Preparation and characterization of ZnO/ZnS hybrid photocatalysts via microwave-hydrothermal method

The photocatalytic performance of ZnO/ZnS hybrid nanocomposite was largely higher than that of the mere ZnO or ZnS nanoparticles, but the complicated procedure and misdistribution of final products limited its large-scale productions. The exploration of a novel synthesis route of ZnO/ZnS hybrid photocatalysts with high catalytic performance is becoming a crucial step for the large-scale application of ZnO/ZnS hybrid photocatalytic technique. Preparation and characterization of nanosized ZnO/ZnS hybrid photocatalysts were studied in this paper. The photocatalysts were obtained via microwave-hydrothermal crystallization with the help of sodium citrate. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), particle size distribution (PSD), and Fourier transformed infrared spectroscopy (FT-IR). The results indicated that so-synthesized ZnO/ZnS samples consisted of the high pure cubic (sphalerite) ZnS and hexagonal ZnO nanocrystallines with a narrow particle size distribution. The possible formation mechanisms of ZnO/ZnS nanocrystallines were mainly attributed to the superficially protective effect of citrate. The photocatalytic experiments demonstrated that the ZnO/ZnS photocatalysts exhibited a higher catalytic activity for the degradation of acid fuchsine than other monocomponents.     

C3N4/BiOBr复合可见光催化剂的性能及其作用机制

利用水热合成法制备了C_3N_4/BiOBr复合可见光催化剂,通过XRD、FT-IR、SEM、DRS、PL等手段对催化剂的物相组成和光化学性能进行了系统表征,利用对罗丹明B(RhB)的降解实验评价了催化剂在可见光照下的光催化降解活性和稳定性并通过ESR分析和自由基捕获实验探究了RhB的光催化降解机制.结果表明,水热合成法可成功制备结晶性能良好的C_3N_4/BiOBr复合可见光催化剂;C_3N_4的复合降低了BiOBr光催化剂的电子-空穴的复合,提高了光催化降解活性,其中15%C_3N_4/BiOBr的活性最佳,可见光照18 min后RhB的脱色率达100%,较纯BiOBr提高了1.5倍,且重复使用5次后仍具有较高的光催化降解活性;复合催化剂光催化降解RhB过程中参与降解的主要活性物种为空穴(h~+)和超氧自由基(·O_2~-),其中h~+影响更为显著.     

AgCl/ZnO/GO光催化降解甲基橙的性能研究

为了提高ZnO对偶氮染料污染物的光催化降解效率,以AgCl和GO（氧化石墨烯）作为改性剂,通过水热法和化学沉积法制备了AgCl/ZnO/GO光催化材料,采用XRD、SEM、XPS、UV-Vis方法对材料的物相组成、微观形貌及光学特性进行表征;以MO（甲基橙）为目标污染物,探究其在可见光下的催化降解性能,考察AgCl含量、催化剂投加量、pH对其可见光催化活性的影响.结果表明:①AgCl的沉积和GO的负载增强了ZnO对可见光的响应能力,提高了光生电子-空穴产生、分离效率,同时增加了材料的分散性及其对MO的吸附率,因此AgCl/ZnO/GO光催化材料对MO有良好的可见光催化降解效率.②AgCl/ZnO/GO对MO的催化降解效率随着AgCl含量的增加而增加,随着催化剂投加量的增加呈先增后降的趋势,溶液pH对其降解效果有一定影响,但不显著.③当AgCl/ZnO（二者物质的量的比）为2:1、AgCl/ZnO/GO投加量为70 mg、pH为7、室温下经过可见光照射50 min后,AgCl/ZnO/GO对质量浓度为10 mg/L的MO的降解率可达98.93%;此外,该催化剂重复使用4次对MO仍具有88%的去除率,显示出良好的稳定性.因此,AgCl/ZnO/GO是一种高效、稳定的可见光光催化剂,在废水净化方面具有良好的应用前景.      

Cu2O@ZnO复合光催化剂对难生物降解有机物的光降解

通过改进的浸渍-还原-空气氧化法成功制备了Cu₂O@ZnO复合光催化剂,考察Cu₂O@ZnO对对硝基苯酚（PNP）和聚丙烯酰胺（PAM）2种不同化学结构污染物的光催化效果,同时探究了催化剂的稳定性和降解机制.结果表明,在模拟太阳光照射下,当铜锌物质的量比为0.15时,Cu₂O@ZnO复合光催化剂具有最佳的光催化降解性能,其中对硝基苯酚的光催化降解率为98.2%,聚丙烯酰胺光催化降解率为99.7%.基于X射线衍射（XRD）、X射线光电子能谱（XPS）、光致发光（PL）光谱、紫外-可见（UV-Vis）吸收光谱等表征手段可以推断,Cu₂O和ZnO形成Ⅱ型异质结,有效地抑制光生电子空穴对的复合.自由基捕获实验指出超氧自由基和空穴为主要活性物种,经过4次循环使用后光催化剂仍具有很高的光催化性能.     

δ-MnO_2对ZnO和TiO_2光催化降解萘酚蓝黑活性影响

以萘酚蓝黑为模型污染物,采用动力学方法研究了δ-MnO2颗粒杂质对亚微米级商品TiO2(C)、ZnO(C)和纳米级自制TiO2(N)、ZnO(N)光催化作用的影响,并通过紫外-可见漫反射光谱(UV-vis DRS)和荧光光致发光光谱(PL)对试样进行了表征。结果表明,δ-MnO2能导致2种TiO2严重失活,而对2种ZnO的光催化活性影响很小。δ-MnO2导致TiO2光催化剂失活的主要原因为:能提高TiO2的带隙能,以及作为深能级杂质促进光生电子与空穴之间的复合。     

g-C3N4/Bi2S3复合物的制备及可见光催化降解MO

采用简单溶剂热方法成功合成可见光催化剂g-C_3N_4/Bi_2S_3.合理地利用X射线衍射(XRD)、傅立叶红外光谱分析仪(FTIR)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM、HRTEM)、紫外可见漫反射光谱(UV-vis DRS)等表征手段对合成的样品进行了表征.与纯g-C_3N_4和Bi_2S_3相比,g-C_3N_4/Bi_2S_3复合物对甲基橙(MO)的可见光催化降解具有更高的降解效率.根据能带分析结果,电子-空穴对的有效分离增强了光催化效率.此外,提出了g-C_3N_4/Bi_2S_3对MO的光催化降解过程以阐明降解机制.提供了一种经济简单并易于规模化扩大开发可见光响应催化剂的方法,并在废水处理中具有潜在的应用价值.     

光催化剂AgBr/Ag2MoO4@AgVO3的结构表征及其抗菌防污性能

目的制备新型的光催化复合材料,提高其光催化性能。方法通过水热法和原位生长法制备不同摩尔比的AgBr/Ag_2MoO_4@AgVO_3光催化剂。采用X射线衍射(XRD)、扫描电镜(SEM)和高分辨透射电子显微镜(HRTEM)等一系列手段对所制备的光催化剂进行表征,并以可见光为光源,有机污染物罗丹明B(RhB)为降解对象,进行光催化活性测试,考察不同复合量的光催化剂对反应活性的影响。同时,以铜绿假单胞菌细胞、金黄色葡萄球菌和大肠杆菌为模式菌,进行抗菌试验考察光催化剂的杀菌性能。结果该复合材料通过AgVO_3的(501)晶面、Ag_2MoO_4的(311)面和AgBr的(200)晶面紧密连接。在罗丹明B(RhB)溶液中加入该复合材料,120 min内降解率达到了94.9%,而纯AgVO_3的降解率为7.8%,说明复合后的材料光催化性能明显提高。此外,在光催化杀菌实验中,超过99.99%的大肠杆菌、金黄色葡萄球菌和铜绿假单胞菌细胞均在90 min内被杀死。结论复合后的AgBr/Ag_2MoO_4@AgVO_3异质结光催化剂具有优异的光催化降解性能、杀菌性能和稳定性,该催化剂对于环境污染的治理以及海洋杀菌防污处理都起到一定的作用。     

A simple and cheap method for preparation of coupled ZrO2/ZnO with high photocatalytic activities

The objective of this study was to prepare a new photocatalyst with high activities for degradation of organic pollutants. Coupled ZrO₂/ZnO photocatalyst was prepared with a simple precipitation method with cheap raw materials zinc acetate and zirconium oxychloride, and was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Reactive brilliant red X-3B was used as a model compound to investigate the photocatalytic activity of synthesized catalysts in water under 254 nm UV irradiation. Results show that the optimal calcination temperature and coupling molar ratio of Zr were 350°C And 2.5%, respectively. At the calcination temperature of 350°C, ZrO₂ was dispersed on the surface of hexagonal ZnO in the form of amorphous clusters. The particle size of ZrO₂/ZnO decreased with the decrease of calcination temperature and the increase of Zr coupling amount. ZrO₂/ZnO has better photocatalytic activity for degradation of reactive brilliant red (RBR) X-3B than pure ZnO and P25-TiO₂.     

Photocatalytic remediation of γ-hexachlorocyclohexane contaminated soils using TiO2 and montmorillonite composite photocatalyst

TiO2 and montmorillonite composite photocatalysts were prepared and applied in degrading γ-hexachlorocyclohexane （γ-HCH） in soils. After being spiked with γ-HCH, soil samples loaded with the composite photocatalysts were exposed to UV-light irradiation. The results indicated that the photocatalytic activities of the composite photocatalysts varied with the content of TiO2 in the order of 10%〈70%〈50% 〈30%, Moreover, the photocatalytic activity of the composite photocatalysts with TiO2 content 30% was higher than that of the pure P25 with the same mass of TiO2. The strong adsorption capacity of the composite photocatalysts and quantum size effect may contribute to its increased photocatalytic activities. In addition, effect of dosage of composite photocatalysts and soil pH on γ-HCH photodegradation was investigated. Pentachlorocyclohexene, trichlorocyclohexene, and dichlorobenzene were detected as photodegradation intermediates, which were gradually degraded with the photodegradation evolution.     

Photocatalytic degradation of methyl orange over ITO/CdS/ZnO interface composite films

ITO/CdS/ZnO interface composite films were successfully prepared by subsequent electrodeposition of CdS and ZnO onto indium tin oxide (ITO) glass substrates. The obtained ITO/CdS/ZnO composite films were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-Vis spectroscopy. The photocatalytic activity of ITO/CdS/ZnO composite films were investigated using methyl orange (MO) as a model organic compound under UV light irradiation. The influence of operating parameters on MO degradation including initial concentration of MO, pH value of solution, and inorganic anion species over the composite films were examined. A blue shift of absorption threshold was observed for the ITO/CdS/ZnO film in comparison with ITO/ZnO film. ITO/CdS/ZnO composite films prepared under specific conditions showed a higher photocatalytic activity than that of ITO/ZnO films. It was also found that the photocatalytic degradation of MO on the composite filing followed pseudo-first order kinetics.     

Enhanced photocatalytic activity of quantum-dot-sensitized one-dimensionally-ordered ZnO nanorod photocatalyst

An efficient photocatalyst was fabricated by assembling quantum dots （QDs） onto one-dimensionally-ordered ZnO nanorods, and the photocatalytic properties for Methyl Orange degradation were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-Vis-NIR absorption spectroscopy and photoluminescence. The results indicate that the catalyst with assembled QDs is more favorable for the degradation than the pristine ZnO nanorods. The QDs with core-shell structure lower the photocatalytic ability due to the higher carder transport barrier of the ZnS shell layer. Besides its degradation efficiency, the photocatalyst has several advantages given that the one-dimensionally-ordered ZnO nanorods have been grown directly on indium tin oxide substrates. The article provides a new method to design an effective and easily recyclable photocatalyst.     

Photocatalytic remediation of γ-hexachlorocyclohexane contaminated soils using TiO2 and montmorillonite composite photocatalyst

TiO2 and montmorillonite composite photocatalysts were prepared and applied in degrading γ-hexachlorocyclohexane(γ-HCH)in soils.After being spiked with γ-HCH,soil samples loaded with the composite photocatalysts were exposed to UV-light irradiation.The results indicated that the photocatalytic activities of the composite photocatalysts varied with the content of TiO2 in the order of 10%＜70%＜50%＜30%.Moreover,the photocatalytic activity of the composite photocatalysts with TiO2 content 30% was higher than that of the pure P25 with the same mass of TiO2.The strong adsorption capacity of the composite photocatalysts and quantum size effect may contribute to its increased photocatalytic activities.In addition,effect of dosage of composite photocatalysts and soil pH on γ-HCH photodegradation was investigated. Pentachlorocyclohexene,trichlorocyclohexene,and dichlorobenzene were detected as photodegradation intermediates,which were gradually degraded with tlle phOtOdegradation evolution.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO2 composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

TiO2-NB/pg-C3N4可见光催化降解17α-乙炔雌二醇的机理

通过煅烧自制的TiO₂纳米带（TiO₂-NB）和多孔氮化碳（pg-C₃N₄）制备出新型的TiO₂纳米带/多孔氮化碳（TiO₂-NB/pg-C₃N₄）光催化剂,优化了其制备条件,并用于可见光条件下催化降解雌激素活性最强的17α-乙炔雌二醇（EE2）.通过SEM、TEM、XRD、UV-vis DRS、PL、XPS和BET等手段对催化剂结构和表面物理化学性质进行表征和分析.结果表明,B型TiO₂纳米带均匀负载至多孔氮化碳薄片上,形成TiO₂-NB/pg-C₃N₄复合光催化剂.最优条件下制备的TiO₂-NB/pg-C₃N₄降解EE2的速率常数（0.02537min^-1）分别是TiO₂-NB （0.00197min^-1）和pg-C₃N₄（0.0077min^-1）的12.88倍和3.29倍.自由基捕获实验结果显示超氧自由基（·O₂^-）是TiO₂-NB/pg-C₃N₄可见光催化降解EE2的主要活性物种.HPLC-MS中间体检测结果显示,可能的降解中间体主要有4个,提出可能的降解途径,而且通过MCF-7雌激素活性测试法可知降解过程产物的雌激素活性基本消除.     

Triton X-100 induced cuboid-like BiVO4 microsphere with high photocatalytic performance

A highly active visible light-induced BiVO₄ photocatalyst was prepared by a simple co-precipitation method using ammonia solution as a pH adjustor and Triton X-100 (TX100) as a structure directing agent. The physical properties of the prepared BiVO₄ photocatalyst were investigated by several techniques such as X-ray diffractometer (XRD), Brunauer–Emmett–Teller (BET) surface area measurement, scanning electron microscopy (SEM), energy dispersive analysis (EDS), Fourier-transformed infrared spectroscopy (FT-IR), photoluminescence (PL), and UV–Vis diffused reflectance spectroscopy (DRS). XRD results revealed the existence of a monoclinic scheelite structure in both the unmodified and the modified samples. The TX100 played a crucial role to control the cuboid-like shape morphology of BiVO₄. The DRS results showed that the as-prepared cuboid BiVO₄ possessed enhanced visible light absorption range compared with that of the unmodified BiVO₄. The photocatalytic activity was evaluated via indigo carmine (IC) degradation under visible light irradiation. The modified BiVO₄ showed higher photocatalytic efficiency than the unmodified BiVO₄ and the commercial P25-TiO₂ which could be ascribed to the better charge separation efficiency.     

Zr/TiO2纳米颗粒的制备及其光催化活性

以钛酸丁酯,乙醇为原料,用固相合成法制备了Zr/TiO2纳米颗粒,用XRD、TEM对其组成、颗粒大小、形貌进行了表征.通过对罗丹明B的降解反应,考察了Zr/TiO2的光催化活性.结果表明,Zr/TiO2为纳米颗粒,平均粒径为12.7 nm左右,且颗粒均匀;掺杂金属离子Zr提高了TiO2光催化效率,掺杂2.0%Zr的催化剂活性最高.Zr/TiO2的光催化反应,首先是反应物在Zr/TiO2表面发生吸附作用,然后进一步发生光催化降解.     

改性微管氮化碳的制备及光催化性能

以三聚氰胺、固体亚磷酸H₃PO₃为原料,通过水热-煅烧法制备了不同质量比的磷掺杂且具有层状堆积结构的六方管状氮化碳（MTCN-x）,x为固体亚磷酸与三聚氰胺的质量比.采用X射线衍射仪（XRD）、傅里叶变换红外光谱（FT-IR）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、比表面积分析仪（BET）、荧光光谱（PL）和紫外-可见漫反射光谱（UV-vis DRS）对最佳质量比X=1.2（MTCN-1.2）和不添加固体亚磷酸X=0（MTCN-0）催化剂形貌结构和光学性能进行了表征,结果表明,磷掺杂抑制了催化剂晶粒的生长,缩小了能带宽度,增加了可见光响应范围及可见光的利用率,有效的抑制了光生电子－空穴的复合,显著增强了光催化性能.通过光降解实验表明,MTCN-1.2在10min对抗生素环丙沙星（CIP）和四环素（TCL）的降解率分别为99.7%和97.8%,其反应速率常数分别是普通氮化碳（BCN）的10.5倍和6.8倍,表明改性的MTCN-1.2具有比MTCN-0、BCN更好的光催化降解性能.同时分别考察了溶液pH值、催化剂投加量、腐殖酸（HA）浓度等因素对光催化降解抗生素的影响,结果表明,CIP与TCL降解效果最佳的pH值分别为5和9.催化剂投加量的过高和HA浓度的升高,都会造成光催化效率的下降.自由基捕获实验证明,该催化体系降解过程中超氧自由基（·O^2-）和空穴（h⁺）占主导作用.     

新型磁性Mn0.6Zn0.4Fe2O4@CdS纳米复合光催化剂的制备及其吸附和光催化特性

以两步水(溶剂)热法制备了一种新型磁性Mn_(0.6)Zn_(0.4)Fe_2O_4@CdS纳米复合光催化剂,并采用X-射线衍射(XRD)、比表面(S_(BET))、扫描电镜-能谱(SEM-EDX)、紫外漫反射(UV-vis)、透射电镜(TEM)、磁滞回线(VSM)和价带能谱(VB-XPS)等手段对制备的铁氧体、CdS和复合材料进行了表征分析.结果发现,得到的材料元素含量与设计预期值吻合,纯相晶格参数与理论值匹配较高,特征峰证实复合材料中存在尖晶石铁氧体和CdS晶格;高分辨透射电镜(HR-TEM)分析表明,CdS有效地附着在铁氧体上,且在可见光区发生了红移.利用该材料对亚甲基蓝(MB)进行了暗室吸附和光催化活性的系统研究,结果表明,复合物吸附速率较快,适宜用Langmuir模型描述吸附平衡,最大吸附容量q_(max)高达79.6 mg·g~(-1);在测试的3个样品中,复合物光催化活性最高,经5次重复光催化实验,MB的降解率仍可保留在50%以上,且易磁分离回收;此外,通过自由基和空穴捕获实验、光致发光(PL)和电子顺磁共振(ESR)测试分析提出了MB降解机理.     

Photocatalytic decomposition of acrylonitrile with N–F codoped TiO2/SiO2 under simulant solar light irradiation

The solid acid catalyst, N–F codoped TiO₂/SiO₂ composite oxide was prepared by a sol–gel method using NH₄F as nitrogen and fluorine source. The prepared materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV–Visible diffuse reflectance spectroscopy (UV–Vis), ammonia adsorption and temperature-programmed desorption (NH₃-TPD), in situ Fourier transform infrared spectroscopy (FT-IR) and N₂ physical adsorption isotherm. The photocatalytic activity of the catalyst for acrylonitrile degradation was investigated under simulant solar irradiation. The results showed that strong Lewis and Brønsted acid sites appear on the surface of the sample after N–F doping. Systematic investigation showed that the highest photocatalytic activity for acrylonitrile degradation was obtained for samples calcined at 450°C with molar ratio (NH₄F to Ti) of 0.8. The degradation ratio of 71.5% was achieved with the prepared catalyst after 6-min irradiation, demonstrating the effectiveness of photocatalytic degradation of acrylonitrile with N–F codoped TiO₂/SiO₂ composite oxide. The photocatalyst is promising for application under solar light irradiation. Moreover, the intermediates generated after irradiation were verified by gas chromatography–mass spectrometry (GC–MS) analysis and UV–Vis spectroscopy to be simple organic acids with lower toxicity, and the degradation pathway was also proposed for acrylonitrile degradation with the prepared catalyst.     

香榧壳生物炭/g-C3N4活化过硫酸盐的光催化性能

采用简便一步热聚合法制备高催化活性的生物炭/g-C₃N₄复合光催化剂,并在可见光下活化过硫酸盐（PS）应用于对-乙酰氨基酚（AAP）废水的降解研究.通过紫外-可见漫反射吸收光谱（UV-vis DRS）、光致发光光谱（PL）对该复合催化剂的光学性质进行了研究.结果表明,生物炭的引入使g-C₃N₄的可见光吸收边界从483nm增强至553nm,并且提高了光致电子-空穴对的分离效率.扫描电子显微镜（SEM）、X射线衍射光谱（XRD）、傅里叶变换红外光谱（FT-IR）及X射线光电子能谱（XPS）的表征结果显示生物炭的引入改善了g-C₃N₄的微结构.在反应体系中引入PS强化了AAP的去除效率,在可见光照射下其降解速率是未添加PS的8.9倍,表明该催化体系可有效活化PS产生更多高活性氧化物质.自由基捕获实验表明该催化系统可能存在·O₂^-、h⁺、·OH和·SO₄^-活性物种,复合材料性能的提升主要归因于生物炭作为电子受体,有效抑制了电子-空穴的复合.