电泳沉积法制备ZnO/SnO_2复合薄膜及其光催化性能研究

在导电玻璃FTO基底上,利用电泳沉积技术成功制备了ZnO/SnO2复合薄膜,并对样品进行了SEM和XRD表征,并以降解罗丹明B为模型反应,考察不同条件下制备的复合薄膜的光催化活性。结果表明电泳沉积时间为20min时,可得到表面致密均匀的ZnO薄膜,膜厚为0.5μm,且随着电泳沉积时间的延长,薄膜的光催化速率不断增加,沉积时间为20min时,光催化速率达到最大（0.016min-1）,如此优异的光催化性能可能是由于异质结构光催化剂ZnO/SnO2减小光生电子-空穴的复合几率,提高了复合催化剂的光催化效率。此外,还研究了热处理温度对ZnO/SnO2复合薄膜光催化效率的影响,结果发现在300℃热处理的光催化薄膜对罗丹明B的降解率最好,活性最高。     

一步法合成高效三元Z型AgBr/Ag/BiVO4光催化剂

采用一锅水热法制得三元Z型溴化银(AgBr)/银(Ag)/钒酸铋(BiVO_4)即(AgBr/Ag/BiVO_4)光催化剂,并对制得的样品的相组成、微观形貌和光催化活性进行了表征。通过可见光照射条件下对罗丹明B的降解来评价AgBr/Ag/BiVO_4的光催化活性。结果表明:AgBr/Ag/BiVO_4呈圆形或不规则的多面体形状,与纯BiVO_4相比,AgBr/Ag/BiVO_4复合材料表现出较高的光催化活性,在硝酸银含量为8%,反应温度为90℃,反应时间为12h条件下,制得的AgBr/Ag/BiVO_4光催化剂的光催化活性最高,对罗丹明B的降解率达到89.8%。这种增强的光催化活性是由于从纯Ag转移BiVO_4可见光下导带电子,然后迅速转移到AgBr的价带,而光生空穴在溴化银价带,抑制光生电子和空穴的复合,导致AgBr/Ag/BiVO_4光催化剂具有较好的光催化活性。     

快速共沉淀法制备Ce掺杂ZnO及其日光催化性能研究

采用氢氧化钠快速共沉淀法制备了Ce掺杂ZnO,以模拟日光催化降解罗丹明B为指标,优化Ce掺杂比例及煅烧温度,考察催化剂套用稳定性和适用性,最后对Ce掺杂ZnO活性机理进行分析。结果表明:Ce最佳掺杂摩尔分数为3%,500℃煅烧2h,对1.0×10~(-5) mol/L罗丹明B溶液40min降解率达到93.8%,6次套用降解率达到90%以上,对仲夏自然阳光和其他染料均有良好的适用性。Ce掺杂降低了光致空穴-电子复合率,有效的提升了光催化活性。     

水热合成Bi2WO6/ZnO异质结型光催化剂及其光催化性能

在不同温度下(120～220℃),利用水热法制备了含1wt%、2wt%、4wt%和8wt%Bi2WO6的异质结型Bi2WO6/ZnO复合光催化剂,采用X射线粉末衍射(XRD)、扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、紫外可见漫反射(UV-Vis)吸收光谱及光致发光光谱(PL)等系列手段对所制备的光催化剂进行了表征,并以紫外光(365nm)为光源,酸性橙II为降解对象,进行光催化活性测试,考察了不同Bi2WO6复合量及不同水热温度对ZnO光催化剂反应活性的影响.研究表明,异质结型Bi2WO6/ZnO复合光催化剂的光催化活性明显优于纯ZnO和Bi2WO6.当复合4wt%Bi2WO6水热处理温度为150℃时,所制备的复合光催化剂的光催化活性最佳,为纯ZnO的2.6倍.活性提高的主要原因是形成的Bi2WO6/ZnO异质结能显著降低光生电子和空穴对的复合几率,并改善了异质结型Bi2WO6/ZnO复合光催化剂的表面性能.     

ZnO/TiO_2纳米管的制备及光降解性能研究

采用水热法合成TiO2纳米管,在碱性条件下与乙酸锌的无水乙醇溶液反应,得到表面负载ZnO的TiO2复合纳米管(ZnO/TNTs),并研究了复合纳米管在紫外光照射下对罗丹明B的光催化降解性能。通过透射电镜(TEM)、电子衍射能谱(EDS)、X射线衍射(XRD)、比表面积(BET)和紫外-可见光谱(UV-Vis)对所合成的材料进行了表征。结果表明,TiO2纳米管管径约5~10nm,管长约0.1~1μm;经ZnO表面修饰后,纳米管的结构没有发生明显变化,且ZnO粒子呈六方晶系纤锌矿结构均匀分散在纳米管的外表面,粒径约为6nm;光谱分析表明,ZnO/TNTs的吸收光谱有明显红移;且ZnO/TNTs的光催化活性较锐钛矿型TiO2纳米粉末、ZnO纳米粉末和TiO2纳米管有显著提高,且其光催化性能重复性好。     

Au修饰ZnO纳米带及其光催化性质研究

采用离子溅射方法在ZnO纳米带表面蒸镀Au层,经过500℃退火,在样品表面形成Au纳米颗粒,通过SEM、XRD对退火后样品进行结构表征,结果表明,随着蒸镀Au量的增加,在500℃退火后的Au颗粒尺寸逐渐减小,且分布均匀。Au颗粒与ZnO纳米带接触可以形成肖特基结,肖特基结能够有效地使电子与空穴分离并且快速导出电子,所以能够有效提高光催化活性。将以上产物作为光催化剂,在紫外光照射下降解甲基橙（Methyl Orange）,研究其光催化性能,与纯zn0相比,金修饰ZnO纳米带的光催化性能有明显的提高,且不同Au颗粒尺寸降解能力不同。     

不同合成过程对溶胶-凝胶法制备的ZnO/Ag纳米复合材料光催化性能的影响

以乙酸锌、硝酸银为前驱体,二乙醇胺作为稳定剂,利用溶胶-凝胶法分别采用一步法和两步法制备得到ZnO以及ZnO/Ag纳米复合粉体。所有ZnO/Ag复合物中Ag的含量均为3%(摩尔分数)。对所制备样品的结构和光学性质通过XRD、SEM、TEM、XPS、PL、UV-vis进行了表征,进而以甲基橙为模拟污染物进行了光催化测试。结果表明,不同方法制备得到的ZnO/Ag纳米粉体晶粒均匀,无明显团聚现象,面心立方结构的金属Ag吸附在纤锌矿结构的ZnO表面形成异质结。与纯ZnO相比,掺Ag极大地改善了样品在紫外光下的光催化活性。对不同合成工艺的比较表明,用溶胶-凝胶一步法制备的ZnO/Ag复合物的光催化活性最高,经紫外光照射70min可完全降解甲基橙。     

Ag/g-C_3N_4复合光催化材料的光物理及光催化性能

通过加热AgNO3与g-C3N4成功制备了Ag/g-C3N4复合光催化材料。利用X射线衍射仪(XRD)、傅里叶红外光谱仪(FTIR)分析热解产物的物相和结构,采用紫外-可见吸收光谱和光致发光谱(PL)表征样品的光吸收和荧光性质。以罗丹明B为模型污染物,评价样品的可见光(λ≥420nm)光催化性能。结果表明:与纯g-C3N4相比,3%载银量的Ag/g-C3N4复合光催化材料在可见光下降解罗丹明B的光催化性能最好。分析表明Ag与g-C3N4的协同作用抑制光致电子空穴对的复合是光催化性能提高的主要原因。     

Yb离子掺杂纳米ZnO的合成及其光催化性能研究

直接沉淀法制备纳米ZnO后利用浸渍法制备其Yb3＋掺杂产物,以XRD、FESEM、HRTEM、XPS、漫反射吸收光谱和分光光度法等研究了粉体的特征及光催化性能。结果表明500℃煅烧获得的纳米ZnO具有六方纤锌矿结构,粒径分布范围较窄;适量的Yb3＋掺杂能有效地提高纳米ZnO对罗丹明B的光催化降解效率。     

Ag-TiO_2空心复合微球制备及其光催化性能

为了提高空心TiO2的光催化活性和拓展其对可见光的响应,以聚苯乙烯为模板合成TiO2空心微球,再通过KBH4还原AgNO3,制备了TiO2空心壳层表面载有Ag单质粒子的复合微球。利用SEM、TEM、XRD和EDS对Ag-TiO2空心微球的形貌结构和组成进行表征,并以有机染料罗丹明B(RhB)为目标降解物,研究该复合微球的光催化性能。在紫外光下,载银量为2%的Ag-TiO2复合微球2h内对RhB的降解率比同条件下空心TiO2提高23.8%;在可见光下,载银量为2%的Ag-TiO2复合微球在6h内对RhB的降解率比同条件下空心TiO2提高28.2%。结果表明,壳层表面载有适量Ag单质粒子的空心TiO2复合微球,其光催化活性和对可见光的响应显著高于纯空心TiO2微球。     

高氧空位氧化锌晶体的制备及光催化性能

利用气相沉积法,在低氧气氛下制备高缺陷的ZnO晶体。分别将样品在800℃、900℃、1000℃下通氧退火1h,对ZnO晶体做表面修饰。PL光谱实验和光催化降解亚甲基蓝实验表明ZnO晶体的氧空位、表面态和光催化活性间存在内在联系。1000℃下退火的样品表面缺陷程度多于800℃和900℃下退火样品,光催化活性也优于后两者。     

莫板法制备ZnO纳米管及其光催化性能的研究

以碳纤维为模板,用原子层沉积（ALD）方法在其上包覆ZnO层,将样品分别进行不同温度的退火处理,利用X-射线衍射和扫描电子显微镜测试样品的结构和形貌,当退火温度为700℃时,获得ZnO纳米管,测试ZnO纳米管的光催化性能对甲基橙的降解作用,随着催化剂用量的增加和光照时间的延长,对甲基橙降解率明显提高。     

Ag-ZnO/生物质炭纳米复合材料的制备及协同可见光催化性能

以醋酸锌(Zn(CH₃COO)₂·2H₂O)为锌源、硝酸银(AgNO₃)为掺杂源、纤维素纳米晶体(Cellulose nanocrystal, CNC)为生物模板，通过溶胶-凝胶法结合碳化处理，制备了Ag-ZnO/生物质炭(Biochar)复合材料。采用TEM、XRD、BET、UV-Vis DRS对所制得的Ag-ZnO/Biochar复合材料进行表征。以亚甲基蓝(MB)为模型污染物，评价Ag-ZnO/Biochar复合材料在可见光源照射下的光催化性能，进一步阐明其光催化机制。结果表明:碳化后纳米ZnO仍保持良好的分散性，球形Ag纳米粒子均匀分散在ZnO表面，形成Ag-ZnO/Biochar三元复合材料。与Ag-ZnO和ZnO/Biochar复合材料相比，Ag-ZnO/Biochar复合材料在可见光下的光催化降解率显著提高。这是由于生物质炭赋予复合体系良好的吸附性能，使MB的光催化降解反应持续发生；而Ag纳米粒子的表面等离子体共振(Surface plasmon resonance, SRP)效应则增强了复合体系在可见光区的吸收。其中，当AgNO₃、CNC、Zn(CH₃COO)₂·2H₂O的质量比为0.01:0.25:1时，制得的Ag-ZnO/Biochar复合材料在可见光下具有最佳的光吸收性能和MB降解效率:室温条件下，黑暗中吸附30 min，再用可见光照射120 min，即可达到99%的MB降解率，显著高于Ag-ZnO(约23%)和ZnO/Biochar复合材料(约64%)。      

均匀沉淀法制备ZnO、Fe/ZnO光催化剂

以六水合硝酸锌、九水合硝酸铁和CO(NH2)2为原料,采用均匀沉淀法并且改变实验条件制备了纯纳米ZnO和纳米Fe/ZnO光催化剂。通过X射线衍射(XRD)和扫描电子显微镜(SEM)对所有样品进行表征,并对部分样品进行了X射线能谱分析仪(EDS)测试。结果显示所有样品均为六方纤锌矿结构。此外,所有样品均由小颗粒聚集在一起而形成了形状、大小各不相同的团聚物或颗粒膜。而且随煅烧温度和Fe掺杂浓度的改变,Fe/ZnO样品的晶粒尺寸和表面形貌也随之变化。以甲基橙溶液作为污染物,在高压汞灯的照射下进行了光降解实验,实验结果表明:Fe掺杂Fe/ZnO样品的光催化性能相较纯纳米ZnO样品得到了改善。当Fe掺杂量为1.5%时Fe/ZnO样品的光催化性能最好;另外,适当煅烧温度也使Fe/ZnO样品的光催化活性得到了提升,其中最适煅烧温度为500℃。无论是Fe的掺杂浓度还是煅烧温度,适当的Fe的掺杂浓度和煅烧温度都有利于改善Fe/ZnO样品光催化剂的性能。     

焙烧温度对1.0wt%Sm-TiO_2纳米粉体可见光催化活性的影响

采用溶胶-凝胶法制备了经不同温度焙烧的1.0wt%Sm掺杂TiO_2纳米粉体(SmTiO_2)。通过对样品进行表征,以亚甲基蓝(MB)作为目标降解物,考察了不同焙烧温度条件下制备的Sm-TiO_2样品对MB的光催化降解效果。结果表明,焙烧温度对Sm的实际掺杂效果影响不大,Sm掺入TiO_2后在表面存在Sm~(3+)和Sm~(2+)两种价态;Sm掺杂抑制了TiO_2从锐钛矿相向金红石相转变,抑制了光生e~-/h~+的复合;焙烧温度升高,样品中金红石相含量增加,晶粒尺寸增大。焙烧温度500℃时样品的吸收光谱阈值红移最大,光生e~-/h~+的复合率低,1.0wt%Sm-TiO_2样品在普通日光灯下对MB在6h内的降解率达96.86%,明显高于同类产品P25的降解率(56.52%)。     

Effect of Surface Roughness on Laser Induced Nonlinear Optical Properties of Annealed ZnO Thin Films

Variation of nonlinear optical properties with surface roughness of ZnO thin films deposited on corning glass substrates at different annealing temperature(TA) was reported.The films were characterized by X-ray diffraction(XRD),UV-Vis-NIR transmission and single beam z-scan technique using second harmonics of Nd:YAG laser.Surface morphology of the samples was investigated by atomic force microscopy(AFM).Surface roughness was found minimum(8.4 nm) for ZnO sample annealed at 450 ℃.The nonlinear optical properties(NLO) were found to be dependent on surface roughness and the highest value of third order nonlinear susceptibility(χ～(3)=4.3×10～(-7) esu) was obtained for ZnO at TA 450 ℃.     

A Novel one-step synthesis of Ag-doped ZnO nanoparticles for high performance photo-catalytic applications

In this report, pure and silver (Ag) doped zinc oxide (ZnO) nanoparticles with various concentrations of silver (5 and 10 wt%) was successfully synthesized by a novel and one step microwave irradiation method. Powder X-ray diffraction results indicates that all of the as-synthesized samples including the highest Ag (10 wt%) doping have a hexagonal wurtzite type structure and average crystalline size was found to be 28, 21 and 16 nm for pure and Ag doped ZnO respectively. Spherical shaped morphology with an average diameter of around 32–13 nm was observed by Transmission electron microscope analysis. UV–Vis spectra revealed that, Ag doped samples exhibits a red shift in the absorption band edge with increasing Ag dopant concentration. The photocatalytic degradation of methyl violet (MV), phenol and rhodamine B (RHB) was investigated by using Ag-ZnO catalyst under UV light irradiation. The result showed that the photocatalytic property was significantly improved by Ag doping. The improved photocatalytic mechanism by Ag doping was also discussed. The samples were further characterized by photoluminescence spectra and Fourier Transform Infrared Spectra (FTIR) analysis.     

Fabrication of ZnO Nanoneedle/nanocolumn Composite Films and Annealing Induced Improvement in Their Microstructural and Photoluminescence Characteristics

ZnO nanoneedle/nanocolumn （NN/NC） composite films were grown via reactive electron beam evaporation （REBE） in the NH3/H2 gaseous mixture by using polycrystalline ZnO ceramic targets as source materials. The growth was performed at low substrate temperatures （450～500℃） without employing any metallic catalysts. As-prepared samples were then rapidly annealed in 02 ambient at a higher temperature （600℃）. Electron microscopic observations revealed the typical composite-structured morphologies of NN/NC/substrate of ZnO nanomaterials grown at 500℃. Such unique morphologies should render potential applications, for instance, as an efficient microwave absorption material utilized in the fabrication of concealed aerostat. In addition, X-ray diffraction and photoluminescence measurements showed remarkable improvement in crystal and optical qualities of ZnO NN/NC composite films after annealing.     

Ag-modified ZnO nanorods and its dual application in visible light-driven photoelectrochemical water oxidation and photocatalytic dye degradation: A correlation between optical and electrochemical properties

In this work, Ag-ZnO composite was prepared at different weight percentages using a modified hydrothermal method for application to the photoelectrochemical (PEC) water oxidation and photocatalytic dye degradation. The resulting samples were studied using structural, surface, optical and photoelectrochemical (PEC) characterization methods. The surface plasmon resonance (SPR) of the optimal catalyst played an essential role in the synergistic improvement of the optical response and the photoinduced charge carrier separation process. The optimal Ag modified ZnO (3 wt% of Ag) showed superior photocatalytic and water oxidation performance. The inclusion of Ag has also played a vital role in the defect concentration and the Schottky junction at the metal–metal oxide interface. As a result, the PEC behavior of the optimal samples showed drastic improvements in terms of water oxidation current response under visible light illumination. Consequently, the photocatalytic performance of the samples also exhibits a linear relationship with the PEC water oxidation performance. The PEC and photocatalytic performance of the optimal sample showed almost five and seven times superior performance than the pristine ZnO in terms of photocurrent value and rate constant value, respectively. This can be attributed to the existence of the Schottky junction leading to the minimum charge transfer resistance and better charge transport across the interface. The superiority of the optimal sample is explained in terms of the physicochemical properties and electrochemistry of the material. To the best of the authors’ knowledge, this is the first report on the role of optimal Ag content in ZnO for its dual application. The combined study offering complete information, the work provides guidelines for noble metal-modified catalyst research moving forward.