Gd,B共掺杂改性TiO_2纳米颗粒的可见光光催化活性

采用溶胶-凝胶法制备了Gd和B共掺杂的TiO2纳米颗粒,研究了TiO2纳米颗粒在可见光下的光催化活性。应用XRD、TEM和UV-Vis等手段对TiO2纳米颗粒的物相、粒径、形貌及光学性能进行了表征。结果表明,掺杂可以抑制TiO2晶粒增长,阻碍TiO2由锐钛矿相向金红石相的转变。紫外-可见吸收光谱显示,共掺杂纳米颗粒在可见光区吸收有较强提高,共掺杂离子以协同作用拓展TiO2光谱响应,使吸收带产生红移,提高光生载流子的分离效率。光催化降解实验表明,共掺杂TiO2纳米颗粒有很高的可见光光催化活性,以500℃热处理的共掺杂摩尔比为0.005 Gd和0.04 B的TiO2纳米颗粒光催化效果最好,在可见光下对甲基橙的降解率为98.9%。     

XPS研究共掺杂TiO2可见光光催化活性

利用X-射线光电子能谱(XPS)分析掺杂元素对二氧化钛中O1s和Ti2p的结合能峰的变化。从实验数据求出△(O-Ti)值,分析变化的原因。数据显示:共掺杂后△(O-Ti)的值的变化范围为71.2～71.5 eV之间,掺杂后△(O-Ti)值大于纯TiO2。可见光光催化氧化4-氯苯酚结果表明:随着△(O-Ti)值的增大,可见光光催化活性逐步提高。     

可见光响应Pt掺杂纳米TiO2的光催化氧化NOx性能

采用溶胶-凝胶法制备不同Pt掺杂比例的Pt-TiO2光催化剂。通过XRD、XPS、UV-vis表征光催化剂结构,在紫外光及可见光下考察其对NOx的光催化氧化活性。结果表明,所制备的Pt-TiO2均为锐钛矿相,对NOx有明显的可见光降解效果,并且以Pt/Ti比为0.4%时,其光催化活性最高。与P25及TiO2相比,Pt-TiO2在紫外光及可见光下的光催化活性均有较大提高,其NO转化率明显提高,NO2选择性生成率明显降低,归因于Pt的掺杂引入了杂质能级并促进了催化剂的光生电子-空穴对的分离。     

日光灯光响应混晶纳米TiO2的制备及光催化性能

采用溶胶-凝胶法,制备了Ce、Fe和Co共掺杂的混晶纳米TiO2粉末并进行了XRD表征。以普通日光灯为光源,考察了掺杂量、焙烧温度及焙烧时间、催化剂加入量对其光催化降解亚甲基蓝性能的影响。结果表明:掺杂样品中金红石相的含量大幅提高,光催化活性也优于纯TiO2。其中,组成为Ce0.0625Fe0.025Co0.002/TiO2的样品在500℃焙烧2h效果最佳。该催化剂加入量为0.4 g/L时,亚甲基蓝2h的降解率可达95.6%。     

V、La共掺杂纳米TiO2光催化活性研究

采用溶胶-凝胶法制备了不掺、单掺和共掺杂的TiO2纳米粒子,对样品进行了XRD、TEM和BET分析,并以甲基橙的光催化降解研究了样品的光催化性能.结果发现V的掺杂对TiO2晶型的转变和晶粒尺寸的长大具有促进作用;而La的掺杂对TiO2晶型的转变和晶粒尺寸的长大具有抑制作用;当两者共掺杂时,促进作用和抑制作用相互中和,且La的抑制作用占优势.V、La的单掺杂提高了TiO2的光催化活性,共掺杂又进一步提高了TiO2的光催化活性;最佳掺杂量为0.05%的V和0.05%的La,最佳煅烧温度为600 ℃.     

Ce-Zn共掺杂改性TiO2纳米管阵列的制备及其光催化性能

采用阳极氧化法在钛网上制得TiO₂纳米管阵列(TNTA),并利用操作简单的微溶剂燃烧合成法将稀土元素Ce和过渡金属元素Zn共掺杂修饰TiO₂纳米管阵列得到复合光催化材料Ce-Zn/TiO₂纳米管阵列(CeZn/TNTA),并对CeZn/TNTA的形貌、组成结构和光催化性能等进行测试。结果表明:阳极氧化时间会影响TNTA的形貌,氧化时间为2 h的TNTA管状结构分布均匀且高度有序,纳米管内径约为50 nm,管壁厚约为25 nm,管长约为1μm。CeZn/TNTA样品中的Ce以CeO₂和Ce₂O₃混合态、Zn以ZnO形式呈簇状不均匀分布在TiO₂纳米管阵列表面。与裸TNTA相比,CeZn/TNTA复合催化剂的光响应范围拓宽至可见光区域,电荷转移阻力减小,光生电子-空穴的分离效率提高,载流子的传输速率较快,且表现出较高的光催化活性,其在1 h内对亚甲基蓝光催化降解率可达85.27%。     

钐掺杂TiO2纳米管阵列的光催化性能研究

以工业级纯钛箔为模板,硝酸钐为钐物种掺杂给体,采用阳极氧化法制备钐掺杂的TiO2光催化剂,用SEM、XRD对制备的样品进行表征,以甲基橙为模拟污染物,考察了钐掺杂的TiO2光催化剂的光催化活性。结果表明:制备的光催化剂为锐钛矿相和少量金红石相的混晶;硝酸钐掺杂浓度为0.001 mol/L,其光催化性能最好,且光催化重复使用性能良好。     

可见光响应铈氮共掺杂二氧化钛及其光催化降解活性

通过溶胶凝胶法制备了具有可将光响应能力的铈、氮共掺杂二氧化钛光催化剂。用XRD、SEM、UV-Vis对催化剂进行了表征,以活性艳红为降解目标,考察了催化剂在500 W氙灯全波段照射下和可见光下的光催化活性。光催化降解活性艳红溶液实验结果表明,当煅烧温度为400℃,铈掺杂量为0.6%(摩尔比),氮掺杂量为6%(摩尔比)时光催化效率最高,活性艳红溶液的降解率可达97.88%。     

氮掺杂纳米TiO2光催化性能的研究

以钛酸丁酯和硝酸氮为主要原料,采用溶胶-凝胶法制备不同掺氮比的纳米TiO2(纳米N-TiO2)光催化剂。研究了不同的氮钛比、焙烧温度对氮掺杂纳米TiO2降解甲基橙溶液催化效果的影响。利用XRD、SEM方法对氮掺杂纳米TiO2的晶体结构及微观形貌进行了表征。结果表明:通过氮掺杂纳米TiO2,抑制了纳米TiO2晶粒的生长和晶型的转变,同时提高了TiO2的光催化活性。在紫外线灯的照射下,煅烧温度为500℃,N/Ti的原料配比为0.5%,制备的催化剂可达到最大的降解效果(为92.49%)。     

纳米TiO2光催化剂共掺杂的研究进展

从金属、稀土、非金属之间的共掺杂,介绍了近几年TiO2光催化剂与双金属、双稀土、双非金属、金属与稀土、金属与非金属、稀土与非金属共掺杂的研究进展。对TiO2进行双元素的共掺杂,当掺入的两种元素选择适当,且掺入的浓度和配比合适时,两种元素分别起不同的作用,进一步提高了TiO2的光催化性能。对该领域今后的研究方向提出了建议。     

水基纳米TiO_2路径制备有序介孔TiO_2-SiO_2及其可见光催化性能

在多巴胺修饰的水基TiO_2纳米微粒(TiO_2NPs)悬浮液中,以正硅酸乙酯为硅源,十六烷基三甲基溴化铵为模板剂,分别采用碱性水热方法或酸性溶胶-凝胶方法,制备了有序介孔TiO_2-SiO_2(TiO_2NPs/MCM-41或TiO_2NPs/SBA-3)。采用XRD、TEM、ICP和N2吸附-脱附实验对样品进行表征。结果表明,制备的介孔TiO_2-SiO_2在TiO_2高负载质量分数(23.98%TiO_2NPs/MCM-41、17.27%TiO_2NPs/SBA-3)时,仍能保持长程有序的介孔氧化硅结构。TiO_2NPs随机地嵌入在有序介孔氧化硅孔道所组成的网络结构中。在可见光下催化甲基橙降解反应中,反应时间120 min时,在P25上甲基橙相对浓度降为57%,在TiO_2NPs/MCM-41上降为33%,而在TiO_2NPs/SBA-3上降为5.7%。     

镍、碳共掺杂纳米二氧化钛薄膜的制备与光催化性能研究

为了增强纳米二氧化钛薄膜在紫外光下光催化降解罗丹明B溶液的能力,分别采用磁控直流溅射与射频溅射的方法,使用二氧化钛靶材、镍靶材、碳靶材,分别制备了碳非金属掺杂、镍金属掺杂以及镍、碳共掺杂的纳米二氧化钛薄膜,并利用扫描电子显微镜（SEM）、X射线衍射仪（XRD）和紫外可见分光光度计（UV-Vis）进行表征。SEM结果表明,与纯二氧化钛薄膜相比镍、碳共掺杂纳米二氧化钛薄膜晶粒细化,比表面积增大,薄膜表面聚集体为不规则的多边形颗粒状,有利于增大与污染物的接触面积;XRD结果表明该薄膜的晶粒减小,加快了光生电子空穴对的分离;薄膜的吸收极限红移,禁带宽度减小。在紫外光照射下,镍、碳共掺杂纳米二氧化钛薄膜的光催化性能最优,1 h降解了29.54%的罗丹明B溶液。     

TiO2光催化降解亚硝酸钠的研究

采用溶胶-凝胶法制备了TiO2光催化剂,以紫外光照射下的光催化降解亚硝酸钠为模型反应,以盐酸萘乙二胺显色法测定样品的吸光度,进而得出亚硝酸钠的转化率,并采用BET、XRD和IR对催化剂进行了表征。结果表明,500℃焙烧的TiO2催化剂比表面积为42.5 m2/g,平均孔径为5.8 nm,热稳定性好。400℃焙烧2 h的TiO2尚存在一定量的无定形相TiO2,500℃焙烧的TiO2完全转变为锐钛矿型TiO2,700℃时完全转化为金红石相。本实验最佳的反应条件为:TiO2(500℃,2 h)催化剂0.2 g,100 mL 0.125μg/mL亚硝酸钠溶液中,紫外光降解150 min,亚硝酸钠的降解率为100%;添加适量浓度的H2O2溶液,可促进亚硝酸钠溶液的转化。     

BiOCl/TiO2复合材料的制备与光催化性能

基于半导体异质结原理,设计并制备了新型氯氧铋/二氧化钛复合光催化材料,以甲基橙为目标污染物,研究了氯氧铋制备条件和复合比例对复合材料的光催化特性的影响,随后利用XRD、UV-Vis DRS、TEM、EPR等方法对催化材料进行表征,从表面形貌、自由基等角度,分析其光催化原理。结果表明,新型复合光催化材料相对氯氧铋、二氧化钛的单体,具有更强的紫外催化能力,对传统有色染料均具有良好的去除效果。这是由于氯氧铋和二氧化钛可以形成半导体异质结,光生电子传递降低了载流子负荷率,羟基自由基生成量增加,因此光催化性能大幅提升。     

Characterization and photocatalytic activity of transition-metal-supported surface bond-conjugated TiO2/SiO2

TM/TiO₂/SiO₂ photocatalysts were prepared by the photodeposition method using transition metal salts (TM=Fe³⁺, Co²⁺, Ni²⁺ and Cu²⁺) as precursors and the surface bond-conjugated TiO₂/SiO₂ as supporter in N₂ atmosphere, and were characterized by XRD, XPS, UV-Vis diffuse reflection and zeta-potential. Their photocatalytic activities were evaluated using reactive brilliant red K-2G (K-2G) and cationic blue X-GRL (CBX) showing different adsorption behavior on the oxides. Fe, Cu supported TiO₂/SiO₂ can efficiently extend the light absorption to the visible region. XPS analysis verified that the introduction of transition metal lead to the changes of the electronic environmental of Ti cations and the zeta-potential of oxides. As a result, K-2G has higher adsorption on the modified TiO₂/SiO₂ than that on the baked one, while the adsorption of CBX has a little change on the both oxides. At the same time, for the photodegradation of K-2G, Fe³⁺, Co²⁺, Ni²⁺-modified catalysts show that their photoactivities are 3.3–2.2 times higher than the bare one. On the contrast, all transition-metal-supported catalysts have no significant activity improvement except that Fe/TiO₂/SiO₂ shows 1.68 times higher activity for the photodegradation of CBX. The results indicate that the photoactivity could be increased in photodegradation of dyes by changing the performances of adsorption to dyes and absorption to light of photocatalyst.     

Plasmonic Au nanoparticles supported on both sides of TiO2 hollow spheres for maximising photocatalytic activity under visible light

A strategy of intensifying the visible light harvesting ability of anatase TiO₂ hollow spheres (HSs) was developed, in which both sides of TiO₂ HSs were utilised for stabilising Au nanoparticles (NPs) through the sacrificial templating method and convex surface-induced confinement. The composite structure of single Au NP yolk-TiO₂ shell-Au NPs, denoted as Au@Au(TiO₂, was rendered and confirmed by the transmission electron microscopy analysis. Au@Au(TiO₂ showed enhanced photocatalytic activity in the degradation of methylene blue and phenol in aqueous phase under visible light surpassing that of other reference materials such as Au(TiO₂ by 77% and Au@P25 by 52%, respectively, in phenol degradation.     

Effects of Sn dopant on the photoinduced charge property and photocatalytic activity of TiO2 nanoparticles

In this paper, Sn-doped TiO₂ nanoparticles were prepared by a sol–gel method, and also were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectrum (IR), ultraviolet–visible diffuse reflection spectrum (UV–vis DRS), photoluminescence spectrum (PL), surface photovoltage spectroscopy (SPS) and electrical field induced surface photovoltage spectroscopy (EFISPS). The sample activity was evaluated by photocatalytic oxidation reactions of phenol solution. The effects of thermal treatment temperature and Sn amount on photoinduced charge property, mainly involving charge separation and bound excitons resulting from surface states, and photocatalytic activity of TiO₂ nanoparticles were principally investigated. The results show that an appropriate calcination temperature and Sn dopant amount can greatly enhance the SPS responses of TiO₂ nanoparticles related not only to the band–band transitions but also to the bound excitons, and obviously weaken the PL signal, while the photocatalytic activity remarkably raises. These demonstrate that the separation rate of photoinduced charges of TiO₂ nanoparticles can be effectively improved by doping Sn, which is responsible for the obvious increase in the photocatalytic activity. Moreover, the existence of bound excitons related to surface states also favor the photocatalytic activity. In addition, it can be found that the SPS responses related to the bound excitons could easily exhibit in the TiO₂ sample consisting of much of anatase and little of rutile, which is possibly ascribed to the heterojunction between the anatase and rutile phase.     

TiO2 deactivation during gas-phase photocatalytic oxidation of ethanol

The deactivation of TiO₂ Degussa P25 during the gas-phase photocatalytic oxidation of ethanol has been studied. Water vapor plays a clear competitive role for surface sites adsorption, thus hampering the ethanol photo-oxidation. Dark adsorption of ethanol on a fresh catalyst shows a Langmuirian behavior with the formation of a monolayer of adsorbate. Dark adsorption in a TiO₂ surface that has been used in consecutive photocatalytic experiments of ethanol degradation gives non-Langmuirian isotherms, indicating the existence of noticeable changes of the catalyst surface structure. After several irradiations the catalyst activity decreases. Such deactivation has been investigated, observing that the rate constant of ethanol and acetaldehyde (its main degradation product) oxidation decreases with irradiation time. Several surface treatments have been studied in order to find suitable procedures for catalytic activity recovery, but regular decay of activity is always observed after every treatment.     

The role of H2O in the photocatalytic oxidation of toluene in vapour phase on anatase TiO2 catalyst: A FTIR study

Photocatalytic oxidation of toluene has been carried out in a gas–solid regime by using polycrystalline anatase TiO₂ in a fixed-bed continuous reactor. Air containing toluene and water vapours in various molar ratios was fed to the photoreactor irradiated by a medium pressure Hg lamp. Toluene was mainly photo-oxidised to benzaldehyde, and small amount of benzene, benzyl alcohol and traces of benzoic acid and phenol were also detected. In the presence of water, no decrease of photoreactivity was observed at steady-state conditions. By removing water vapour from the feed, the conversion of toluene to benzaldehyde was almost completely inhibited, and an irreversible deactivation of the catalyst occurred. FTIR investigations indicated that benzaldehyde is photoproduced on the TiO₂ surface even in the absence of water vapour, but exposure of the catalyst to the UV light in a dry atmosphere results in an irreversible consumption of surface hydroxyl groups. As these species play a key role in the photoreactive process, this dehydroxylation should be the reason of the catalyst deactivation observed in the catalytic runs carried out in the absence of water vapour.