Structure and photocatalytic properties of TiO<Subscript>2</Subscript>-Graphene Oxide intercalated composite

TiO2-Graphene Oxide intercalated composite (TiO2-Graphene Oxide) has been successfully prepared at low temperature (80°C) with graphite oxide (GO) and titanium sulfate (Ti(SO4)2) as initial reactants.GO was firstly exfoliated by NaOH and formed single and multi-layered graphite oxide mixture which can be defined as graphene oxide,[TiO]2+ induced by the hydrolysis of Ti(SO4)2 diffused into graphene oxide interlayer by electrostatic attraction.The nucleation and growth of TiO2 crystallites took place at low temperature and TiO2-Graphene Oxide composite was successfully synthesized.Furthermore,the photocatalytic properties of TiO2-Graphene Oxide under the irradiation of UV light were also studied.The results show that the degradation rate of methyl orange is 1.16 mg min-1 g-1(refer to the efficiency of the initial 15 min).Compared with P25 powder,this kind of intercalation composite owns much better efficiency.On the other hand,the reusable properties and stable properties of TiO2-Graphene Oxide intercalated composite are also discussed in this paper.At last,crystalline structure,interface status,thermal properties and microscopic structure of TiO2-Graphene Oxide were characterized by X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS),thermogravimetric analysis (TGA),field emission scanning electron microscopy (FESEM) and high-resolution Transmission Electron Microscopy (HRTEM).Also,we have analyzed major influencing factors and mechanism of the composite structures which evidently improve the photocatalytic properties.     

石墨烯基TiO_2复合材料的表征及其可见光催化活性研究

以氧化石墨烯与石墨烯为碳源,在熔盐介质中与钛粉反应原位生成石墨烯基TiC中间产物,并通过后续控制氧化制得石墨烯基TiO_2复合光催化剂,结合FTIR、XRD、Raman、SEM等手段,对两种石墨烯材料的结构及形貌差异进行表征,并分析了其对所制复合材料结构、形貌及可见光催化活性的影响。结果表明,所制复合材料仍保持碳源的层片状结构,TiC和TiO_2颗粒均匀包覆在碳源表面;以石墨烯为碳源更有利于表面原位生成TiC晶粒的生长,其晶体结构更为完善;两种结构的石墨烯基TiO_2复合材料均对目标污染物亚甲基蓝有较强的吸附能力和可见光降解能力。     

Preparation, characterization and photodegradation of methylene blue based on TiO2 microparticles modified with thiophene substituents

The new microparticles,2-formylthiophene(FT)/TiO2 and(E)-1,2-bis(5-formyl-2-thienyl) ethylene(EBFTE)/TiO2 were synthesized with a silane coupling agent.The prepared TiO2 composites were characterized using Ultraviolet-Vis absorption(UV-Vis),X-ray diffraction(XRD),scanning electron microscope(SEM) and thermogravimetric analyzer(TGA).Methylene blue was used as a model material to examine the photocatalytic activities of the prepared catalysts under both Ultraviolet-Vis(UV) and visible(Vis) light.The enhanced photocatalytic activities were observed in the presence of(FT)/TiO2 and EBFTE/TiO2 under Vis light.It suggests that FT or EBFTE plays a block or active role in the photodegradation mechanisms under UV and Vis light irradiation,respectively.     

水热体系下二氧化钛与氧化石墨烯复合纳米晶的合成

 200 ℃下四方结构的二氧化钛(TiO2)与氧化石墨烯(GO)复合纳米晶在一个装有适量钛酸四丁酯、无水乙醇、氧化石墨烯和蒸馏水的密闭的水热釜中加热12 h后被制备。X射线粉末衍射仪（XRD)、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等一系列分析仪器被运用来揭示二氧化钛与氧化石墨烯复合纳米晶是由粒径大约160 nm的四方结构的二氧化钛纳米晶与氧化石墨烯复合而成,通过紫外吸收对其光学性能进行了必要的测试。
     

银掺杂多孔氧化钛光催化甲基橙降解反应条件的探究

利用溶胶-凝胶法结合光还原法制备Ag掺杂多孔TiO_2光催化剂,以甲基橙的降解效果为评价标准,考查了光照降解时间、光催化剂用量、甲基橙溶液初始浓度、溶液pH值对光催化剂催化降解甲基橙的影响。结果表明,本方法制备的光催化剂无论是在紫外光还是可见光下均具有优良的光催化性能:在浓度为10 mg/L的甲基橙溶液中,4 g/L光催化剂,紫外光照射80 min,甲基橙可实现100%完全降解;相同催化条件下,可见光照100 min,甲基橙完全降解;当反应溶液pH=2时,紫外光和可见光都可在20 min内实现甲基橙的完全降解。     

CdS修饰低密度TiO2纳米棒阵列复合膜的制备及光电性能

为了提高CdS光敏层在TiO₂一维纳米棒阵列中的填充率,在TiO₂种子层的基础上,采用水热法于FTO导电玻璃表面生长了棒长较短、棒间距较大的低密度TiO₂一维纳米棒阵列膜,通过化学浴沉积在TiO₂纳米棒表面包覆CdS种子层,以此为基底采用水热法于TiO₂一维纳米阵列中生长CdS光敏层。采用SEM,XRD及紫外-可见吸收光谱对不同CdS水热生长时间的TiO₂/CdS复合膜结构进行了表征,并对其光电性能进行了研究。结果表明,低密度TiO₂纳米棒阵列有利于CdS生长液在阵列中渗入形成完全包覆的CdS种子层,CdS光敏层通过水热过程在整个TiO₂纳米棒表面均匀生长,逐渐形成CdS对TiO₂纳米棒阵列的完全填充和包覆,并在阵列顶端形成由CdS纳米短棒组成的花状修饰层;CdS的修饰将TiO₂一维纳米阵列膜的光吸收拓展至可见光区,水热生长7 h所得到的TiO₂/CdS复合膜具有最高光电流。所制备的CdS修饰低密度TiO₂纳米棒复合膜在太阳电池器件中具有很好的应用前景。     

Photocatalytic Oxidation of NOx with Porous TiO2 Nanometer Thin Film

A new kind of porous nano-TiO2 composite films was prepared on the glass substrate with the water glass as hinders and the sodium fluorosilicate as solidifying reagent. The morphologies of the films were studied by scanning electron microscope(SEM). The UV-Vis spectrophotometer was also used to investigate the absorption of the films. The gasphase photocatalytic oxidation of nitrogen oxides on the composite film was carried out in TiO2 UV system, and some important factors affecting the photocatalytic oxidation were also studied such as the catalyst concentration, vapor pressure and the presence of oxygen. The results showed the conversion of NOx reached 97.5% after 2 h UV-irradiation. The final product of photo-oxidation was detected to be HNO3 hy FT-IR. The way of photocatalytic oxidation of NOx was possibly useful in the practical application.     

二氧化钛-硫化镉/还原氧化石墨烯复合材料光催化降解废水中有机物的研究

采用溶剂热法制备出二氧化钛-硫化镉/还原氧化石墨烯(TiO_2-CdS/rGO)三元复合光催化材料,研究其对亚甲基蓝、罗丹明B的光催化降解效果.结果表明,TiO_2-CdS/rGO对亚甲基蓝、罗丹明B的光催化降解效果优于TiO_2-CdS的,催化效率得到明显提高,降解时间大大缩短.在可见光照射下,以TiO_2-CdS/rGO为光催化剂,当光反应时间为40min时,亚甲基蓝、罗丹明B的降解率可达100%.     

二氧化钛-硫化镉/氧化石墨烯复合材料光催化降解废水中有机物的研究

本论文采用溶剂热法制备出TiO₂-CdS/rGO三元复合光催化材料,并对其降解亚甲基蓝、罗丹明B的光催化活性进行研究,发现TiO₂-CdS/rGO对于亚甲基蓝、罗丹明B的光催化降解活性优于TiO₂-CdS,催化效率明显提高,降解时间大大缩短;在可见光照射下,以TiO₂-CdS/rGO为光催化剂,光反应时间40 min,亚甲基蓝、罗丹明B的降解率可达100%。本文还研究了催化材料的稳定性、催化剂用量对光催化降解效果的影响。     

不同酸介质对TiO2光催化还原Cr(Ⅵ)体系的影响

 研究了不同酸介质对TiO₂光催化还原低浓度Cr(Ⅵ)体系的影响,发现在110 W紫外灯3、h照射条件下Cr(Ⅵ)质量浓度低于20μg/mL时受空白影响大.通过在无TiO₂光催化剂的空白实验,表明在HCl介质中不用考虑空白带来的影响,而H₂SO₄,HNO₃,CH₃COOH均有不可忽略的影响.     

A novel TiO2 with a large amount of bulk intrinsic defects-Visible-light-responded photocatalytic activity induced by foreign trap

A novel TiO2 (anatase) containing a large amount of single electron trapped oxygen vacancies (SETOV) was prepared by dehydration of titanic acid nanotubes. This novel TiO2 contains high concentration intrinsic defects in bulk structure, while its surface still remains the stoichiometric structure to protect them. And this novel TiO2 itself has the visible light absorption without any doping, so we call it as the third generation of TiO2 . However, it is regretted that this novel TiO2 (A) only has photocatalytic activity under UV light irradiation, and was inactive for the visible light. The true reasons for this phenomenon were investigated by the transient IR absorption and photoluminescence spectra. Through constructing the foreign electron traps (PdO, PtO2 ), the photocatalytic oxidation of propylene under visible light irradiation was successfully achieved. The removal yield of propylene (C3H6 ) reached 7.6% and 28% on 2 wt.% PtO2 /novel TiO2 and 2 wt.% PdO/novel TiO2 , respectively. By comparison with the noble metal electron traps (Pt, Pd), we found that the effective foreign electron traps need to satisfy two conditions: (1) its work function should situate in the range of Eg(TiO2 ); (2) O2 adsorbes on it undissociatively. This work opens up a new route for the investiga- tion of solar-energy-available TiO2 .     

Cu2O/(rGO-TiO2)复合薄膜的制备及其光催化产氢性能

在氧化亚铜（Cu_2O）和二氧化钛（TiO_2）的复合材料中,引入石墨烯（rGO）,制备出新型的Cu_2O/(rGO-TiO_2)光催化薄膜. 首先通过电化学沉积法在铜片上制备Cu_2O;然后通过水热法在TiO_2悬浊液中,将氧化石墨烯（GO）还原为rGO,并制备出rGO-TiO_2复合光催化颗粒;最后将rGO-TiO_2涂覆在Cu_2O表面制备出Cu_2O/(rGO-TiO_2)光催化剂. 催化剂的形貌和表面特征采用扫描电镜（SEM）、透射电镜（TEM）进行表征,材料晶体结构采用X射线衍射（XRD）和拉曼光谱（Raman）分析,其光学特性采用紫外-可见漫反射分光光度计（UV-Vis DRS）、荧光分光光度计（PL）进行表征. 结果表明:与Cu_2O-TiO_2比较,Cu_2O/(rGO-TiO_2)薄膜表现出很强的光催化产氢性能,其中负载rGO质量分数为1.0%的样品Cu_2O/(1.0% rGO-TiO_2)薄膜在300 W氙灯的照射下,对体积分数为20%的甲醇溶液进行光催化反应,其产氢速率（326 mmolh-1m-2）是Cu_2O-TiO_2薄膜产氢速率的3.5倍. 此外,分别探讨牺牲剂类型和pH对Cu_2O/(rGO-TiO_2)光催化薄膜的光催化产氢活性的影响. 结果表明:在体积分数为20%的甲醇水溶液（中性）中,该催化剂的产氢性能最佳.     

TiO2/SiO2/GQDs双层增透膜的制备及其在太阳能板中的应用

采用溶胶-凝胶法制备了SiO₂ 和TiO₂ 纳米溶胶,采用水热法制备了石墨烯量子点（graphene quantum dots,GQDs）。为进一步提高光伏太阳能板的透光率,设计了一种TiO₂/SiO₂/GQDs双层增透膜结构。探究了薄膜的结构、自清洁性能和增透性能,并进一步讨论了GQDs在增透性中的作用。结果表明,SiO₂-TiO₂/TiO₂-GQDs结构的双层薄膜厚度为120 nm时,太阳能板上的光透过率由未涂敷的85%增加至95%。接触角实验和室外耐环境性能实验测试表明,复合膜层接触角为10°,并具有良好的亲水性和耐环境性能。此外,户外实验结果表明,涂覆该薄膜的太阳能电板发电效率提高6%。由此说明双层增透膜可有效地提高太阳能电池板的光能利用率和使用寿命,可高效地利用太阳能。     

Photocatalytic activity of ferric oxide/titanium dioxide nanocomposite films on stainless steel fabricated by anodization and ion implantation

A simple surface treatment was used to develop photocatalytic activity for stainless steel. AISI 304 stainless steel specimens after anodization were implanted by Ti ions at an extracting voltage of 50 kV with an implantation dose of 3 × 1015 atoms·cm?2 and then annealed in air at 450℃ for 2 h. The morphology was observed by scanning electron microscopy. The microstructure was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The photocatalytic degradation of methylene blue solution was carried out under ultraviolet light. The corrosion resistance of the stainless steel was evaluated in NaCl solution (3.5 wt%) by electrochemical polarization curves. It is found that the Ti ions depth profile resembles a Gaussian distribution in the implanted layer. The nanostructured Fe₂O₃/TiO₂ composite film exhibits a remarkable enhancement in photocatalytic activity referenced to the mechanically polished specimen and anodized specimen. Meanwhile, the annealed Ti-implanted specimen remains good corrosion resistance.     

Synthesis of Cu–TiO2/CuS p-n heterojunction via in situ sulfidation for highly efficient photocatalytic NO removal

Cu doped TiO₂/CuS (Cu–TiO₂/CuS) p-n heterojunction was synthesized via in situ sulfidation method for efficient photocatalytic removal of NO at ppb-level. The results show that optimized Cu–TiO₂/CuS heterojunction possessed a maximum efficiency of 85% for the removal of NO under visible light irradiation, which was approximately 8.5, 4.3 and 1.2 times that of CuS, TiO₂ and Cu–TiO₂, respectively. The improved photocatalytic performance is attributed to the enhancement of visible light absorption and charge carrier separation induced by the construction of p-n heterojunction. Meanwhile, the p-n heterojunction charge transfer mechanism of Cu–TiO₂/CuS was verified by systematic investigations. The appropriate band structures of the two components and the internal electric field formed at the interface of the heterojunction were two factors for this charge transfer mechanism. Furthermore, the role of active species in NO removal was explored, and the corresponding mechanism for NO removal of the heterojunction was proposed. This work provides a promising approach for the synthesis of heterojunction photocatalysts and facilitates the application of photocatalysts in sustainable and efficient pollutant removal.     

Preparation of narrow band gap V2O5/TiO2 composite films by micro-arc oxidation

V₂O₅/TiO₂ composite films were prepared on pure titanium substrates via micro-arc oxidation (MAO) in electrolytes consisting of NaVO₃. Their morphology and elements were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis. Phase composition and valence states of species in the films were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS) were also employed to evaluate the photophysical property of the films. The V₂O₅/TiO₂ composite films show a sheet-like morphology. Not only V₂O₅ phase appears in the films when the NaVO₃ concentration of the electrolyte is higher than 6.10 g/L and is loaded at the surface of anatase, but also V⁴⁺ is incorporated into the crystal lattice of anatase. In comparison with pure TiO₂ films the V₂O₅/TiO₂ composite films exhibit significantly narrow band gap energy. The film prepared in an electrolyte consisting of NaVO₃ with a concentration of 8.54 g/L exhibits the narrowest band gap energy, which is approximately 1.89 eV. The V₂O₅/TiO₂ composite films also have the significantly enhanced visible light photocatalytic activity. The film prepared in an electrolyte consisting of NaVO₃ with a concentration of 8.54 g/L exhibits the best photocatalytic activity and about 93% of rhodamine is degraded after 14 h visible light radiation.     

Visible-light-driven Ag/Ag3PO4-based plasmonic photocatalysts: Enhanced photocatalytic performance by hybridization with graphene oxide

An efficient visible-light-driven plasmonic photocatalyst with regard to graphene oxide(GO) hybridized Ag/Ag3PO4(Ag/Ag3PO4/GO) nanostructures has been facilely synthesized via a deposition-precipitation method.The synthesized nanostructures have been characterized by means of scanning electron microscopy(SEM),energy-dispersive X-ray spectroscopy(EDX),X-ray diffraction(XRD),UV-vis spectra,Fourier transform infrared spectra(FT-IR),X-ray photoelectron spectroscopy(XPS),and Raman spectra.It has been disclosed that compared with the bare Ag/Ag3PO4 nanospecies,the GO hybridized nanostructures display enhanced photocatalytic activity for the photodegradation of methyl orange pollutant under visible-light irradiation.It is suggested that the reinforced charge transfer and the suppressed recombination of electron-hole pairs in Ag/Ag3PO4 /GO,the smaller size of Ag/Ag3PO4 nanospecies in Ag/Ag3PO4/GO,all of which are the consequences of the hybridization of GO,are responsible for the enhanced photocatalytic performance.The investigation might open up new opportunities to obtain highly efficient Ag3PO4-based visible-light-driven plasmonic photocatalyst for the photodegradation of organic pollutants.     

Photocatalytic and electrochemical degradation of methylene blue by titanium dioxide

A photoanode structure for dye-sensitized solar cells has been applied into the photocatalytic/electro- chemical cooperative degradation of methylene blue solu- tions. The low eutectic point of titanium dioxide （TiO2） with a fluorine-doped tin dioxide （FTO） conductive layer results in a high reactivity of TiO2 for the photocatalytic process as well as a good electron transfer for the elec- trochemical process. The porous TiO2 layer maintains a large surface area for the degradations. Through the com- binational process, the degradation velocity was improved by - 36 %, compared to a pure photocatalytic process.     

纳米TiO2/玻璃膜的制备及其光催化性能

以钛醇盐为原料, 采用溶胶-凝胶法制备了纳米TiO2/玻璃薄膜. XRD、AFM和厚度分析表明,纳米TiO2/玻璃薄膜中TiO2为锐钛矿型结构, 粒径为纳米级, 三层膜的总厚度为200#nm.通过调节热处理温度, 能有效控制薄膜中粒子的大小.UV-VIS吸收光谱表明,TiO2/玻璃薄膜可以有效地降解罗丹明B染料废水,其光催化活性随TiO2粒径的减小而增大,受膜厚增加的影响不大.     

Enhanced photocatalytic degradation of tetracycline hydrochloride by molecular imprinted film modified TiO<Subscript>2</Subscript> nanotubes

To enhance the photocatalytic activity of TiO2 nanotubes,tetracycline hydrochloride(TC) molecularly imprinted titania modified TiO2 nanotubes(MIP-TiO2) was prepared by liquid phase deposition,which improved the molecular recognition ability of the photocatalyst toward template molecules.This MIP-TiO2 photocatalyst was characterized by ESEM and XRD,which showed that the imprinted titania was deposited on the nanotube uniformly and was of well-crystalized anatase-type.In the adsorption experiments,MIP-TiO2 exhibited a high adsorption capacity(about 1.6 times higher than that of TiO2 nanotubes) for TC mainly because of its imprinted sites and high surface area.Under UV irradiation MIP-TiO2 showed enhanced photocatalytic activity with an apparent first-order rate constant 1.9-fold that of TiO 2 nanotubes.