Enhanced photocatalytic activity in metal phthalocyanine-sensitized TiO2 nanorods

Research on Chemical Intermediates - Two novel metal phthalocyanines (Zn Tetra(butylformate-phenoxy)phthalocyanine (ZnTBPP) and Zn Tetra(tert-butyl-phenoxy)phthalocyanine (ZnTTPP)) were...     

Efficient silver modification of TiO2 nanotubes with enhanced photocatalytic activity

In this paper, Ag(CH₃NH₂)₂⁺, Ag(NH₃)₂⁺ and Ag⁺ with different radii have been used as silver sources to find out the distribution of Ag ions on the H-TNT surface, which is critical to the final performance. The influence of this distribution on visible photocatalytic activity is further studied. The results indicate that, when Ag⁺ used as silver source with low concentration, these small sized silver ions mainly distribute on interlayer spacing of H-TNT. After heat-treatment and photo-reduction, the generated silver nanoparticles uniformly embed in the anatase TiO₂ nanotube walls, and bring large interfacial area between Ag particles and TiO₂ nanotubes. The separation effect of photogenerated electron-hole pair in TiO₂ is enhanced by Ag particles, and achieves the best at 0.15 g/L, much higher than P25, TiO₂/0, Ag-N@TiO₂ and Ag-C-N@TiO₂. This paper provides new ideas for the modification of TiO₂ nanotubes.     

The photocatalytic properties of amorphous TiO2 composite films deposited by magnetron sputtering

The preparation of amorphous TiO₂ film coupled with various metal-oxide semiconductors and their photocatalytic activities evaluated by photo-degradation of methylene blue and rhodamine B aqueous solution are briefly reviewed. The proposed photoreaction mechanism of the amorphous composite semiconductor and the differences between amorphous TiO₂-based films and crystalline TiO₂ photocatalytic materials in terms of preparation and usage are addressed. The inactive intrinsic amorphous TiO₂ film coupled with various metal oxides were found to gain high photocatalytic activity. These dopants induce forming new energy levels in the band gap of TiO₂ to enhance the charge separation of the photoinduced electrons and holes and extend the light absorption of TiO₂-based photocatalytic films into the visible region. In addition, two different effects of coupling metal oxides have been proved: the introduction of oxides of W, Cr, V, Ag, and Mo can significantly increase the photo-reactivity of amorphous TiO₂ film, while the combination of oxides of Zr, Sn, Sb, Cu, Ta, Fe, and Ni cannot affect the inactivity of pure amorphous TiO₂ film.     

氮硫共掺杂TiO_2的光电荷分离效应及其光催化性能研究

以硫脲为掺杂剂,采用溶胶-凝胶法制备了氮硫共掺杂TiO2(N,S-TiO2)。用比表面孔隙仪(BET)、X射线衍射仪(XRD)、紫外-可见漫反射(UV-Vis DRS)和X射线光电子能谱(XPS)对制备的光催化剂进行了表征,用表面光电压仪(SPS)和捕获剂研究了光催化剂的光生电荷分离效应。以甲基橙为模拟污染物,在模拟自然光照射下考察了样品的光催化性能。结果表明:硫脲/Ti的摩尔比为30%所制备氮硫共掺杂TiO2具有较高的光催化活性,光催化活性是纯TiO2的5倍。氮硫共掺杂使TiO2具有更高的比表面和光生电荷分离效应,从而有利于提高光催化活性。     

具有高光催化活性的黑色TiO2（B）/锐钛矿双晶TiO2-x纳米纤维

高效TiO2基光催化材料的开发一直是催化领域的研究热点,主要的策略是如何有效地分离光生载流子.制备多晶相的TiO2材料可引入异质/相结结构使电子与空穴朝不同方向移动,从而避免电子与空穴复合;另外,在TiO2中掺杂其他金属或非金属也可以有效地降低电子与空穴的复合率,掺杂的元素作为电子捕获阱俘获光生电子,以实现电子空穴的有效分离.近些年,作为一种全新的掺杂剂,氧空穴可以有效改善TiO2的光催化活性,所制TiO2具有可见光的全光谱吸收能力,因此该类TiO2呈现出黑色.通过上述方法均可以制备出高活性TiO2基光催化材料,如果能够将这些方法耦合一起,则可能制备出活性更高的光催化剂.因此,本文将异相结结构和空穴掺杂耦合起来,用多孔钛酸盐衍生物在H2中高温焙烧制得一种全新的黑色TiO2(B)/锐钛矿双晶TiO2–x纳米纤维.不同于其他TiO2基光催化材料,该样品仅由Ti和O元素组成,通过Ti和O元素的组合,形成了双晶结构和空穴掺杂两种特殊的结构,借助场发射(FESEM)、拉曼光谱(Raman)、氮气物理吸脱附、X射线光电子能谱(XPS)、热重(TG)、紫外可见漫反射光谱(UV-Vis)和荧光光谱(PL)等表征分析了样品的结构及其光催化性能间构效关系. FESEM结果显示,黑色TiO2(B)/锐钛矿双晶TiO2–x为长1–5mm、宽0.2mm的纤维结构, Raman结果表明,锐钛矿相在特征波段(140 cm–1左右)和TiO2(B)的特征波段(220–260 cm–1)均发生蓝移,说明该两相中均存在氧空穴;该样表面未检测到Ti3+,因此氧空穴可能分散在TiO2(B)和锐钛矿相的体相中.根据黑色TiO2(B)/锐钛矿双晶TiO2–x和白色TiO2(B)/锐钛矿双晶TiO2的失重差,估算出前者的O/Ti原子比为1.97.光催化降解甲基橙实验结果显示,黑色TiO2(B)/锐钛矿双晶TiO2–x的光催化活性是白色双晶TiO2的4.2倍,锐钛矿TiO2的10.5倍,且连续反应10次后未出现失活现象,显示出了良好的光催化稳定性.前期,我们已经证明了白色TiO2(B)/锐钛矿双晶TiO2由于具有TiO2(B)和锐钛矿的异相结结构,致使其电子空穴有效地分离,从而表现出优异的光催化活性;本文的PL结果显示,由于氧空穴的引入,异相结与氧空穴两者共同作用,进一步促进了黑色TiO2(B)/锐钛矿双晶TiO2–x电子与空穴的有效分离,因此黑色TiO2(B)/锐钛矿双晶TiO2–x表现出高的光催化活性.由于其特殊的结构,黑色TiO2(B)/锐钛矿双晶TiO2–x纳米纤维将在环境与能源领域表现出良好的应用前景.     

自支撑黑色TiO_2圆球的制备及其光催化性能的研究

为探索自支撑黑色Ti O2在可见光下降解有机污染物的催化性能,以粒径为385 nm的单分散白色Ti O2圆球为前驱体,再经H2氛500℃处理得到形貌尺寸未有明显改变的黑色Ti O2圆球。XRD和Raman结果表明黑色和白色Ti O2圆球的晶型为锐钛矿相;与白色Ti O2圆球相比,黑色Ti O2圆球的比表面积增大但是其带隙宽度降低为2.72 e V;黑色、白色Ti O2圆球和P25在可见光照下催化降解MB结果表明,黑色Ti O2圆球具有较好的催化活性,循环使用10次后,其催化活性没有明显衰减。     

负载型混晶纳米TiO_2/硅藻土复合材料的制备及其光催化性能

选用市售硅藻土作为载体,采用液相沉积法制备了负载型混晶纳米TiO2/硅藻土复合材料;采用扫描电镜、X射线衍射仪及红外光谱仪分析了复合材料的表面形貌和晶体结构;基于甲醛光催化降解实验考察了不同组成的负载型TiO2/硅藻土复合材料的光催化性能.结果表明,TiO2负载量为33.3%(TiO2与硅藻土的质量比为1∶2)的复合材料对甲醛光催化降解具有最佳催化活性.     

Characterization and photocatalytic properties of silver and silver chloride doped TiO2 hollow nanoparticles

Using polystyrene（PSt） particles as template,PSt/TiO₂ composite particles with AgCl incorporation were prepared through hydrolysis of tetrabutyl titanate in the presence of AgNO₃ and NaCl.AgCl doped TiO₂ hollow particles were successfully prepared with the PSt/TiO₂ composite microspheres pretreated at 180℃followed by calcination.The morphology of PSt/TiO₂ particles and the crystal structures of the AgCl doped TiO₂ hollow particles were characterized.The photocatalytic activity of the doped TiO₂ hollow particles in degradation of Rhodamine B was tested under UV and visible lights and compared to that with Ag doped TiO₂ particles.The results showed that TiO₂ hollow particles,either doped with Ag or AgCl,demonstrated higher photocatalytic activity than the pure TiO₂ particles.This enhancement in photocatalytic activity was more significant with AgCl doped TiO₂ than that with Ag doped,and more distinct when the degradation was done under visible light than that under LTV light.     

Enhanced photocatalytic activity of cobalt-doped CeO2 nanorods

In this paper, CeO₂ and cobalt-doped CeO₂ nanorods synthesized by surfactant free co-precipitation method. The microstructures of the synthesized products were characterized by XRD, FESEM and TEM. The structural properties of the grown nanorods have been investigated using electron diffraction and X-ray diffraction. High resolution transmission electron microscopy studies show the polycrystalline nature of the Co-doped cerium oxide nanorods with a length of about 300?nm and a diameter of about 10?nm were produced. The X-ray Photoelectron spectrum confirms the presence of cobalt in cerium oxide nanorods. From BET, the specific surface area of the CeO₂ (Co-doped) nanostructures (131 m²?g^??) is found to be significantly higher than that of pure CeO₂ (52 m²?g^??). The Co-doped cerium nanorods exhibit an excellent photocatalytic performance in rapidly degrading azodyes acid orange 7 (AO7) in aqueous solution under UV illumination.     

具有SPR效应的Ag/Ag2MoO4材料在可见光区的光催化性能研究

作为一类新兴的光催化材料,钼酸盐纳米材料具有高表面能、多活性位点和高选择性等优点,在可见光催化降解污染物方面有着重要应用,近年来受到广泛关注.作为钼酸盐家族重要的一员,钼酸银在杀菌、表面增强拉曼光谱、气敏材料等方面均有重要应用,但其光催化性能却鲜见报道.这是由于它的光谱响应范围窄和广生载流子分离效率低所致.虽然近来有少量基于钼酸银的复合材料的光催化研究,但催化效果不佳.众所周知,作为自由电子体系,诸多金属纳米粒子,如贵金属、碱金属等,存在表面等离子体共振效应(SPR),使得贵金属,特别是Ag,Au等纳米粒子在可见区域有较强的吸收.利用这一特性,Awazu等将Ag纳米颗粒沉积在TiO2表面,创造性地将SPR应用于光催化反应,开发出在可见光谱区具有宽光谱吸收特征的Ag/TiO2.随后陆续合成出基于SPR效应的Ag@AgCl,Ag/Ag3PO4材料均具有良好的光催化性能.基于此,本文在十二烷基硫酸钠(SDS)的存在下,采用水热法一步合成了具有SPR效应的Ag/Ag2MoO4可见光催化材料,并利用X射线粉末衍射(XRD)、紫外可见漫反射(DRS)、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)等技术对材料进行了表征.系统地探讨了体系pH值、反应时间、表面活性剂用量对产物的晶相和微观形貌等的影响.此外,还利用罗丹明B降解实验考察了上述合成条件对材料可见光催化活性的影响,并通过捕获剂实验深入地研究了起催化作用的活性物种.XRD结果表明,体系的pH值对材料的晶型有极大影响,随着pH由酸性变至中性、碱性,最终得到的钼酸银也由Ag2Mo2O7过渡到Ag2MoO4.SEM图显示在最优条件(pH为7,加入0.5 g SDS,160oC下水热14 h)下制得的钼酸银为八面体的Ag2MoO4,且其表面均匀地分布着Ag纳米颗粒,与XPS图谱结果一致.另外表面活性剂SDS的用量对所合成材料的形貌影响很大.本文可一步得到以八面体Ag2MoO4为主的Ag/Ag2MoO4复合材料,是因为SDS的疏水长链可以诱导Ag2MoO4的各向异性生长.DRS结果表明,Ag2MoO4八面体上Ag颗粒的引入使其在可见光区的吸收明显加强,因而它在可见光下催化降解罗丹明B降解反应活性增加.捕获剂实验结果表明,起决定性作用的活性物种是光生空穴,另外?OH也起了一定作用.     

Preparation of Ag deposited TiO2 (Ag/TiO2) composites and investigation on visible-light photocatalytic degradation activity in magnetic field

In this study, Ag deposited TiO₂ (Ag/TiO₂) composites were prepared by three different methods (Ultraviolet Irradiation Deposition (UID), Vitamin C Reduction (VCR) and Sodium Borohydride Reduction (SBR)) for the visible-light photocatalytic degradation of organic dyes in magnetic field. And then the prepared Ag deposited TiO₂ (Ag/TiO₂) composites were characterized physically by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The visible-light photocatalytic activities of these three kinds of Ag deposited TiO₂ (Ag/TiO₂) composites were examined and compared through the degradation of several organic dyes under visible-light irradiation in magnetic field. In addition, some influence factors such as visible-light irradiation time, organic dye concentration, revolution speed, magnetic field intensity and organic dye kind on the visible-light photocatalytic activity of Ag deposited TiO₂ (Ag/TiO₂) composite were reviewed. The research results showed that the presence of magnetic field significantly enhanced the visible-light photocatalytic activity of Ag deposited TiO₂ (Ag/TiO₂) composites and then contributed to the degradation of organic dyes.     

Near monodisperse TiO2 nanoparticles and nanorods

Highly crystalline, near monodisperse TiO2 nanoparticles, nanorods and their metal-ion-doped (Sn4+, Fe3+, Co2+, and Ni2+, etc.) derivatives have been prepared by well-controlled solvothermal reactions. Through adjusting the reaction parameters, such as reaction temperature, duration, and concentration of the reactants, the size, shape, and dispersibility of the products can be controlled. A possible reaction mechanism can be proposed based on experimental evidence.     

Effects of simultaneously doped and deposited Ag on the photocatalytic activity and surface states of TiO2

Ag-TiO2 catalysts with different Ag contents were prepared via a sol-gel method in the absence of light. Based on the characterizations of XRD, photoluminescence (PL), surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), and XPS as well as the evaluation of the photocatalytic activity for degrading rhodamine B(RhB) solutions, it was found that the Ag dopant promoted the phase transformation as well as had an inhibition effect on the growth of anatase crystallite. The PL and SPS intensities were decreased with increasing Ag content, indicating that the Ag dopant could effectively inhibit the recombination of the photoinduced electrons and holes. However, the active sites capturing the photoinduced electrons reduced, while the Ag content exceeded 5 mol %. At rather low Ag dopant concentrations, the migration and diffusion of Ag+ ions were predominant, while at rather high Ag dopant concentrations, the migration, diffusion, and reduction of Ag ions simultaneously occurred. The Ag-TiO2 photocatalysts with appropriate content of Ag (Ag species concentration is from about 3 to 5 mol %) possessed abundant electron traps so as to be favorable for the separation of the photoinduced electron-hole pairs, which could greatly enhance the activity of the photocatalysts. From the results of FISPS measurements, it could be found that the impurity bands and abundant surface states were introduced into the interfacial layer of TiO2 because of Ag simultaneously doping and depositing, which could improve the absorption capability for visible light of the photocatalysts.     

Improved photocatalytic performance of anatase TiO2 synthesized through ethanol supercritical drying technique

Anatase titania (TiO₂) nanoparticles were synthesized via a self‐developed ethanol vapor‐thermal method at 240°C (T240) and 250°C (T250), i.e. at temperatures lower and higher, respectively, than the supercritical temperature (243.5°C, 7.0 MPa) of ethanol. Compared to T240, T250 exhibited a higher ratio of exposed (001) facets, oxygen vacancies, and concomitant TiO_x. The specific surface area of T250 was 119.0 m² g^?1, smaller than that of T240 (144.2 m² g^?1). During the degradation of methylene blue, T250 exhibited a high apparent rate constant (K_app) of 14.5 × 10^?2 min^?1, which was 6.3 times larger than that for T240. Furthermore, compared to T240, T250 exhibited better performance toward degradation of phenol. Results of electron spin resonance spectroscopy and photoluminescence indicated that the photogenerated electron–hole pairs possessed higher separation efficiency for T250 than for T240. In summary, the excellent photocatalytic performance of T250 originates from the higher ratios of exposed (001) facets, oxygen vacancies or TiO_x, C═O groups adsorbed at the surface of particles, and higher separation efficiency of photogenerated electron–hole pairs. By employing this self‐developed vapor‐thermal method, a variety of catalysts and their composites can be synthesized, which may exhibit novel morphological characteristics and properties as well as excellent photocatalytic performance.     

S掺杂的还原态TiO2-x的制备及其可见光催化性能

作为一种稳定、价廉的光催化剂,TiO2被广泛应用于各种污染物的降解;但是,较大的宽禁带(~3.2 eV)和较低的电子迁移率不仅使TiO2很难吸收可见光,而且光生电子和空穴的复合几率高,从而导致TiO2的总体光电效率不高.因此,设计能够被可见光激发、并具有快速光生电子传输的TiO2一直是研究热点.研究表明,Ti3+自掺杂的TiO2(还原态TiO2-x)不仅能够被可见光激发,而且使TiO2具有良好的电子导电性,从而有利于提高TiO2的光电转换效率.另外,非金属元素的掺杂能够减小TiO2的禁带宽度,使TiO2能够响应可见光并具有良好的可见光催化性能,其中S元素的掺杂被广泛研究.目前,S掺杂纳米TiO2的制备通常采用TiS2,单质S,硫脲、二甲亚砜等为S源,但这类原料通常价格昂贵或者具有一定的毒性,因而实际应用受到限制.而制备Ti3+自掺杂TiO2的方法大都是基于"还原法",在真空或强还原性气氛如H2,CO中加热TiO2,或采用高能粒子(电子、氩离子)轰击.在实际应用中,这些方法存在步骤多、条件苛刻、反应时间长和设备昂贵等不足.而且,还原法反应通常发生在颗粒的表面,形成的Ti3+很容易被空气和水中的溶解O2氧化,降低材料的稳定性.虽然在温和的液相中还原Ti4+可用于制备Ti3+掺杂的TiO2,但是由于反应过程中有副产物生成,需要进行后续处理才能得到纯的Ti3+自掺杂TiO2.因此,设计一种简单的制备S掺杂还原态TiO2-x光催化剂仍具有十分重要的意义.前期我们采用H2O2氧化TiH2得到不同状态的前驱体凝胶,然后进行不同方式的后处理得到Ti3+自掺杂的纳米TiO2.本文以TiH2和H2O2反应得到的黄色前驱体凝胶为Ti源,以价格低廉、无毒、稳定的二氧化硫脲为S源和还原剂,采用不同的方法制备了S掺杂的还原态TiO2-x光催化剂.本文初步研究了在凝胶中加入二氧化硫脲后进行水热处理,以及将干燥的凝胶粉末与二氧化硫脲混合热处理对所得产物的影响.并与纯的TiO2、还原态TiO2-x和S掺杂TiO2的光吸收、电化学、光催化性能进行对比研究.采用X射线衍射、透射电子显微镜、高分辨透射电子显微镜、X-射线光电子能谱、紫外-可见漫反射光谱、比表面分析和电化学工作站等技术对产物的结构、形貌和光电性能进行了表征.以罗丹明B(RhB)溶液为模拟废水,考察样品的可见光催化性能.结果表明,不同的后续处理方式不仅影响S掺杂TiO2-x的结晶性和形貌,而且影响产物的光吸收性能和电子传输性能,从而使不同条件下所得产物的可见光催化性能不同.其中,采用热处理方式得到的S掺杂TiO2-x样品在可见光下降解RhB的速率分别是纯的TiO2,TiO2-x和S掺杂TiO2的31,2.5和3.6倍,而且样品具有良好的循环稳定性.     

Synthesis of sponge-like TiO2 with surface-phase junctions for enhanced visible-light photocatalytic performance

Maximizing adsorption and catalytic active sites and promoting the photo-excited charge separation are two key factors to achieve excellent photocatalytic performance. In this study, we report a sol-gel synthesis approach to obtain non-metal doped TiO₂ with sponge-like structure and surface-phase junctions all at once. While doping of carbon and nitrogen shifted the activation wavelength to the visible-light region, the innovative use of perchloric acid as a pore-making agent led to the formation of three-dimensional lamellar and porous structure with surface-phase junctions. High surface area with catalytic active sites rendered by the sponge-like structure and surface-phase junctions contributed to the much improved photocatalytic degradation efficiency toward rhodamine B, tetracycline and Disperse Red 60 with excellent reusability and stability. The improved generation and separation efficiency of the photo-induced charge carriers of the as-prepared TiO₂ were supported by electrochemical impedance measurements and transient photocurrent responses. This method could also be applied to other photocatalysts to achieve structural alteration and element doping simultaneously.     

Facilely anchoring Cu2O nanoparticles on mesoporous TiO2 nanorods for enhanced photocatalytic CO2 reduction through efficient charge transfer

Semiconductor-employed photocatalytic CO₂ reduction has been regarded as a promising approach for environmental-friendly conversion of CO₂ into solar fuels. Herein, TiO₂/Cu₂O composite nanorods have been successfully fabricated by a facile chemical reduction method and applied for photocatalytic CO₂ reduction. The composition and structure characterization indicates that the Cu₂O nanoparticles are coupled with TiO₂ nanorods with an intimate contact. Under light illumination, all the TiO₂/Cu₂O composite nanorods enhance the photocatalytic CO₂ reduction. In particular, the TiO₂/Cu₂O-15% sample exhibits the highest CH₄ yield (1.35 µmol g^-1 h^-1) within 4 h irradiation, and it is 3.07 and 15 times higher than that of pristine TiO₂ nanorods and Cu₂O nanoparticles, respectively. The enhanced photoreduction capability of the TiO₂/Cu₂O-15% is attributed to the intimate construction of Cu₂O nanoparticles on TiO₂ nanorods with formed p-n junction to accelerate the separation of photogenerated electron-hole pairs. This work provides a reference for rational design of a p-n heterojunction photocatalyst for CO₂ photoreduction.