by X-ray diffraction, UV-vis diffuse reflectance spectroscopy, photoluminescence spectra and Fourier transformation infrared spectroscopy techniques. The photocatalytic oxidation activity in a course of removal and destruction of organic compounds such as methyl orange dye using Ag/TiO₂ hybrid material was studied. The results suggest that SCR synthesized Ag/TiO₂ exhibited better photocatalytic performance that that obtained by PD method. The relationship between the synthesis method and photocatalytic activity of synthesized Ag/TiO₂ was analyzed with a focus on the plasmonic photocatalysis of silver. When compared to PD method, the SCR produced more homogeneous and smaller silver particles with a better dispersion than photodeposition that results in a relative increase of material activity in the photocatalytic degradation of dye pollutant.     

Plasmon-resonance-enhanced visible-light photocatalytic activity of Ag quantum dots/TiO2 microspheres for methyl orange degradation

We successfully prepared Ag quantum dots modified TiO₂ microspheres by facile solvothermal and calcination method. The as-prepared Ag quantum dots/TiO₂ microspheres were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The Ag quantum dots/TiO₂ photocatalyst showed excellent visible light absorption and efficient photocatalytic activity for methyl orange degradation. And the sample with the molar ratio of 0.05 (Ag to Ti) showed the best visible light photocatalytic activity for methyl orange degradation, mainly because of the surface plasmon resonance (SPR) effects of Ag quantum dots to generate electron and hole pairs for enhanced visible light photocatalysis. Finally, possible visible light photocatalytic mechanism of Ag quantum dots/TiO₂ microspheres for methyl orange degradation was proposed in detail.     

Silver Quantum Cluster (Ag9)‐Grafted Graphitic Carbon Nitride Nanosheets for Photocatalytic Hydrogen Generation and Dye Degradation

We report the visible‐light photocatalytic properties of a composite system consisting of silver quantum clusters [Ag₉(H₂MSA)₇] (H₂MSA=mercaptosuccinic acid) embedded on graphitic carbon nitride nanosheets (AgQCs‐GCN). The composites were prepared through a simple chemical route; their structural, chemical, morphological, and optical properties were characterized by using X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy, transmission electron microscopy, UV/Vis diffuse reflectance spectroscopy, and photoluminescence spectroscopy. Embedment of [Ag₉(H₂MSA)₇] on graphitic carbon nitride nanosheets (GCN) resulted in extended visible‐light absorption through multiple single‐electron transitions in Ag quantum clusters and an effective electronic structure for hydroxyl radical generation, which enabled increased activity in the photocatalytic degradation of methylene blue and methyl orange dye molecules compared with pristine GCN and silver nanoparticle‐grafted GCN (AgNPs‐GCN). Similarly, the amount of hydrogen generated by using AgQCs‐GCN was 1.7 times higher than pristine GCN. However, the rate of hydrogen generated using AgQCs‐GCN was slightly less than that of AgNPs‐GCN because of surface hydroxyl radical formation. The plausible photocatalytic processes are discussed in detail.     

复合Ag/ZnO分级结构微球的制备及其光催化性能研究

采用化学沉淀法制备ZnO微球,利用柠檬酸三钠（TCD）避光还原硝酸银在ZnO表面沉积银粒子制备Ag/ZnO复合材料.利用XRD、SEM、TEM、EDS、FTIR、UV-vis DRS、PL、BET等对Ag/ZnO的结构、组分、形貌及光谱性质进行了表征,通过紫外及可见光照降解甲基橙溶液评价样品的光催化性能.结果表明：ZnO纳米微球是由ZnO纳米片相互交错构筑而成的具有丰富孔道的分级结构,Ag纳米粒子均匀沉积在ZnO纳米片上.Ag的沉积显著增加了ZnO的可见光吸收,猝灭了ZnO荧光,提高了ZnO催化活性.     

Ag/BiOX (X=Cl,Br, I)复合光催化剂的制备、表征及其光催化性能

采用光化学沉积法制备了一系列不同Ag含量的新型Ag/BiOX(X=Cl,Br,I)复合光催化剂,应用X射线粉末衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)、光致发光(PL)谱、紫外-可见(UV-Vis)光谱和N2物理吸附等手段对催化剂进行表征,并以420nm<λ<660nm的可见光为光源,评价了该催化剂光催化降解酸性橙II的活性,考察了不同含量的Ag沉积对BiOX样品光催化性能的影响.N2物理吸附测试结果表明,沉积银在一定程度降低了催化剂的比表面积.UV-Vis测试结果表明,Ag能产生表面等离子共振吸收,有效增强BiOCl和BiOBr对可见光的吸收能力.PL测试结果则表明,Ag能显著抑制光生电子(e-)和空穴(h+)的复合.Ag的存在大幅度提高了BiOX对染料的光催化降解活性.当负载Ag的质量分数(w)为1%-2%时,可使BiOCl、BiOBr和BiOI光催化活性分别提高了10、13和2倍.Ag/BiOX复合光催化剂具有更高催化活性的原因是复合光催化剂对可见光有很强的吸收能力,同时产生了银等离子体光催化作用和银抑制了Ag/BiOX(X=Cl,Br,I)的光生电子-空穴的复合.     

Magnetic retrievable Ag/AgBr/ZnFe2O4 photocatalyst for efficient removal of organic pollutant under visible light

In the present work, a visible-light-driven Ag/AgBr/ZnFe₂O₄ photocatalyst has been successfully synthesized via a deposition–precipitation and photoreduction method. The crystal structure, chemical composition, morphology and optical properties of the as-prepared nanocomposites were characterized by X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscope, UV–vis diffuse reflectance spectroscopy and photoluminescence. The photocatalytic activities of the Ag/AgBr/ZnFe₂O₄ nanocomposites were evaluated through the photodegradation of gaseous toluene and methyl orange (MO) under visible light. The results revealed that the as-prepared Ag/AgBr/ZnFe₂O₄ nanocomposite exhibited excellent photocatalytic activity. The degrading efficiency of MO could still reach 90% after four cycles, and the Ag/AgBr/ZnFe₂O₄ nanocomposite could be recycled easily by a magnet. Additionally, the enhanced photocatalytic mechanism was discussed according to the trapping experiments, which indicated that the photo-generated holes (h⁺) and •O₂⁻ played important roles in photodegradation process. At last, a possible photocatalytic oxidation pathways of toluene was proposed based on the results of GC–MS. The Ag/AgBr/ZnFe₂O₄ composites showed potential application for efficient removal of organic pollutant.     

Synergetic effect of heterojunction and doping of silver on ZnNb2O6 for superior visible-light photocatalytic activity and recyclability

This work reports the synthesis of Ag/ZnNb₂O₆ heterojunctions by solid-state approach followed with the photoreduction of silver. It was found that Ag decorated ZnNb₂O₆ catalyst was provided with dual roles of silver, including homogeneous doping of Ag ions into ZnNb₂O₆ host lattice and a large amount of heterojunctions due to the monodispersion of tiny Ag nanoparticles deposited on ZnNb₂O₆ surface, thereby showing the abnormal visible-light absorption ascribed to the interband introduction and the strong surface plasmon resonance. The photocatalytic effects of silver doping and heterojunctions in visible-light irradiation were investigated, which showed Ag(6 wt.%)/ZnNb₂O₆ catalyst had the optimal photocatalytic efficiency (96.5–98.2% within 2 h) for the photodegradation of five various dyes and high recyclability during the photocatalytic degradation of methyl orange.     

Decomposition of rhodamine 6G in the presence of titania coupling coupled with carbon source as photocatalyst under visible light excitation

Heterogeneous photocatalytic degradation of N-containing R6G dye was achieved by visible light-activated carbon doped TiO₂ (C-TiO₂) nanoparticles, synthesized by a low-temperature wet-chemical technique using glucose as carbon source. The structural and physicochemical properties of C-TiO₂ were characterized by X-ray diffraction (XRD), Raman spectroscopy, UV-vis diffuse reflectance spectroscopy (UV-vis DRS) and FT-IR spectroscopy. Compared with the pure TiO₂, the carbon modified nanomaterials exhibited enhanced absorption in the broad visible-light region together with an apparent red shift in the optical absorption edge. The resulting carbon-doped TiO₂ catalyst was employed as an effective photocatalyst for degradation of Rhodamine 6G (R6G) in aqueous solutions under visible light irradiation (λ > 420 nm). In addition, the intrinsic mechanism of visible light-induced photocatalytic oxidation of organic compounds on the carbon-doped titania was proposed and discussed.     

生物质C-N-P自掺杂TiO_2的合成及其对亚甲基兰的光催化降解活性

采用溶胶-超声辐照技术同步合成了生物质C-N-P自掺杂TiO_2复合催化剂,通过X射线光电子能谱(XPS)、X射线衍射(XRD)、扫描电子显微镜(FESEM)、紫外-可见漫反射光谱(UV-Vis-DRS)及光致发光光谱(PL)对样品进行了表征.以亚甲基兰(MB)为目标污染物,研究了C-N-P共掺杂TiO_2的可见光光催化性能.实验结果表明,在可见光照射下,光催化反应时间为2 h时,C-N-P共掺杂TiO_2复合催化剂对亚甲基兰的降解效率最高可达9 8.5%;相比纯TiO_2,C-N-P共掺杂TiO_2复合催化剂的比表面积增大,吸收边带红移,禁带宽度减小,相变温度升高,光生载流子复合率降低.     

A New p‐Metal‐n Structure AgBr‐Ag‐BiOBr with Superior Visible‐Light‐Responsive Catalytic Performance

A novel visible‐light‐driven AgBr‐Ag‐BiOBr photocatalyst was synthesized by a facile hydrothermal method. Taking advantage of both p‐n heterojunctions and localized surface plasmon resonance, the p‐metal‐n structure exhibited a superior performance concerning degradation of methyl orange under visible‐light irradiation (λ>420 nm). A possible photodegradation mechanism in the presence of AgBr‐Ag‐BiOBr composites was proposed, and the radical species involved in the degradation reaction were investigated. HO₂^?/^?O₂^? played the same important role as ^?OH in the AgBr‐Ag‐BiOBr photocatalytic system, and both the electron and hole were fully used for degradation of organic pollutants. A dual role of metallic Ag in the photocatalysis was proposed, one being surface plasmon resonance and the other being an electron‐hole bridge. Due to the distinctive p‐metal‐n structure, the visible‐light absorption, the separation of photogenerated carriers and the photocatalysis efficiency were greatly enhanced.     

Morphology-Controlled Synthesis and Applications of Silver Halide Photocatalytic Materials

Semiconductor photocatalysis is considered to be one of the most promising technologies to solve the worldwide environmental and energy issues. In recent years, silver halide (AgX)-based photocatalytic materials have received increasing research attention owing to its excellent visible light-driven photocatalytic performances in the applications of organic pollutant degradation, H₂/O₂ generation, and disinfection. AgX-based materials used in photocatalytic fields can be classified into three categories: AgX (Ag/AgX), AgX composites, and supported AgX materials. For the AgX (Ag/AgX) photocatalysts, it has been widely accepted that the final photocatalytic performances of photocatalysts are severely dependent on their morphological structures as well as exposed crystal facets. As a result, considerable efforts have been devoted to fabricating different morphological AgX photocatalysts as well as exploring the relationship between the morphological structures and photocatalytic performances. In this review, we mainly introduce the recent developments made in fabricating morphology and facet-controllable AgX (Ag/AgX) photocatalytic materials. Moreover, this review also deals with the photocatalytic mechanism and applications of AgX (Ag/AgX) and supported AgX materials.     

Synthesis of BiVO4 nanosheets-graphene composites toward improved visible light photoactivity

Two-dimensional (2-D) BiVO₄ nanosheets-graphene (GR) composites with different weight addition ratios of GR have been prepared via a facile wet chemistry process. X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectra (XPS), UV-vis diffuse reflectance spectra (DRS), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), nitrogen adsorption-desorption, transient photocurrent response and photoluminescence (PL) spectra were employed to determine the properties of the samples. It is found that BiVO₄ nanosheets could pave well on the surface of graphene sheets. BiVO₄ nanosheets-GR composites with a proper addition amount of GR exhibited higher photocatalytic activity than bare BiVO₄ nanosheets toward liquid-phase degradation of rhodamine B (RhB) and methyl orange (MO) under visible light irradiation. The enhancement of photocatalytic activities of BiVO₄ nanosheets-GR composites can be attributed to the effective separation of photoexcited electron-hole pairs. This work not only provides a simple strategy for fabricating specific 2-D semiconductor-2-D GR composites, but also opens a new window of such 2-D semiconductor-2-D GR composites as visible light photocatalysts toward an improved visible light photoactivity in purifying polluted water resources.     

Solar light-induced photodegradation of chrysene in seawater in the presence of carbon-modified n-TiO2 nanoparticles

Photocatalytic degradation of chrysene in polluted seawater was successfully achieved under illumination of natural sunlight using carbon modified titanium oxide (C-TiO₂) nanoparticles. The morphological and structural characteristics of the as-synthesized nanoparticles were investigated by X-ray diffraction (XRD), UV–Vis spectra, scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS). The characterization results confirmed the successful incorporation of carbon into C-TiO₂ nanoparticles. As a result of C-modification, a significant enhancement of the photocatalytic degradation efficiency was observed for C-TiO₂, compared with pure TiO₂. In order to optimize the operating parameters, the impacts of catalyst loading and pH on the photocatalytic degradation of chrysene were investigated. The best degradation rate was obtained at pH 3 and C-TiO₂ loading of 1.0 g L⁻¹. The photodegradation of chrysene in seawater by using C-TiO₂ was found to follow a pseudo first-order kinetics in terms of the Langmuir-Hinshelwood model.     

MIL-101/P25复合材料的制备及光催化性能

采用水热法,将MIL-101负载到预处理过的P25表面,制得MIL-101/P25复合光催化材料,通过X射线衍射(XRD)、傅里叶变换红外(FTIR)、低温N2物理吸附-脱附(BET)、热重(TG)、场发射透射电镜(FETEM)和光致发光光谱(PL)等对催化剂进行结构表征,同时考察MIL-101及复合材料的稳定性,并且提出协同因子指标来定量评价复合带来的协同效应。结果表明MIL-101呈片状,与P25部分结合。复合后,MIL-101的稳定性得到提高。在适当的配比下,复合具有协同效应,当Cr(NO3)3·9H2O与P25的物质的量之比为1∶1时,复合材料对罗丹明B的可见光催化活性最高,协同因子达到1.64。复合材料对无色有机污染物水杨酸同样表现出良好的光催化效果。     

Visible‐light‐driven self‐cleaning SERS substrate of silver nanoparticles and graphene oxide decorated nitrogen‐doped titania nanotube array

Graphene oxide (GO) and silver nanoparticles (Ag NPs) sequentially decorated nitrogen‐doped titania nanotube array (N‐TiO₂ NTA) had been designed as visible‐light‐driven self‐cleaning surface‐enhanced Raman scattering (SERS) substrate for a recyclable SERS detection application. N‐TiO₂ NTA was fabricated by anodic oxidation and then doping nitrogen treatment in ammonia atmosphere, acting as a visible‐light‐driven photocatalyst and supporting substrate. Ag/GO/N‐TiO₂ NTA was prepared by decorating GO monolayer through an impregnation process and then depositing Ag NPs through a polyol process on the surface of N‐TiO₂ NTA, acting as the collection of organic molecule and Raman enhancement. The SERS activity of Ag/GO/N‐TiO₂ NTA was evaluated using methyl blue as an organic probe molecule, revealing the analytical enhancement factor of 4.54 × 10⁴. Ag/GO/N‐TiO₂ NTA was applied as active SERS substrate to determine a low‐affinity organic pollutant of bisphenol A, revealing the detection limit of as low as 5 × 10^?7 m . Ag/GO/N‐TiO₂ NTA could also achieve self‐cleaning function for a recycling utilization through visible‐light‐driven photocatalytic degradation of the adsorbed organic molecules. Ag/GO/N‐TiO₂ NTA has been successfully reused for five times without an obvious decay in accuracy and sensitivity for organic molecule detection. The unique properties of this SERS substrate enable it to have a promising application for the sensitive and recyclable SERS detection of low‐affinity organic molecules. Copyright © 2016 John Wiley & Sons, Ltd.     

Studies on photocatalytic activity of Ag/TiO2 films

Ag/TiO₂ photocatalytic films were produced by hybrid sol-gel method. The photocatalytic degradation of methyl orange (MO) in aqueous solution under 365 nm irradiation on TiO₂ and Ag/TiO₂ thin films was investigated. The state and amount of Ag species within the film and the enhancement mechanism of photocatalytic activity of Ag/TiO₂ were discussed. With a loading molar ratio of Ag/Ti = 0.135 in TiO₂ film, the maximum catalytic efficiency was observed. __________ Translated from Journal of Beijing Normal University (Natural Sciences), 2005, 41(6) (in Chinese)     

MIL-101/P25复合材料的制备及光催化性能

本文采用水热法,将MIL-101负载到预处理过的P25表面,制得MIL-101/P25复合光催化材料,通过X射线衍射（XRD）、傅里叶变换红外（FTIR）、低温N₂物理吸附-脱附（BET）、热重（TG）、场发射透射电镜（FETEM）和光致发光光谱（PL）等对催化剂进行结构表征,同时考察MIL-101及复合材料的稳定性,并且提出协同因子指标来定量评价复合带来的协同效应。结果表明MIL-101呈片状,与P₂₅部分结合。复合后,MIL-101的稳定性得到提高。在适当的配比下,复合具有协同效应,当Cr（NO₃）₃·9H₂O与P25的物质的量之比为1：1时,复合材料对罗丹明B的可见光催化活性最高,协同因子达到1.64。复合材料对无色有机污染物水杨酸同样表现出良好的光催化效果。     

Preparation and characterization of silver and indium vanadate co-doped TiO2 thin films as visible-light-activated photocatalyst

Novel visible-light-activated photocatalytic Ag/InVO₄-TiO₂ thin films were developed in this paper through a sol-gel method from the TiO₂ sol containing Ag and InVO₄. The photocatalytic activities of Ag/InVO₄-TiO₂ thin films were investigated based on the oxidation decomposition of methyl orange in aqueous solution. The Ag/InVO₄-TiO₂ thin films were characterized by X-Ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectroscopy (UV-vis). The results revealed that the Ag/InVO₄-TiO₂ thin films extended the light absorption spectrum toward the visible region; the Ag and InVO₄ co-doped thin films significantly enhanced the methyl orange photodegradation under visible light irradiation. It has been confirmed that the Ag/InVO₄-TiO₂ thin films could be excited by visible light (E < 3.2 eV). The significant enhancement in the Ag/InVO₄-TiO₂ photo activity under visible light irradiation can be ascribed to the simultaneous effects of doped noble metal Ag by acting as electron traps and InVO₄ as narrow band gap sensitizer.     

Improved Photocatalytic Activity and Stability of Nano‐sized Ag/Ag2CO3 Plasmonic Photocatalyst by Surface Modification of Fe(III) Nanocluster

The surface modification of Ag/Ag₂CO₃ with Fe(III) ions has been achieved through simply photoreduction‐impregnation method. The obtained products were characterized by means of X‐ray diffraction (XRD), scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), and UV‐vis absorption spectroscopy. Under visible‐light irradiation (γ>420 nm), the Fe(III)/Ag/Ag₂CO₃ sample displays a higher photocatalytic activity and stability than pure Ag₂CO₃ and Ag/Ag₂CO₃ samples for the degradation of methyl orange (MO). The improved photocatalytic activity and stability of this ternary system could be ascribed to the synergetic effect between Ag nanoparticles and Fe(III) nanocluster. The metallic Ag nanoparticles cause an obviously enhanced visible‐light absorption to produce more photogenerated charges, while the Fe(III) works as an active site for the following oxygen reduction to reduce the recombination rate of photogenerated electrons and holes.     

Characterization, activity and mechanisms of a visible light driven photocatalyst: Manganese and iron co-modified TiO2 nanoparticles

An attempt was made to prepare Mn,Fe-codoped nanostructured TiO₂ photocatalyst for visible light assisted degradation of an azo dye (methylene blue) in aqueous solutions by a sol-gel process. The asprepared nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS) and photoluminescence spectra (PL) techniques. The photocatalytic activity of Mn,Fe-codoped TiO₂ catalyst was evaluated by measuring degradation rates of methylene blue (MB) under visible light. The results showed that doping with the manganese and iron ions significantly enhanced the photocatalytic activity for MB degradation under visible light irradiation. This was ascribed to the fact that a small amount of manganese and iron dopants simultaneously increased MB adsorption capacity and separation efficiency of electron-hole pairs. The results of DRS showed that Mn,Fe-codoped TiO₂ had significant absorption between 400 and 500 nm, which increased with the increase of manganese ion content. It is found that the stronger the PL intensity, the higher the photocatalytic activity. This could be explained by the points that PL spectra mainly resulted from surface oxygen vacancies and defects during the process of PL, while surface oxygen vacancies and defects could be favorable in capturing the photoinduced electrons during the process of photocatalytic reactions, so that the recombination of photoinduced electrons and holes could be effectively inhibited.