Fabrication of visible-light responsive S-F-codoped TiO<Subscript>2</Subscript> nanotubes

Fabrication and S-F-codoping of TiO2 nanotubes were carried out by a one-step electrochemical anodization process to extend the photoresponse of TiO2 to the visible-light region. The prepared samples were annealed in air and detected by SEM, XRD, XPS and UV-vis DRS spectrophotometer. The results showed that the average tube diameter of the nanotubes was 150 nm and the average tube length was 400 nm. The doped TiO2 nanotubes exhibited strong absorption in visible-light region. Photoelectrocatalytic degradation efficiency of 4-CP over S-F-codoped TiO2 nanotubes was 39.7% higher than that of only-F-doped sample. Moreover, sulfur and fluorine codoped into substitutional sites of TiO2 had been proven to be indispensable for strong response and high photocatalytic activity under visible light, as assessed by XPS.     

I-doping of anodized TiO<Subscript>2</Subscript> nanotubes using an electrochemical method

In order to obtain TiO2 with high photocatalytic activity, a cathode reduction was used to dope I⁷⁺ and I⁵⁺ into TiO₂ nanotubes of anodized Ti in C₂H₂O₄•2H₂O + NH₄F electrolyte. SEM images show that the anodization method integrated the preparation with the doping process, which for nonmetals-doping is advantageous to maintain the morphological integrity of TiO₂ nanotubes. I⁷⁺-I⁵⁺-doping enhances the UV response of TiO₂ and result in a red-shift. Under UV/visible irradiation, a I⁷⁺-I⁵⁺-doped sample (400°C) showed the highest I_ph and photocatalytic efficiency. A part of I^– in the I⁷⁺-I⁵⁺-doped sample is involved in the UV response, the red-shift and the higher I_ph.     

Carboxyl-modified hierarchical wrinkled mesoporous silica supported TiO2 nanocomposite particles with excellent photocatalytic performances

Titanium dioxide (TiO₂) is a common photocatalyst for organic pollutants degradation. However, in practical application, the poor adsorption capacity of pure TiO₂ seriously impeded its efficiency in the degradation of organic molecules. In this work, a series of hierarchical wrinkle mesoporous silica supported TiO₂ nano-composite particles (TiO₂ @WMS-COOH) were successfully prepared. Thanks to their high surface areas, large pore volumes and mesoporous structures, these materials showed high adsorption capacity and excellent photocatalytic performance towards dye molecules, which is comparable to or even better than commercial catalyst P25. Moreover, their photocatalytic efficiency can be further enhanced by increasing the calcination temperature during preparation process. Therefore it can be concluded that the TiO₂ @WMS-COOH particles may find promising applications in the photodegradation of organic pollutants.     

Photocatalytic degradation of metronidazole in aqueous solution by niobate K<Subscript>6</Subscript>Nb<Subscript>10.8</Subscript>O<Subscript>30</Subscript>

The photocatalytic degradation of antibiotic metroni-dazole in aqueous solution by niobate K6Nb10.8O30 photocatalyst that was prepared using a soft-chemical method was studied by Fourier transform infrared spectroscopy and UV-Vis absorption spectrum. Metronidazole is very stable and is difficult to degrade under UV irradiation. K6Nb10.8O30 photocatalyst cannot degrade metronidazole without UV irradiation and shows very high photo-catalytic activity for the degradation of metronidazole under UV irradiation. The photocatalytic degradation rate of metronidazole increased with increasing the dosage of K6Nb10.8O30 photocatalyst. The photocatalytic degradation reaction of metronidazole by nio-bate K6Nb10.8O30 follows the first-order kinetic equation.     

Preparation of Zn-doped TiO2 nanotubes electrode and its application in pentachlorophenol photoelectrocatalytic degradation

Zn-doped titanium oxide （TiO2） nanotubes electrode was prepared on a titanium plate by direct anodic oxidation and immersing method in sequence. Field emission scanning electron microscopy （FESEM） showed that the Zn-doped TiO2 nanotubes were well aligned and organized into high density uniform arrays with diameter ranging from 50 to 90 nm. The length and the thickness were about 200 and 15 nm respectively. TiO2 anatase phase was identified by X-ray diffraction （XRD）. X-ray photoelectronspectroscopy （XPS） indicated that Zn ions were mainly located on the surface of TiO2 nanotubes in form of ZnO clusters. Compared with TiO2 nanotubes electrode, about 20 nm red shift in the spectrum of UV-vis absorption was observed. The degradation of pentachlorophenol （PCP） in aqueous solution under the same condition （initial concentration of PCP： 20 mg/L; concentration of Na2SO4：0.01 mol/L and pH： 7.03） was carried out using Zn-doped TiO2 nanotubes electrode and TiO2 nanotubes electrode. The degradation rates of PCP using Zn-doped TiO2 nanotubes electrode were found to be twice and 5.8 times as high as that using TiO2 nanotubes electrode by UV radiation （400 μw/cm^2） and visible light radiation （4500 μw/cm^2）, respectively. 73.5% of PCP was removed using Zn-doped TiO2 nanotubes electrode against 45.5% removed using TiO2 nanotubes electrode in 120 min under UV radiation. While under visible light radiation, the degradation efficiency of PCP was 18.4% using Zn-doped TiO2 nanotubes electrode against 3.2% using TiO2 nanotubes electrode in 120 min. The optimum concentration of Zn doping was found to be 0.909%. The PCP degradation efficiencies of the 10 repeated experiments by Zn-doped TiO2 nanotubes electrode were rather stable with the deviation within 3.0%.     

Preparation and characterization of in-site regenerated TiO<Subscript>2</Subscript>-ACFs photocatalyst

In-site regenerated titanium dioxide-activated carbon fibers (TiO₂-ACFs) photocatalyst was prepared by the sol-gel method. Detailed surface and structural characterization of the TiO₂-ACFs photocatalyst was carried out. The photoactivity of TiO₂-ACFs under ultraviolet irradiation was compared with original ACFs and pure TiO₂ by the degradation of methylene blue aqueous solution. The degradation efficiency by the TiO₂ (5wt%)-ACFs sample is much higher than that by TiO₂ and ACFs. The results show that the photocatalysis by TiO₂-ACFs is a six-step process. The adsorption-transfer-photocatalysis rate of TiO₂-ACFs is higher than the adsorption-photocatalysis rate of TiO₂, so the photocatalysis rate of the TiO₂-ACFs system is higher than that of TiO₂ photocatalyst.     

Preparation and photocatalytic properties of ilmenite NiTiO<Subscript>3</Subscript> powders for degradation of humic acid in water

The powders of ilmenite structure NiTiO₃ were prepared by a modified Pechini process using tetrabutyl titanate and nickel acetate as raw materials, and using citric acid and ethanol as a chelating agent and a solvent respectively. The powder samples were characterized by thermogravimetric and differential thermal analysis (TG-DTA) and X-ray diffraction (XRD). The photocatalytic activity of NiTiO₃ under the irradiation of ultraviolet rays (UV) light was evaluated by degrading humic acid (HA) in water as a probe reaction. The possible photodegradation mechanism was studied by the examination of active species ·OH, ·O₂⁻, and holes (h⁺) through adding scavengers. The TG-DTA and XRD results indicated that the good crystal structure of ilmenite phase NiTiO₃ could be obtained when the Ni-Ti citrate complex was calcined at 600°C. The photocatalytic activity experiments indicated that NiTiO₃ had favourable photocatalytic activity under the irradiation of UV light, and the photocatalytic degradation rate of HA reached 95.3% after a 2.5 h reaction with the photocatalyst calcined at 600°C and a photocatalyst dosage of 0.4 g/L. The possible photocatalytic mechanism was deduced that holes (h⁺) and ·OH radicals are the major reactive active species in the photocatalytic reaction, and dissolved oxygen plays a weak role in the degradation of HA.     

A review of TiO<Subscript>2</Subscript> nanoparticles

Climate change and the consumption of non-renewable resources are considered as the greatest problems facing humankind.Because of this,photocatalysis research has been rapidly expanding.TiO2 nanoparticles have been extensively investigated for photocatalytic applications including the decomposition of organic compounds and production of H2 as a fuel using solar energy. This article reviews the structure and electronic properties of TiO2,compares TiO2 with other common semiconductors used for photocatalytic applications and clarifies the advantages of using TiO2 nanoparticles.TiO2 is considered close to an ideal semi- conductor for photocatalysis but possesses certain limitations such as poor absorption of visible radiation and rapid recombination of photogenerated electron/hole pairs.In this review article,various methods used to enhance the photocatalytic characteristics of TiO2 including dye sensitization,doping,coupling and capping are discussed.Environmental and energy applications of TiO2, including photocatalytic treatment of wastewater,pesticide degradation and water splitting to produce hydrogen have been summarized.     

Photocatalytic degradation of microcystin-LR using TiO2 nanotubes under irradiation with UV and natural sunlight

In order to investigate the catalytic performance of anodic TiO2 nanotubes and their practical application in the treatment of refractory microcystins(MCs) in natural-water samples,TiO2 nanotubes of diameter of 50-80 nm were fabricated by anodization in C2H2O4·2H2O containing NH4F.Under irradiation with natural sunlight,MC-LR was totally degraded after 1 d using the anodic TiO2 nanotubes.In contrast,the removal efficiency without TiO2 nanotubes was as low as 47.7% within 20 d.In addition,a mixture of anatase and rutile TiO2 gave higher photocatalytic activity than the single phase did.The pH also influenced the adsorption capacity of the TiO2 nanotubes.The order of MC-LR degradation efficiencies at different pH values was 3.5 > 8.0 > 10.0.After five repeated experiments on the degradation of MC-LR for 7 h,the degradation efficiency was still stable.     

Array of single crystalline anatase TiO2 nanotubes with significant enhancement of photoresponse

Anatase TiO₂ nanotubes array (ATONA) has attracted tremendous attention owing to its promising applications in solar cells, water splitting and organic pollutants photocatalytic degradation. However, the activity of ATONAs was greatly suppressed by the grain boundaries existed in the tube walls, which acted as carrier scattering and recombination centers. Herein, we report a novel strategy to prepare array of single crystalline anatase TiO₂ nanotubes (SC-ATONAs) with significant enhancement of the photocatalytic activity and UV photo response performance compared to the polycrystalline counterparts. The growth of SC-ATONAs was achieved by establishing a crystallization temperature gradient along the tube wall, which ensured the crystallization started from the nucleation of a single nucleus at the bottom of amorphous TiO₂ nanotubes prepared by Ti anodization. These findings pave the way to prepare single-crystalline nanotubes with superior performance for other materials.     

Visible light photocatalytic decoloration of methylene blue on novel N-doped TiO2

Novel N-doped TiO2 (denoted as N-NTA600) was prepared by treating nanotube titanic acid (NTA) in NH3 flow. Its visible light photocatalytic activity,evaluated by decoloration reaction of methylene blue,is higher than that of N-P25(600) prepared by treatment of P25-TiO2 in the same condition. It is suggested that the origin of visible-light photocatalytic activity is single-electron-trapped oxygen vacancy (Vo·) modified by chemisorbed NO.     

Catalysis of organic pollutant photodegradation by metal phthalocyanines immobilized on TiO<Subscript>2</Subscript>@SiO<Subscript>2</Subscript>

A TiO2@SiO2 hybrid support was prepared by the sol-precipitation method using n-octylamine as a template.The photocatalyst manganese phthalocyanine tetrasulfonic acid (MnPcS) was immobilized on the support to form MnPcS-TiO2@SiO2.X-ray diffraction (XRD) and UV-Visible diffuse reflectance spectra (UV-Vis DRS) were employed to characterize the catalyst.The photocatalytic degradation of rhodamine B (RhB) and the catalytic oxidation of o-phenylenediamine (OPDA) under visible light irradiation were used as probe reactions.The mineralization efficiency and the degradation mechanism were evaluated using chemical oxygen demand (COD Cr) assays and electron spin resonance (ESR),respectively.RhB was efficiently degraded by immobilized MnPcS-TiO2@SiO2 under visible light irradiation.Complete decolorization of RhB occurred after 240 min of irradiation and 64.02% COD Cr removal occurred after 24 h of irradiation.ESR results indicated that the oxidation process was dominated by the hydroxyl radical (·OH) and superoxide radical (O-·2) generated in the system.     

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.     

Preparation and photocatalytic activity of Cu-doped TiO2/SiO2

Cu²⁺-doped nanostructured TiO₂-coated SiO₂ (TiO₂/SiO₂) particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO₂ colloids were synthesized by the sol-gel method using TiOSO₄ as a precursor. The experimental results showed that TiO₂ nanopowders on the surface of SiO₂ particles were well distributed and compact. The amount of TiO₂ increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550°C. The 2-layer coated TiO₂ particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu²⁺-doped TiO₂/SiO₂ was higher than that of undoped TiO₂/SiO₂. The optimum dopant content was about 0.10wt%.     

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。     

NO2对光催化降解庚烯的作用

以TiO₂/SiO₂为光催化剂, 在紫外光作用下, 讨论了NO₂存在时, 庚烯在TiO₂/SiO₂上的吸附和光催化降解作用. 通过GC-MS和FT-IR, 分别测定了3种不同体系的反应产物, 从而推测出可能的反应机理. 实验结果表明, TiO₂/SiO₂对庚烯的最大吸附量M_max=3.10　 mg, 当存在NO₂（44.64 μmol/L）时M_max=3.80　mg. 在光催化降解庚烯的反应中, 当NO₂加入量较大(NO₂≥89.28 μmol/L)时, 庚烯降解反应速率加快, 但矿化度比无 NO₂时的小.     

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%.     

Ag/TiO_2/AC光催化氧化NO性能研究

以活性炭(AC)为载体,采用溶胶-凝胶法和浸渍法制备新型光催化剂Ag/TiO_2/AC,利用SEM、XRD、BET和UV-Vis光谱等手段对样品进行了表征,并以模拟烟气中的NO为对象,进行光催化氧化性能测试。结果表明,Ag/TiO_2/AC的比表面积为895.21 m~2/g,且对光响应波长已扩展到可见光区,该催化剂在光催化氧化NO反应中具有优异的活性,NO的氧化率高于60.5%。     

A review on TiO2 nanotube arrays: Fabrication, properties, and sensing applications

Fabrication, properties, and sensing applications of TiO₂ nanotubes have been reviewed, and the highly ordered TiO₂ nanotube arrays made by anodic oxidation in fluoride-contained electrolytes highlighted. The effect of anodization parameters (electrolyte, pH, and voltage) on the titania nanotube size and shape were discussed. The excellent biocompatibility of TiO₂, the high orientation, the large surface area with tunable pore sizes, as well as the high electron transfer rate along with the nanotubes make TiO₂ nanotube array an ideal substrate for the sensor’s fabrication and application. The sensors based on the TiO₂ nanotube arrays for sensing hydrogen, oxygen, humidity, glucose and hydrogen peroxide all exhibited low detection limit, high stability, very good reproducibility and high sensitivity.     

Mechanochemical preparation of sulfur-doped nanosized TiO2 and its photocatalytic activity under visible light

In order to make nanosized TiO2 photocatalyst responsive to visible light and effectively utilize solar energy, we have, for the first time, prepared S-doped nanosized TiO2 by a mechanochemical method with hydrolysis of TiCl4. The as-prepared S-doped nanosized TiO2 possesses strong absorption for visible light of 400-650 nm and shows high photocatalytic activity for decomposition of methylene blue under irradiation of visible light. The oxidation states of the S atoms incorporated into TiO2 were determined to be S^6＋ and S^4＋. The comparative study of fluorescence emission spectra shows that S-doping has also improved the separation of electron-hole pairs.