Synthesis,performance and action mechanism of carbon black/Ag3PO4 photocatalysts

Novel carbon black (CB)/Ag₃PO₄ compound photocatalysts were synthesized from a hydrothermal method and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and electrochemical methods. The photocatalytic oxidation ability of CB/Ag₃PO₄ was evaluated through methyl orange degradation experiments under visible light irradiation. The CB/Ag₃PO₄ showed higher photocatalytic activity than pure Ag₃PO₄. It was indicated the compound catalysts could absorb and utilize more optical energy to improve the photocatalytic activity, which was attributed to the ability of carbon black to accelerate the electron-hole separation. In particular, the methyl orange photocatalytic degradation rate over the 7?mg/L CB/Ag₃PO₄ was 1.6 times that of Ag₃PO₄. And the results of the cyclic experiment show that the photocatalyst has good stability. Moreover, the mechanism about the photocatalytic activity of CB/Ag₃PO₄ compounds was investigated. In this photocatalytic reaction, ?OH was the major active substrate responsible for the visible-light-driven degradation.     

Ag3PO4的制备及其复合材料研究进展

能源与环境已成为当前亟需解决的问题,半导体光催化技术因具有氧化降解有机污染物完全、不产生二次污染、易操作等优点,在环境治理和新能源开发领域成为热点研究课题之一。Ag3PO4因具有高量子效率、可见光响应及较高的光催化效率等特点而引起了广大研究者的关注,并具有广泛的应用前景。本文总结了Ag3PO4的制备方法、不同形貌Ag3PO4的可控合成及其复合材料的研究进展。     

One step synthesis of Ag/Ag3PO4/BiPO4 double-heterostructured nanocomposites with enhanced visible-light photocatalytic activity and stability

Heterogeneous Ag/Ag₃PO₄/BiPO₄ photocatalyst was synthesized by a one-step low temperature chemical bath method and exhibited better photocatalytic activity and better stability than those of individual Ag₃PO₄ or BiPO₄ nanoparticles for photodegradation of organic compounds (Rhodamine B) in the absence of electron accepters under visible light (λ>420 nm). The enhanced photocatalytic performance is mainly ascribed to the strong visible-light absorption originating from high efficient separations of photogenerated electron–hole pairs through Ag₃PO₄/BiPO₄ and Ag/Ag₃PO₄ heterostructures.     

Enhanced photocatalytic activity of La1-xSrxCoO3/Ag3PO4 induced by the synergistic effect of doping and heterojunction

This study sought to design and synthesize a series of perovskite-based La_1-xSr_xCoO₃/Ag₃PO₄ (with x = 0–1) heterojunction photocatalysts with different Strontium (Sr) doping contents by a simple sol-gel method and properties of the material were comprehensively characterized. Moreover, tetracycline (TC) was chosen as the target pollutant to assess the effect of Sr doping on the catalytic performance of LaCoO₃/Ag₃PO₄. Our results demonstrated that the partial replacement of La³⁺ with Sr²⁺ coupled with shifting Co³⁺ to the mixed-valence state of Co³⁺-Co⁴⁺ led to the formation of substantially more oxygen vacancies in the crystal lattice of La_1-xSr_xCoO₃/Ag₃PO₄. Therefore, the doped catalyst La_1-xSr_xCoO₃/Ag₃PO₄ exhibited enhanced photocatalytic performance. When x = 0.9, the obtained La_0·1Sr_0·9CoO₃/Ag₃PO₄ exhibit an optimal performance for TC degradation. Kinetic analyses demonstrated that the degradation rate constant of TC in La_0·1Sr_0·9CoO₃/Ag₃PO₄ system was 0.0098 min^?1, which is 1.78 times that of LaCoO₃/Ag₃PO₄, and 2.45 times that of SrCoO₃/Ag₃PO₄. Additionally, free radical sequestration experiments indicated that OH^?, h⁺, and O₂^?? all participated in the degradation of TC in the following order: h⁺>O₂^??>OH^?. Finally, analyses of photocatalytic mechanisms suggested that the enhanced photocatalytic activity of La_0·1Sr_0·9CoO₃/Ag₃PO₄ was due to its strong electron transfer properties and the formation of substantially more surface oxygen vacancies in Sr-doped La_0·1Sr_0·9CoO₃.     

Rice spike-like g-C3N4/TiO2 heterojunctions with tight-binding interface by using sodium titanate ultralong nanotube as precursor and template

A novel rice spike-like g-C₃N₄/TiO₂ nanowire heterojunctions are fabricated by hydrothermal treating Na₂Ti₃O₇ ultralong nanotubes in the presence of g-C₃N₄. The presence of g-C₃N₄ promotes the hydrolysis of Na₂Ti₃O₇ ultralong nanotubes. The partially replaced O of TiO₂ by N from g-C₃N₄ leads to the formation of a tight-binding interface between one dimensional TiO₂ and two dimensional g-C₃N₄, which is crucial for fast and effective transfer of photogenerated electrons in heterostructured photocatalysts. As a result, the g-C₃N₄/TiO₂ nanowire heterojunctions exhibit excellent visible-light photocatalytic activity. The kinetic constant (k) of g-C₃N₄/TiO₂ (0.024?min^?1) for degradation of methylene blue under visible light irradiation is 1.85 and 4 times than that of pure g-C₃N₄ and P25, respectively.     

The role of graphene and europium on TiO2 performance for photocatalytic hydrogen evolution

Highly efficient Eu-TiO₂/graphene composites were synthesized by a two-step method such as sol-gel and hydrothermal process. The synthesized photocatalysts were characterized by XRD, TEM, XPS, UV–vis diffuse reflectance spectroscopy and photoluminescence (PL) spectroscopy. The results confirmed that anatase Eu-TiO₂ nanoparticles with average 10 nm sizes were successfully deposited on two-dimensional graphene sheets. The UV–visible spectroscopy showed a red shift in the absorption edge of TiO₂ due to Eu doping and graphene incorporation. Moreover, effective charge separation in Eu-TiO₂/graphene composites was confirmed by PL emission spectroscopy compared to TiO₂/graphene, Eu-TiO₂ and pure TiO₂. The photocatalytic activity for H₂ evolution over prepared composites was studied under visible light irradiation (λ ≥ 400 nm). The results demonstrate that photocatalytic performance of the photocatalysts for hydrogen production increases with increasing doping concentration of Eu upto 2 at%. However, further increase in doping content above this optimum level has decreased the performance of photocatalyst. The enhanced photocatalytic performance for H₂ evolution is attributed to extended visible light absorption, suppressed recombination of electron-hole pairs due to synergistic effects of Eu and graphene.     

Enhancement of the visible light photocatalytic performance of C-doped TiO2 by loading with V2O5

V₂O₅ was loaded on the surface of C-doped TiO₂ (C-TiO₂) by incipient wetness impregnation in order to enhance the visible light photocatalytic performance. The physicochemical properties of the C-TiO₂/V₂O₅ composite were characterized by XRD, Raman, TEM, XPS, UV–vis diffuse reflectance spectra, and PL in detail. The result indicated that a heterojunction between C-TiO₂ and V₂O₅ was formed and the separation of excited electron–hole pairs on C-TiO₂/V₂O₅ is greatly promoted. Thus, this composite photocatalyst exhibited enhanced visible light photocatalytic activity in degradation of gas-phase toluene compared with the pristine C-TiO₂.     

金负载多孔g-C3N4纳米片制备及可见光催化产氢性能

石墨相氮化碳（g-C₃N₄）作为一种不含金属的光催化剂,因成本低、简单易得和良好的光响应特性受到关注。然而,电子-空穴对的高复合率阻碍了其广泛的应用。以三聚氰胺为原料、尿素为致孔剂,通过水热结合煅烧方法制备出多孔g-C₃N₄纳米片（PCNS）,然后采用化学还原法将金（Au）负载在PCNS表面,并对反应体系中的金含量进行调控。通过X射线衍射（XRD）、红外光谱（FT-IR）、拉曼（Raman）光谱、透射电镜（TEM）、紫外-可见漫反射光谱（UV-Vis DRS）和电化学测试等对复合材料进行了表征。与PCNS相比,Au/PCNS复合材料不仅具有更强的光吸收性能,而且电子和空穴的复合率也明显降低。同时对复合材料的可见光分解水产氢性能进行了研究,结果发现0.5%Au/PCNS呈现出最优的光催化产氢速率[84.09 μmol/（g·h）],是0.5%Au/g-C₃N₄[1.88 μmol/（g·h）]的44.7倍。     

Electrochemical beaviour of the solid ionic conductor Ag7I4PO4

Electrochemical investigation of the solid superionic conductor Ag₇I₄PO₄ (0.8 AgI + 0.2 Ag₃PO₄) at room temperature and at 40°C were performed by means of cyclic voltammetry, cyclic chronoamperometry and cyclic chronocoulometry, normal pulse polarography and ac polarography. It was shown that the Ag⁺ ↔ Ag redox process on Pt and Ag working electrode occurs with a certain overvoltage, ie that for Ag⁺ → Ag⁺ oxidation and the return of Ag⁺ ions into the electrolyte a certain overvoltage is necessary. From the determined values of the exchange current one estimates the redox process as a rather fast one. The silver working electrode is electrochemically inactive, while only cathodically deposited silver is electrochemically active and can be oxidized to Ag⁺ ions. Chronoamperometry and chronocoulometry show that there is a certain difference in the behaviour of Pt and Ag working electrodes due to uneven passivating anodic processes. On the basis of measurements of faradaic and capacitance currents and their dependence on frequency, diagrams of complex impedance of the Pt/Ag₇I₄PO₄ interface at various anodic and cathodic polarizations of the Pt electrode were plotted. The dependence of the serial capacity of the interface on the dc potential and temperature are discussed.     

超分子前体制备g-C3N4/g-C3N4同质结及光催化性能研究

通过混合煅烧二氰二胺水热法和三聚氰胺-三聚氰酸共沉淀法制备的超分子前驱体,制备了兼具多孔纳米片和中空纳米管形貌的g-C₃N₄/g-C₃N₄同质结（CN-HP）。通过X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、紫外-可见漫反射光谱（UV-Vis DRS）、光致发光光谱（PL）等对光催化剂进行了表征。结果表明,CN-HP-1/1在75 min内对亚甲基蓝（MB）的降解率可达99.8%,伪一级动力学常数为4.02 h^-1,是块体g-C₃N₄的5倍,同时单位比表面积的反应常数提升至单体的1.8倍。PL测试表明,合适比例的三聚氰胺-三聚氰酸（MCA-H、MCA-P）超分子制备的同质结,其光生电子-空穴复合率较单体g-C₃N₄进一步降低。自由基捕获实验表明,光生空穴是光催化降解过程中的主要活性物种,并结合X射线光电子能谱价带谱测试提出了Z型电子传输机制。     

Z型Ag2CO3/BiOCl异质结光催化剂的制备及其可见光催化机理分析

通过溶剂热法制备BiOCl纳米片,共沉淀法制备Ag2 CO3和复合催化剂Ag2 CO3/BiOCl,研究各材料可见光催化降解罗丹明B的效果,确定Ag2 CO3与BiOCl的最佳配比,并通过表征分析复合材料的结构和异质结光催化降解机理.结果表明,当Ag2 CO3与BiOCl的质量比为50％时,Ag2 CO3/BiOCl异...     

Fabrication and characterization of CdS/BiVO4 nanocomposites with efficient visible light driven photocatalytic activities

Novel CdS/BiVO₄ nanocomposites were synthesized by simple solvothermal method. The as-prepared samples were characterized by transmission electron microscopy (TEM), scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Raman spectroscopy, UV–vis diffuse reflectance spectra (DRS), Fourier transform infrared spectra (FT-IR) and photoluminescence (PL). In the nanocomposites, CdS particles were deposited on the surface of the BiVO₄. The photocatalytic tests showed that the CdS/BiVO₄ nanocomposites possessed a higher rate for degradation of malachite green (MG) than the pure BiVO₄ under visible light irradiation. The 1.5-CdS/BiVO₄ nanocomposite photocatalyst was found to degrade 98.3% of MG under visible light irradiation. Moreover, the photocatalytic mechanism of CdS/BiVO₄ nanocomposites was also discussed. The results showed that the nanocomposite construction between CdS and BiVO₄ played a very important role in their photocatalytic properties, which has the potential application in solving environmental pollution issues utilizing solar energy effectively.     

Synthesis of a CoTiO3/BiOBr heterojunction composite with enhanced photocatalytic performance

A novel heterojunction CoTiO₃/BiOBr nanocomposite with enhanced photocatalytic performance was synthesized by a precipitation-deposition method. The samples were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV–vis spectrophotometry. Moreover, the photocatalytic activities were evaluated by decomposing the dye molecule Rhodamine B under visible light irradiation. The results showed that high photocatalytic performance can be achieved on the heterojunction photocatalysts, with the 0.15CoTiO₃/0.85BiOBr composite displaying the highest activity. The results of the study concluded that it was the introduction of CoTiO₃ into the catalyst that mainly enhanced the activity of the photocatalyst by promoting the separation of the electron-hole group on the interface between BiOBr and CoTiO₃.     

BiOI/g-C3N4光催化降解甲基橙研究

以三聚氰胺为前驱物采用热聚合法制备了石墨相氮化碳（g-C₃N₄）,并在其表面原位合成了碘氧化铋（BiOI）,构筑了石墨相氮化碳-碘氧化铋复合材料。采用X射线衍射仪（XRD）、傅里叶变换红外光谱仪（FT-IR）、紫外可见漫反射仪（UV-Vis-DRS）等对催化剂进行了表征。结果表明,当BiOI与g-C₃N₄物质的量比为0.5时,BiOI/g-C₃N₄催化剂具有高分散的BiOI颗粒及适中的禁带宽度,吸附和降解甲基橙性能最佳。回流温度为120 ℃时制备的BiOI/g-C₃N₄催化剂具有适中的粒径、比表面积和表面羟基浓度,吸附和降解甲基橙性能最佳,且该催化剂具有良好的重复使用性能。     

Photocatalytic degradation of bisphenol A and dye by graphene-oxide/Ag3PO4 composite under visible light irradiation

A facile, one-step synthesis of graphene-oxide (GO)/Ag₃PO₄ was prepared. The as-prepared samples were characterized by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS) and fourier transformed infrared (FT-IR) spectroscopy. The SEM image indicated that Ag₃PO₄ particles were mainly distributed on the surface of GO sheets uniformly. DRS analysis revealed that the samples had good visible light response. The photocatalytic activity of the composites was evaluated by the degradation of Rhodamine B (RhB) and Bisphenol A (BPA). The results indicated that the photocatalytic performance of GO/Ag₃PO₄ was greatly enhanced after introduction of GO. The photocatalytic degradation efficiency of colorless chemical pollutants (BPA) over GO/Ag₃PO₄ was higher than that of Ag₃PO₄, and the possible degradation path was proposed by liquid chromatography mass spectrometry (LC-MS) analysis. Moreover, the photocatalytic stability was discussed by XRD and FT-IR spectroscopy analysis. Based on the experimental results, a possible visible-light photocatalytic degradation mechanism was also discussed.     

Fabrication of CdS and CuWO4 modified TiO2 nanoparticles and its photocatalytic activity under visible light irradiation

CdS and CuWO₄ modified TiO₂ nanoparticles (CdS–CuWO₄-TiO₂) were prepared by the chemical impregnation method. The as-prepared nanoparticles were characterized using UV–visible-diffuse reflectance spectroscopy (UV–vis-DRS), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and B.E.T. surface area analysis techniques. The photocatalytic activity was evaluated based on the degradation of a dye (eosin-Y) and inactivation of a bacterium (Pseudomonas aeruginosa). The results revealed that CdS–CuWO₄-TiO₂ showed high photocatalytic activity over CdS-TiO₂, CuWO₄-TiO₂ and TiO₂. Moreover the reusability and stability of the photocatalyst for the degradation of eosin-Y was also studied.     

氮掺杂对SrTiO3光催化性能的影响

以尿素为氮源,利用溶胶-凝胶法制备了掺氮的N-SrTiO₃光催化剂。采用XRD、SEM和UV-Vis对N-SrTiO₃的物相、形貌和吸光性能进行表征,以高压汞灯为光源,通过甲基橙脱色率考察催化剂活性。结果表明,氮元素的掺杂增强了SrTiO₃在可见光区的吸收强度,当制备过程pH=3～4、n(N)∶n(Sr)=6∶1和焙烧温度800 ℃时,甲基橙溶液降解率达72.69%,未掺杂样品降解率为28.55%。     

Optical properties of Ni and Cu nanowire arrays and Ni/Cu superlattice nanowire arrays

In this study, Ni and Cu nanowire arrays and Ni/Cu superlattice nanowire arrays are fabricated using standard techniques such as electrochemical deposition of metals into porous anodic alumina oxide templates having pore diameters of about 50 nm. We perform optical measurements on these nanowire array structures. Optical reflectance (OR) of the as-prepared samples is recorded using an imaging spectrometer in the wavelength range from 400 to 2,000 nm (i.e., from visible to near-infrared bandwidth). The measurements are carried out at temperatures set to be 4.2, 70, 150, and 200 K and at room temperature. We find that the intensity of the OR spectrum for nanowire arrays depends strongly on the temperature. The strongest OR can be observed at about T = 200 K for all samples in visible regime. The OR spectra for these samples show different features in the visible and near-infrared bandwidths. We discuss the physical mechanisms responsible for these interesting experimental findings. This study is relevant to the application of metal nanowire arrays as optical and optoelectronic devices.     

ML-WO3/TiO2异质结的制备及其对罗丹明B的光催化降解

采用空间限域法制备了单层三氧化钨纳米片(ML-WO₃),然后将其与TiO₂复合得到ML-WO₃/TiO₂纳米材料,被用来在模拟太阳光下对罗丹明B进行光催化降解。ML-WO₃/TiO₂的组成和光学特性通过扫描电镜、透射电镜、高分辨透射电镜、X射线衍射、紫外-可见吸收光谱和光致发光光谱手段进行表征。结果证实,纳米ML-WO₃/TiO₂克服了纯TiO₂带隙较大的缺陷,在全波段太阳光表现出比ML-WO₃和TiO₂更强的吸收性能,ML-WO₃与TiO₂之间具有明显的协同效应。活性物种捕获实验表明.OH和.O_2^-自由基是RhB降解的主要活性物种。ML-WO₃和TiO₂之间构建的Z型异质结电荷转移路径能够保证光生载流子的高效分离和重组。在5次循环实验后ML-WO₃/TiO₂的光催化活性仍能接近80%,具有良好的光化学稳定性。通过高效液相色谱-质谱检测RhB的中间产物,推测了RhB可能的降解路径。     

Nanocomposites of SnO2 and g-C3N4: Preparation,characterization and photocatalysis under visible LED irradiation

Tin dioxide nanoparticles were prepared in the presence of graphitized carbon nitride (g-C₃N₄) forming nanocomposites with different contents of SnO₂ up to 40 %. G-C₃N₄ was synthetized by heating of melamine at 550 °C in the open air and Sn²⁺ ions were precipitated by sodium hydroxide in g-C₃N₄ aqueous dispersions. Resulting mixtures were dried by freezing at ?20 °C and calcined at 450 °C to obtain SnO₂/g-C₃N₄ nanocomposites.The nanocomposites were characterized by common characterization methods in solid state and in their aqueous dispersions using dynamic light scattering (DLS) analysis and photocatalysis. SnO₂ nanoparticles in the nanocomposites were found to have an average size of 4 nm, however, those precipitated without g-C₃N₄ had an average size of 14 nm. Separation of photoinduced electron and holes via heterojunction between SnO₂ and g-C₃N₄ was demonstrated by photocatalytic decomposition of Rhodamine B (RhB) under LED visible irradiation (416 nm) and photocurrent measurements. The most photocatalytically active nanocomposite contained 10 % of SnO₂. Graphitized carbon nitride was assumed to serve as a template structure for the preparation of SnO₂ nanoparticles with a narrow size distribution without using any stabilizing additives.