铈掺杂TiO2/Ti光电极制备及可见光下光电催化性能的研究

采用阳极氧化法制备铈掺杂TiO2／Ti光电极，用SEM、XRD、XRF、XPS和UV／VIS／NIR对光电极的性能进行表征，并对其可见光照射下的光电催化性能进行了测试．研究结果表明：在成膜电压为160V，电流密度为100mA／cm^2，Ce（NO3）3浓度为960mg／L条件下制备的铈掺杂TiO2／Ti光电极在降解罗丹明B的实验中表现出良好的光电催化活性．     

氮掺杂TiO2纳米管电极制备及可见光电催化活性

采用氮气中500℃和600℃热处理由阳极氧化法制备的TiO2纳米管阵列,制备了氮掺杂TiO2纳米管阵列电极.分别用环境扫描电镜(ESEM)、X射线光电子能谱(XPS),X射线衍射(XRD)和紫外可见漫反射吸收光谱对电极进行了表征.结果表明氮成功地掺入TiO2纳米管中.氮的引入使所制备的电极表现出可见光电催化活性,其中氮气中500℃下热处理得到的TiO2纳米管阵列电极表现出最好的可见光电催化活性.     

S、RE共掺杂TiO2的制备及其可见光分解水制氢性能

采用溶胶-凝胶法制备了系列稀土(La、Eu、Nd、Tb、Er)和硫共掺杂TiO2光催化剂RE/S/TiO2。通过紫外-可见(UV-Vis)漫反射、X射线衍射(XRD)对催化剂进行了表征。以EDTA为电子给体,考察了光催化剂在可见光照射下的制氢活性。研究结果表明,S/TiO2具有可见光活性,稀土掺杂进一步提高了S/TiO2可见光活性,其活性顺序依次为Eu/S/TiO2>La/S/TiO2>Nd/S/TiO2>Tb/S/TiO2>Er/S/TiO2。与纯TiO2和S/TiO2光催化剂相比,稀土掺杂使催化剂的粒径减小,晶格畸变应力增大,从而提高了催化剂可见光制氢活性。     

N掺杂TiO2纳米粉体的表面特性及可见光活性

旨在探究N掺杂纳米TiO2具有可见光活性的本质,采用XPS、ESR、XRD、SEM、DRS、SPS和PL分析技术对sol-gel法制备的未掺杂和N掺杂TiO2纳米粉体进行了对比研究,并以亚甲基蓝(MB)溶液在可见光下的光催化脱色评价其可见光活性。结果表明,N掺杂TiO2纳米粉体具有良好的可见光活性,未掺杂样品几乎没有可见光活性。N取代TiO2晶格中O形成了N─Ti─O和O─N─Ti键合结构产生杂质能级,N掺杂导致TiO2表面形成了大量束缚单电子的氧空位产生缺陷能级,二者协同作用致使带隙窄化,光吸收带边红移,产生可见光活性。N掺杂导致TiO2晶格中p-n结的形成及表面氧空位和表面羟基的增加均能促进光生e-/h+分离,有效抑制光生e-/h+复合,提高量子效率,进而提高其光活性。     

可见光响应的TiO_2/石墨烯复合材料的制备及其光电催化性能

对Hummers方法进行改进,制备出氧化石墨烯。采用氧化石墨烯和Ti(SO4)2作为初始反应物,利用Ti(SO4)2水解,在氧化石墨烯层间成核生长纳米TiO2颗粒,制得TiO2/氧化石墨烯复合材料,再通过水合肼进行还原,制得TiO2/石墨烯复合材料。通过XRD、FE-SEM、HR-TEM、TGA、UV-Vis、BET和电化学性能测试等测试手段对复合材料进行表征。以复合材料为工作电极,铂电极为对电极,饱和甘汞电极为参比电极,在可见光照射(λ420nm)下,通过光电催化降解含偶氮化学健的酸性红B,对复合材料的催化性能进行研究。结果表明,复合材料对可见光响应良好;在外加电极电压的条件下,复合材料的催化活性得到进一步增强。     

玻璃基底TiO2纳米管阵列的制备及其光电性能研究

提高二氧化钛纳米管阵列电极的机械稳定性,改善电极的透光性能,有助于提高其光电催化性能,拓展电极的应用范围.通过室温射频溅射方法在玻璃基底上溅射一层金属钛膜,然后在含0.5%HF的电解液,10V阳极氧化电压下进行阳极氧化,得到玻璃基TiO2纳米管阵列电极.扫描电子显微镜和X射线衍射分析表明,玻璃基表面形成了孔径为20～30nm,管长约130nm排列有序的锐钛矿型TiO2纳米管阵列.光电性能测试表明,玻璃基TiO2纳米管阵列与金属钛基TiO2纳米管阵列表现出相似的光电催化性能,明显优于磁控溅射制备的TiO2薄膜.     

具有高可见光催化性能W掺杂纳米TiO_2的制备与表征

利用水热合成法成功地制备具有高活性可见光响应的W掺杂TiO2纳米粉体,采用X射线衍射、场发射扫描电镜、场发射透射电镜、可见光吸收光谱、光致发光光谱等对W掺杂TiO2纳米粉体进行表征;W掺杂TiO2纳米粉体的光催化性能通过测试其在可见光和紫外光照射下降解罗明丹B染料的催化效率来检验。结果表明,W掺杂TiO2纳米粉体在可见光照射下的光催化效率要远远大于商品P25和纯TiO2,W的最佳掺杂摩尔分数为40%。     

TiO_2纳米管半导体特性与光电催化动力学研究

通过阳极氧化法在有机溶液中制备TiO2纳米管阵列,随着氧化时间的不同,TiO2纳米管阵列呈现各异的形貌。通过光电流测试,考察了不同氧化时间和施加不同电压下的Ti/TiO2纳米管阵列光电极的光电化学响应,阳极氧化6h表面规整纳米管阵列并施加偏压0.1V光电流响应最强。通过测试Mott-Schott-ky曲线,计算不同氧化时间的TiO2纳米管阵列的半导体载流子浓度、平带电位、空间电荷层宽度和能带弯曲量等特征参数,理论上提出了TiO2纳米管阵列生长机理。在光电催化降解无机氨氮的实验中,所得到的电化学阻抗谱(EIS)表明,外加偏压0.1V时,TiO2纳米管阵列电极的光电催化活性最强,同时通过拟合电路分析可知,光电催化降低了电极界面的反应阻抗,加速了光生载流子的转移,在TiO2纳米管阵列电极/溶液界面Helmholtz层中发生的氧化还原反应是整个光电催化反应的速率控制步骤。     

Ag/TiO_(2-x)N_x纳米管的光电催化性能

在0.5wt%NaF+1mol/L Na2SO4溶液中,20V电压下,通过阳极氧化的方法,在纯Ti片表面制备出与基底垂直、排列整齐有序的TiO2纳米管,将制得的TiO2纳米管在500℃、氨气的气氛下退火2h,然后,在0.5mol/L AgNO3溶液中用12W的紫外灯照射24h,制备出Ag/TiO2-xNx纳米管,并用XRD,SEM和XPS进行表征.实验结果显示,在紫外光下,Ag/TiO2-xNx纳米管的光电催化降解效率比TiO2纳米管的光电催化降解效率提高了39.68%;在可见光下,Ag/TiO2-xNx纳米管的光电催化降解效率比TiO2-xNx纳米管可见光光电催化的降解效率提高了12%.可见光光电催化16h后,初始浓度为10×10-6mol/L的亚甲基蓝降解率达到50.53%.     

TiO2掺杂PbO2电极及其在电解法制臭氧中的应用研究

为了提高电极对臭氧生成反应的电催化活性,采用纳米复合电镀技术制备了TiO2改性PbO2电极.分别采用X射线衍射和X射线荧光光谱分析了其晶体结构和组分含量。将该电极用于电解法制备臭氧,并考察了电流密度、电镀极间距、电镀液pH值以及TiO2颗粒粒径对电极性能的影响.实验结果表明,改性后的PbO2电极使臭氧生成反应的电流效率由11.9%提高到了12.9%.电镀电流密度和电镀极间距的提高有利于提高电极催化活性.TiO2的掺杂会降低PbO2电极的晶胞粒径,有利于提高电极的电催化活性.     

Preparation and characterization of sulfur-doped TiO(2)/Ti photoelectrodes and their photoelectrocatalytic performance

Sulfur-doped TiO(2)/Ti photoelectrodes were prepared by anodization and characterized by SEM, AFM, XRD, XPS, UV-vis and SPS. The results of investigation indicated that S(4+) and S(6+) were dispersed on the surface of TiO(2) nanoparticles. The doping with an appropriate amount of sulfur expanded the response range of TiO(2)/Ti photoelectrodes to visible light, and enhanced the separation of photoinduced electrons from cavities. The photoelectrocatalytic performance test run with sulfur-doped TiO(2)/Ti photoelectrodes under Xenon light indicated that Na(2)SO(3) concentration of 750 mg/L and voltage of 160 V were the optimal conditions for preparation of sulfur-doped TiO(2)/Ti photoelectrodes.     

Fabrication of TiO2/Ti electrode by laser-assisted anodic oxidation and its application on photoelectrocatalytic degradation of methylene blue

A TiO2/Ti mesh electrode by laser calcination was prepared in this article. The resulting TiO2 film was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS), and it illuminated that the prepared electrode mainly consisted of anatase TiO2 nanoparticles on its surface and exhibited a superior photocatalytic activity. The photodegradation of methylene blue (MB) using the proposed electrode under different experimental conditions was investigated in terms of both UV absorbance at 664 nm and chemical oxygen demand (COD) removal. The electrical bias applied in photoelectrocatalytic (PEC) oxidation was also studied. The experimental results showed that under the optimal potential of +0.50 V (versus SCE), UV absorbance and COD removal during the photodegradation of MB by the proposed TiO2/Ti mesh electrode were 97.3% and 87.0%, respectively. Through the comparison between photocatalytic (PC) oxidation and photoelectrocatalytic (PEC) oxidation, it was found that PEC oxidation was a convenient and effective way to mineralize the organic matters and that laser-treated photoelectrode exceeded the oven-treated one.     

Photocatalytic degradation of methyl orange using a TiO2/Ti mesh electrode with 3D nanotube arrays

To further improve the photocatalytic techniques for water purification and wastewater treatment, we successfully prepared a new type of TiO(2)/Ti mesh photoelectrode, by anodization in ethylene glycol solution. The three-dimensional arrays of nanotubes formed on Ti mesh show a significant improvement in photocatalytic activity, compared to the nanotube arrays formed on foil. This can be demonstrated by about 22 and 38% enhancement in the degradation efficiency per mass and per area, respectively, when TiO(2)/Ti mesh electrode was used to photocatalyze methyl orange (MO). Furthermore, the effects of different parameters on MO photodegradation were investigated, such as different photoelectrode calcination temperature, the initial pH value of MO solution, and the present of hydrogen peroxide. The superior photocatalytic activity could be achieved by the TiO(2)/Ti mesh photoelectrode calcinated at 550 °C, due to the appearance of mixed crystal phases of anatase and rutile. In strong acidic or caustic conditions, such as pH 1 or 13, a high degradation efficiency can be both obtained. The presence of H(2)O(2) in photocatalytic reactions can promote photocatalytic degradation efficiencies. Moreover, the experimental results demonstrated the excellent stability and reliability of the TiO(2)/Ti mesh electrode.     

Comparative study of photocatalytic and photoelectrocatalytic properties of alachlor using different morphology TiO2/Ti photoelectrodes

Wormhole-shaped TiO(2)/Ti (WT) and nanotube-shaped TiO(2)/Ti (TNT) photoelectrodes were prepared by anodic oxidation method. The morphology and structure were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It was found that both crystal types of WT and TNT photoelectrodes were composed of anatase and rutile TiO(2) phases; however TNT photoelectrodes had highly ordered nanostructure. The photoelectrochemical (PECH) and photoelectrocatalytic (PEC) properties of WT and TNT photoelectrodes were investigated by photocurrent transient, open-circuit potential and degradation rate of alachlor under the artificial solar light illumination. All results showed that TNT photoelectrodes prepared in NaF-Na(2)SO(4) solution have more excellent photoelectron properties than WT photoelectrodes prepared in H(2)SO(4) solution. The photocatalytic (PC) and PEC experiments of alachlor showed that PC and PEC activities of TNT photoelectrodes were superior to WT photoelectrodes. At applied bias potentials the degradation rate of alachlor at TNT photoelectrodes increased significantly to 94.5%. The higher PC and PEC performance of TNT photoelectrodes were ascribed to the long-range ordered structure and short-orientation diffusion distance of photogenerated carries.     

Ag掺杂APS改性的TiO2颗粒的制备及其光催化降解作用

为提高Ag/TiO2纳米颗粒的光催化降解作用,采用聚合凝胶工艺路线,以钛酸四丁酯为前驱体,硝酸银为银源,通过向反应体系引入鳌合剂醋酸、表面改性剂γ-氨丙基三乙氧基硅烷(APS)以及还原剂甲醛等添加剂,制备出TiO2粉体及Ag/TiO2纳米复合粉体。利用FT-IR、XRD、TG-DTA、TEM和UV-Vis-NIR等手段对样品进行表征。结果表明,经γ-氨丙基三乙氧基硅烷改性的TiO2颗粒掺Ag后分散性得到改善,粒径约1 nm的Ag颗粒较均匀地分布在10～15 nm TiO2颗粒上;可见光的利用和锐钛矿热稳定性都得到提高;Ag/TiO2纳米颗粒在光照下对甲基橙具有良好的光催化降解效果。     

镍、硫共掺杂纳米TiO2的制备及其可见光催化性能

为提高纳米TiO2的可见光催化活性,采用沉淀-浸渍法制备了一种新型Ni和S共掺杂TiO2纳米复合光催化剂.通过紫外-可见(UV-Vis-)漫反射、X-射线衍射(XRD)、透射电子显微镜(TEM)和X-荧光(EDX)等手段对其结晶形态、晶粒尺寸、元素掺杂量和吸光性能等进行了表征.结果显示,催化剂Ni/S/TiO2为锐钛矿晶相,平均粒径约为6～7nm,比表面积高达260.42m2/g,感光范围可拓展到可见光区,且与纯TiO2,S掺杂TiO2和Ni掺杂TiO2相比,光催化剂Ni/S/TiO2的颗粒粒径更小,比表面积更大,光吸收边红移程度更显著.以活性艳蓝198染料溶液为模拟废水,以氙光灯为光源,对光催化剂Ni/S/TiO2的催化活性进行了评价.结果表明,Ni/S/TiO2具有比纯TiO2、S掺杂TiO2和Ni掺杂TiO2更高的可见光催化活性,氙光灯照射120min,活性艳蓝198降解率可达到98.5%.     

A visible light response TiO2 photocatalyst realized by cationic S-doping and its application for phenol degradation

S-doped TiO2 photocatalyst with high visible light activity was prepared by acid catalyzed hydrolysis method using thiourea (TU) as sulfur source. The catalyst was characterized by DRS, XPS, XRD, FTIR, SEM and N2 adsorption. It was found that cation S6+ was homogeneously incorporated into the bulk phase of TiO2 and substitutes for some of the lattice titanium (Ti4+). Doped S can form a new band above the valence band and narrow the band-gap of the photocatalyst, giving rise to a second absorption edge in the visible light region. The activity of the catalyst was examined by photodegradation of phenol in aqueous solution under both artificial visible light and solar light irradiation. The activity of catalyst was found to be dependent on the doping amount of S and the maximum activity was observed when the catalyst was obtained by calcinated at 600 degrees C with the mass ratio of TU/TiO2=1. Too much of new-generated band-gap structures due to higher S-doping could act as recombination centers for electron-hole pairs. Catalyst with optimum S-doping exhibited the highest activity under both artificial light and solar irradiation for phenol degradation. In addition, doped S also beneficial for the better dispersion, large S(BET) and phase transformation retardation of TiO2.     

复合电沉积制备SnO2/TiO2薄膜及其光电催化性能

为了寻求廉价、高效和稳定的光催化剂,用复合电沉积技术在紫铜片上制备了Sn/TiO2薄膜,经300℃热氧化使之形成SnO2/TiO2复合电极.利用SEM,XRD对薄膜进行了表征,以甲基橙为模型化合物,对复合电极的光催化和光电催化性能进行了测定.研究表明:该薄膜由0.3~1μm的颗粒构成,每个颗粒又由纳米晶粒形成;电极具有多孔结构,膜中的SnO2以两种不同的晶体结构存在;在薄膜质量相等的情况下,SnO2/TiO2薄膜的光催化活性是纯TiO2粒子膜的2.87倍;外加一定偏压下,其催化性能大幅度提高.     

微波加热法制备Ag/TiO_2及光催化降解气相甲苯

以钛酸四丁酯为钛源,分别使用微波加热法和水热法制备Ag改性的TiO2,采用X射线衍射(XRD)、X射线荧光探针(XRF)、紫外-可见漫反射(UV-Vis)和扫描电镜(SEM)对其进行表征.以气相甲苯为降解对象,分别在紫外和可见光辐照下,对样品进行光催化活性试验.结果表明:与水热法比较,微波加热法更有利于Ag对TiO2微观结构的改性,所制备的Ag改性TiO2包含了锐钛矿、金红石和板钛矿三种晶相,其粒径更小(16.4nm)、孔道结构更丰富、团聚体更小(80~200nm)、带隙能更低(2.87eV),表现出对气相甲苯更有效的紫外光和可见光降解能力.     

Cu掺杂FeVO4光催化剂的制备及其光催化性能

为进一步提高钒酸铁(FeVO4)光催化活性,采用液相沉淀法分别制备钒酸铁和钒酸铜前躯体,再将钒酸铁和钒酸铜前驱体混合后进行热处理,制备了铜掺杂钒酸铁光催化剂,并采用X射线衍射(XRD)、扫描电子显微镜(SEM)、表面积(BET)和X射线光电子能谱分析(XPS)对样品进行表征和分析.在可见光照射下,通过光催化降解甲基橙溶液评价Cu掺杂对FeVO4光催化剂活的影响.结果表明,Cu/FeVO4光催化剂为三斜型,当掺杂质量分数大于5%时,晶体中出现新相Cu3Fe4(VO4)6;掺杂后样品的表面形貌产生了变化,但其比表面积变化较小;Cu/FeVO4样品的光催化活性大幅提高,主要是由于FeVO4和新相间起到类似复合半导体的作用;在所进行实验的条件下,钒酸铜的最佳掺杂质量分数为5%时,掺杂后的FeVO4对甲基橙溶液的脱色率较未掺杂前提高30%左右.