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.     

Synthesis,characterization, and theoretical study of N,S-codoped nano-TiO<Subscript>2</Subscript> with photocatalytic activities

Nitrogen and sulfur doped titanium dioxide photocatalysts were prepared by the sol-gel method. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-visible diffuse reflectance spectra (DRS). Photocatalytic activities of the samples were investigated on the degradation of methyl orange (MO). The effect of the dopants on the electronic structure of TiO₂ was studied by the first-principles calculations based on the density functional theory (DFT). The orbital hybridization resulted in energy gap narrowing and electronic delocalization in the crystal of doped TiO₂. Mobile electrons of varied energetic states could offer enhanced electron transfer, together with optical absorption improvement. The results show that the doping elements of N and S play a cooperative role in the modification of electronic structure, which enhances the photocatalytic performance. The experimentally observed absorption edges of N-doped TiO₂, S-doped TiO₂, and N, S-codoped TiO₂ are 420, 413, and 429 nm, respectively, which can be explained by the theoretical calculation results.     

TiO<Subscript>2</Subscript>@MgO core-shell film: Fabrication and application to dye-sensitized solar cells

In this study,TiO2@MgO core-shell film was obtained by using a simple chemical bath deposition method to coat a thin MgO film around TiO2 nanoparticles. The core-shell configuration was characterized by X-ray diffractometer (XRD),scanning elec-tron microscopy (SEM),energy dispersive X-ray spectroscopy (EDX),and high-resolution transmission electron microscopy (HRTEM). Lattice fringes were observed for the TiO2 particles,and the MgO shell showed an amorphous structure,revealing a clear distinction between the core and shell materials. Applying the core-shell film as photoanode to the dye-sensitized solar cells (DSSCs),it shows a superior performance compared to the pure TiO2 electrode. Under the illumination of simulated sunlight (75 mW-cm-2),the short circuit photocurrent (Jsc),the open circuit photovoltage (Voc),and the fill factor (fF) are 8.80 mA-cm-2,646 mV,and 0.69,respectively,and the conversion efficiency (η) in-creased by 21.8% (from 4.32% to 5.26%) when dipping for opti-mum condition.     

Influence of catalyst on structural and morphological properties of TiO2 nanostructured films prepared by sol–gel on glass

Transparent TiO2 thin films have been prepared by the sol-gel method using titanium alkoxides as precursors.Thin films were deposited on glass supports by the dip-coating technique.The TiO2 layer acts as a self-cleaning coating generated from its photocatalysis and photoinduced superhydrophilicity.The crystalline structure of TiO2 films was dominantly identified as the anatase phase,consisted of uniform spherical particles of about 14-50 nm in size,which strongly depends upon catalyst-type and heat treatment temperature.Increasing heat treating temperature can lead to an increase in crystalline size.The results indicated that the sample S.S(sample derived from sol containing sulfuric acid as catalyst) exhibits superhydrophilic nature and better photocatalytic activity,which can be attributed to its higher anatase content and lower crystalline size.Morphological studies,carried out using Atomic Force Microscopy(AFM),confirm the presence of crystalline phase with such a grain size and low surface roughness.Thus,the applied films exhibiting high photocatalytic activity,superhydrophilic behavior,and low surface roughness can be used as an efficient self-cleaning coating on glass and other optical applications.     

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.     

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.     

Dissolution of Al<Subscript>2</Subscript>TiO<Subscript>5</Subscript> inclusions in CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> slags at 1823 K

Al-Ti-O inclusions always clog submerged nozzles in Ti-bearing Al-killed steel. A typical synthesized Al₂TiO₅ inclusion was immersed in a CaO-SiO₂-Al₂O₃ molten slag for different durations at 1823 K. The Al₂TiO₅ dissolution paths and mechanism were revealed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Decreased amounts of Ti and Al and increased amounts of Si and Ca at the dissolution boundary prove that inclusion dissolution and slag penetration simultaneously occur. SiO₂ diffuses or penetrates the inclusion more quickly than CaO, as indicated by the w(CaO)/w(SiO₂) value in the reaction region. A liquid product (containing 0.7–1.2 w(CaO)/w(SiO₂), 15wt%–20wt% Al₂O₃, and 5wt%–15wt% TiO₂) forms on the inclusion surface when Al₂TiO₅ is dissolved in the slag. Al₂TiO₅ initially dissolves faster than the diffusion rate of the liquid product toward the bulk slag. With increasing reaction time, the boundary reaches its largest distance, the Al₂TiO₅ dissolution rate equals the liquid product diffusion rate, and the dissolution process remains stable until the inclusion is completely dissolved.     

可见光驱动的Ti基半导体光催化剂的研究进展

半导体光催化技术在太阳能转换以及环境治理方面具有巨大潜力。TiO₂由于其高的光催化效率、良好的稳定性以及合适的带边电位等,成为了当前研究最多的光催化材料。但TiO₂是宽带隙半导体,对可见光几乎不响应,这极大限制了TiO₂的应用。为了提高TiO₂对可见光的响应能力,提高太阳能的转化效率,相继开发了一系列由TiO₂衍生的Ti基可见光催化剂。首先简单地介绍了半导体光催化机制,然后综述了Ti基半导体光催化剂的分类、增强可见光响应策略以及Ti基可见光催化剂应用现状,最后总结了Ti基可见光催化剂制备及应用过程中所面临的挑战,同时也对未来Ti基可见光催化剂的合成及发展进行了展望。     

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.     

Blue TiO2 polymorph: An efficient material for dye-sensitized solar cells fabricated using a low-temperature sintering process

Recently,surface-disordered or non-stoichiometric TiO_2,such as blue TiO_2(B-TiO_2),has received much attention owing to its unique properties,such as structural disorder near the surface and the existence of Ti~(3+)ions and oxygen vacancies.Therefore,surface-disordered TiO_2has been applied for microwave absorption,photocatalysis,in photoelectrochemical sensors and rechargeable lithium-ion batteries.In this work B-TiO_2,a polymorph consisting of nanoparticles,nanotubes and nanosheets,was successfully synthesized and employed as a semiconductor layer in dye-sensitized solar cells(DSSCs)fabricated using a low-temperature heat treatment process(120°C).Based on the analyses of the experimental results regarding the structure and those from the characterization of B-TiO_2,and its application to DSSCs,it has been found that the B-TiO_2 material has an effect on electron-hole pair separation.The conversion efficiency of the B-TiO_2 DSSC(BTiO_2-DSSC)was 6.18%,whereas that of the TiO_2-P25 DSSC(P25-DSSC)was 3.61%,and that of the TiO_2 polymorph DSSC(PTiO_2-DSSC)which is the precursor of B-TiO_2 was 4.51%.     

界面反应法制备Ag@AgCl纳米棒及其光催化性能研究

采用界面反应法合成了一种表面负载Ag纳米颗粒的Ag@AgCl纳米棒复合物。通过IR、XRD、SEM、TEM、XPS等手段对所制备材料进行表征。结果表明,采用界面法可以在常温、常压下将纳米颗粒负载在Ag纳米棒上。对所制备材料的光催化性能进行研究,由测试结果可知,该纳米复合材料在可见光下催化亚甲基蓝（MB）的活性要明显优于二氧化钛（P-25）,且光照15 min后MB的降解可达96%。研究结果将为银/卤化银体系材料的开发及在可见光光催化领域的应用提供新的思路。     

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.     

Layered Fe（Ⅲ） doped TiO2 thin-film electrodes for the photoelectrocatalytic oxidation of glucose and potassium hydrogen phthalate

Four types of TiO 2 thin-film electrodes were fabricated from TiO 2 and Fe(III) doped TiO 2 sols using a layer-by-layer dip-coating technique. Electrodes fabricated were TF (pure TiO 2 surface, Fe(III)-TiO 2 bottom layer), FT (Fe(III)-TiO 2 surface, pure TiO 2 bottom layer), TT (both layers pure TiO 2 ) and FF (both layers Fe(III)-TiO 2 ). The photoelectrochemical behavior of these electrodes was characterized using linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and steady-state photocurrent measurements in aqueous 0.1 mol L –1 NaNO 3 containing varying concentrations of glucose or potassium hydrogen phthalate (KHP). EIS and LSV results revealed that exciton separation efficiency followed the sequence of TF﹥TT﹥FT > FF. Under a constant potential of +0.3 V, steady-state photocurrent profiles were recorded with varying organic compound concentrations. The TF electrode possessed the greatest photocatalytic capacity for oxidizing glucose and KHP, and possessed a KHP anti-poisoning effect. Enhanced photoelectrochemical performance of the TF electrode was attributed to effective exciton separation because of the layered TF structure.     

Comparison between P25 and anatase-based TiO<Subscript>2</Subscript> quasi-solid state dye sensitized solar cells

Pure anatase TiO2 films have been made via hydration of titanium isopropoxide using a sol-gel tech-nique, while mixed TiO2 films which contained both anatase and rutile TiO2 were made from commercial P25 powder. Quasi-solid state dye-sensitized solar cells were fabricated with these two kinds of mesoporous films and a comparison study was carried out. The result showed that the open-circuit photovoltages （Voc） for both kinds of cells were essentially the same, whereas the short-circuit photo-currents （1sc） of the anatase-based cells were about 33% higher than that of the P25-based cells. The highest photocurrent intensity of the anatase-based cell was 6.12 mA/cm^2 and that of the P25-based cell was 4.60 mA/cm^2. Under an illumination with the light intensity of 30 mW/cm^2, the corresponding energy conversion efficiency was measured to be 7.07% and 6.89% for anatase-based cells and P25-based cells, respectively.     

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.     

自由基抑制剂对不同晶型TiO2光催化反应的影响

以荧光光谱法研究了不同晶型 TiO₂ 的光催化反应体系中羟基自由基(·OH)的产生情况,表明在H₂O₂存在条件下,金红石型 TiO₂ 经可见光激发可持续稳定产生·OH,而以锐钛矿型 TiO₂ 作光催化剂时,则检测不到·OH的生成。光催化结果表明,在H₂O₂存在条件下,苯酚可被 TiO₂ 可见光催化降解;往反应体系加入自由基抑制剂(叔丁醇或甲醇)时,明显降低了金红石型 TiO₂ 的降解效率,但对锐钛矿型 TiO₂ 的影响较弱。以金红石型 TiO₂ 作光催化剂时,苯酚的降解反应主要发生在溶液中;而以锐钛矿型 TiO₂ 作光催化剂时,则苯酚的降解反应主要发生在催化剂的表面。     

Synthesis and characterization of monoclinic TiO<Subscript>2</Subscript> nanosheets

A novel two-step method for the synthesis of monoclinic titanium oxide （i.e. TiO2（B）） nanosheets is presented in this report. The method is featured by two steps： 1） synthesis of hydrogen titanate nanosheets, followed by 2） calcination of the titanate nanosheets at elevated temperatures. The hydrogen titanate nanosheets were prepared first by autoclaving anatase TiO2 powders, obtained by air cal- cining an ethanol-gel of Ti（OH）4 at 500℃, in aqueous NaOH （10 mol/L） at 150-200℃, and then by washing with hydro- chloric acid under supersonic irradiation. While sizes of the nanosheets were found to increase with increasing the temperature of the hydrothermal treatment, the calcination at 400-500℃ of the hydrogen titanate nanosheets that were synthesized at higher autoclaving temperatures （180-200℃） produced monoclinic TiO2 nanosheets with a uniform morphology. By contrast, the same calcination of the titanate nanosheets synthesized at the autoclaving temperature 180℃ led to anatase TiO2 nanoparticles.     

Photoelectrochemical synergetic degradation of Acid Orange II with TiO2 modified β-PbO2 electrode

Electrochemically assisted photocatalysis is an effective approach to improve photocatalytic efficiency. In this paper, modified β-PbO2 electrode was prepared by TiO2 co-deposition and characterized by SEM and XRD. Then 2.0g TiO2 modified β-PbO2 electrode (2.0 g TiO2 involved in the 200 mL co-deposition solution) was used in electrochemically assisted photocatalytic degradation of Acid Orange II and the influence of initial pH values was investigated when the potential applied across the electrodes was 1.5 V. When the potential applied was 2.5 V, the difference of the degradation process and the final products were studied. The results indicated that 2.0 g TiO2 modified β-PbO2 electrode was different from the unmodified one in that the β-PbO2 crystals became finer and the electrode became more compact and more uniform. The synergetic effect in electrochemically assisted photocatalytic degradation of Acid Orange Ⅱ was observed and degradation efficiency and TOC removal were the highest at initial solution pH 2.0. By UV-visible spectral analysis, it was proved that photoelectrochemical synergetic degradation of Acid Orange Ⅱ went through the step of producing main product maleic acid for the solution at the initial pH 2.0 within 2 h, but the degradation was slow for the solution at the initial pH 12.0.     

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%.