Synthesis of C-Cl-codoped titania/attapulgite composites with enhanced visible-light photocatalytic activity

We demonstrate the synthesis of C-Cl-codoped titania/attapulgite（TiO2/ATT） composites containing a mixture of TiO2 phases by a facile sol-gel method at 70 ℃ using titanium tetraisopropoxide as the TiO2 precursor and ATT as a support for the TiO2 nanoparticles.The photocatalytic activity of the C-Cl-codoped TiO2/ATT composites with mixed anatase/brookite/rutile phases obtained at pH= 3.0 was much higher than that of commercially available Degussa P25 for the photocatalytic degradation of acid red G under visible-light irradiation.The excellent photocatalytic activity of the developed composite originates from the nonmetal codoping,which extends the absorption edge of TiO2 into visible region,and the presence of multiple phases,which slow the recombination of photoexcited electron/hole pairs.The formation of hydroxyl radicals during the photocatalytic degradation process was detected by photoluminescence probing using terephthalic acid.A mechanism for photocatalysis over the C-Cl-codoped TiO2/ATT composites was proposed.

Synthesis of rutile from high titania slag by pyrometallurgical route

A new technique was developed for the conversion of high titania slag,containing 70%-75% TiO2 and with MgO,FeO,CaO,Al2O3 and SiO2 as main impurities,into a synthetic rutile,90%-95% TiO2,which satisfies the requirements for fluidizing chlorination process with respect to impurity contents.After a pre-oxidation at around 1 042 ℃ and a heat-treatment above 1 510 ℃,the Ti components in high titania slag can be enriched into the rutile phase which can precipitate and grow,and can be separated with dilute hydrochloric and sulfuric acid,respectively.The results show that the average crystal size of rutile phase is over 25 μm,and the synthetic rutile containing more than 95% TiO2 can be produced by selective leaching.

High temperature oxidation behavior of electroconductive TiN/O′-Sialon ceramics prepared from high titania slag-based mixture

The oxidation behavior of electroconductive TiN/O′-Sialon ceramics prepared using high titania slag as main starting material was studied at 1 200-1 300 °C in air. The isothermal and non-isothermal oxidation processes were investigated by DTA-TG. Phase compositions and morphologies of the oxidized products were analyzed by XRD, SEM and EDS. The results indicate that the oxidation of TiN and O′-Sialon occurs at about 500 °C and 1 050 °C, respectively. After oxidation at 1 200-1 300 °C, a protective scale that consists of Fe2MgTi3O10, SiO2 and TiO2 is formed on the surface of the materials, which effectively prevents the oxidation process. The formation of a protective scale is relative to TiN content and apparent porosity of the samples, the amount of SiO2 and amorphous phase in the oxidation product. At the initial oxidation stage, the oxidation kinetics of the materials follows perfectly the linear law with the apparent activation energy of 1.574×105 J/mol, and at the late-mid stage, the oxidation of the samples obeys the parabolic law with the apparent activation energy of 2.693×105 J/mol. With the increase of TiN content, mass gain of the materials increases significantly.

Preparation of bismuth oxide/titania composite particles and their photocatalytic activity to degradation of 4-chlorophenol

Bismuth oxide/titania, one interfacial composite semiconductor with high photocatalytic activity under solar light, was prepared at low temperature. The structure was characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, brunauer-emmett-teller （BET）, X-ray photoelectron spectroscopy （XPS） and diffuse reflection spectra （DRS）. The results indicate that deposited titania nanoparticles on bismuth oxide surface have micro-nano structure, and this composite material exhibits porosity and increased surface hydroxyl groups. Furthermore, the as-prepared photocatalyst shows higher photocatalytic activity to the degradation of 4-chlorophenol than pure titania or P25 under sunlight.

Preparation and photocatalytic activity of neodymium doping titania loaded to silicon dioxide

Neodymium doping titania was loaded to silicon dioxide to prepare Nd/TiO2-SiO2 by sol-gel method and Nd/TiO2-SiO2 was characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, Fourier transform-infrared spectroscopy （FT-IR） and diffuse reflectance spectra （DRS）. Photocatalytic activities of Nd/TiO2-SiO2 with different neodymium contents were evaluated by degradation of methyl orange. The light absorption of Nd/TiO2-SiO2 increased with increasing doping neodymium in a visible light range of 388-619 nm, and Nd doping was in favor of decreasing the recombination of photo-generated electrons with holes. Nd and SiO2 improved the photocatalytic activity of TiO2. The optimal molar fraction of Nd to Ti was 0.1%, and the optimum calcination temperature was 600 ℃. The highest degradation rate of methyl orange was 82.9% after irradiation for 1 h.

Preparation, Characterization, Photocatalytic Activity of S and Ag co-Doped Mesoporous Titania Photocatalysts

In order to improve the photocatalytic performance of mesoporous titania under visible light, a series of photocatalysts of S and Ag co-doped mesoporous titania have been successfully prepared by template method using thiourea, AgNO3 and tetrabutyl titanate as precursors and Pluronic P123 （EO20PO70EO20） as template. Scanning electron microscopy （SEM）, X-ray diffraction （XRD）, nitrogen adsorption-desorption measurements, and UV-visible spectroscopy （UV-Vis） were employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. The microcrystal of the photocatalysts consisted of anatase phase and was approximately present in the form of spherical particle. The photocatalytic performance was studied by photodegradation methyl orange （MO） in water under UV and visible light irradiation. The calcination temperature and the doping content influenced the photoactivity. In addition, the possibility of cyclic usage of co-doped mesoporous titania was also confirmed, the photocatalytic activity of mesoporous titania remained above 89% of that of the fresh sample after being used four times. It was shown that the co-doped mesoporous titania could be activated by visible light and could thus be potentially applied for the treatment of water contaminated by organic pollutants. The synergistic effect of sulfur and silver co-doping played an important role in improving the photocatalytic activity.

Investigation on Quick Surface Metallization of Nano Titania Powder

Quick surface metallization of titania powder was carried out by electrolesschemical deposition of nickel. The fabricated product was characterized by XRD, SEM, FTIR andcross-section metallography. The analysis results show that titania particles are completely coatedby a thin nickel shell about 600 nm thick composed of nano-sized crystalline nickel particles.Mechanism of nickel chemical deposition on nano powder is proposed.

Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers （DMMn） were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.

Molybdosphoric Acid Mixed with Titania Used as a Catalyst to Synthesize Diphenyl Carbonate via Transesterification of Dimethyl Carbonate and Phenol

The 12-molybdosphoric acid mixed with titania （MPA-TiO2） was found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate （DPC） via transesterification of dimethyl carbonate （DMC） and phenol. The X-ray diffraction （XRD） and infrared （IR） techniques were employed to characterize the prepared catalysts. The effect of the weight ratio of the 12-molybdosphoric acid to titania on the transesterification was investigated. A 13.1% yield of DPC and an 11.6% yield of methyl phenyl carbonate （MPC） were obtained over MPA-TiO2 with the weight ratio of MPA to TiO2 as 5：1.

Enhancement of formaldehyde degradation by amine functionalized silica/titania films

Doping amine functional groups into SiO2/TiO2 films for enhancing the decomposition of formaldehyde has been investigated using the modified sol-gel method to prepare organic-inorganic hybrid photocatalysts via the co-condensation reaction of methyltrimethoxysilane （MTMOS） and amine functional groups, n-（2-Aminoethyl）-3-aminopropyl-trimethoxysilane （AEAPTMS） and 3-aminopropyl-trimethoxysilane （APTMS） were selected to study the effect of amine functional groups on the enhancement of formaldehyde adsorption and degradation under a UV irradiation process. Physicocbemical properties of prepared photocatalysts were characterized with nitrogen adsorption-desorption isotherms measurement, X-ray diffraction （XRD） and Fourier transform infrared （FT-IR） spectroscopy. The results indicated that the APTMS/SiO2/TiO2 film demonstrated a degradation efficiency of 79% superior to those of SiO2/TrO2 and AEAPTMS/SiO2/TiO2 films due to the synergetic effect of adsorption and photocatalytic properties. The APTMS/SiO2/TiO2 film can be recycled with about 7% decreasing of degradation efficiency after seven cycles.

Preparation of nitrogen-doped titania and its photocatalytic activity

Yellowish nitrogen-doped titania was produced through sol-gel method in mild condition, with the elemental nitrogen derived from aqua ammonia. The titania catalysts were characterized using XRD, BET, TEM, XPS, and UV-Vis diffuse reflectance spectrophotometer, and their photocatalytic activities were evaluated under UV and visible light, respec tively. The XRD results showed that all titania catalysts were anatase. More significantly, the crystallite size of nitrogen-doped titania increased with an increase in N/Ti proportion, and the doping of nitrogen could extend the absorption shoulder into the visible-light region, thus it possessed a higher visible-light activity illustrated by decolorization of methyl orange （65.3%） under the irradiation of visible light, whereas pure titania showed little of such kind of visible light activity. The UV-light activity of nitrogen-doped titania catalysts was worse than that of pure titania and Degussa P25. In the range of N/Ti proportion of 4-10 mol%, the activity of nitrogen-doped titania weakened appreciably in the visible-light region as the N/Ti proportion increased, whereas a reverse relationship existed under the irradiation of UV light.

Synthesis and Characterization of Co-Doped Brookite Titania Photocatalysts with High Photocatalytic Activity

Transition metal-doping could effectively extend the light response range of TiO _2 photocatalysts from the ultraviolet(UV)to the visible region.Co-doped brookite titanium dioxide(Co–TiO_2)photocatalysts were synthesized via the hydrothermal method with titanium tetrachloride as the raw material and cobalt chloride hexahydrate as the dopant.The prepared Co–TiO_2 photocatalysts were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),Raman spectroscopy,X-ray photoelectron spectroscopy(XPS)and UV–Vis diffuse reflectance spectroscopy(UV–Vis DRS).The photocatalytic activities of Co–TiO _2 photocatalysts were evaluated by photocatalytic degradation of isopropanol alcohol(IPA),a typical volatile organic compound(VOC),under visible light.The influences ofdifferent Co doping rates,initial concentrations of IPA gas and the amounts of photocatalyst addition were also studied.At the same time,the enhancement mechanism ofcobalt ions as a trap for photogenerated holes was discussed.Thus,we found the optimum doping rate,initial concentration of IPA gas and amount of photocatalyst to add.The results show that the mesoporous Co–TiO _2 photocatalysts possess smaller size particles,larger specific surface area,lower forbidden bandgap energy(Eg)and better photocatalytic activity than pure brookite TiO _2.When the doping of Co was 7% by mass,the initial concentration ofIPA gas was 1.0×10^(-6 )mol/L and the addition of Co–TiO_2 photocatalysts was 50 mg,the best photocatalytic activity was achieved.Furthermore,the degradation rate ofIPA was up to 91%,which shows great potential for waste water treatment.

Synthesis of Nanoscale Shell-core Titania Coated Silica Particles in the Presence of Polyether Polyamine and the Phase Transition

The nanoscale titania coated silica was prepared via a two-step precipitating approach, where the nanoscale silica nuclei were first prepared by passing an aqueous solution of sodium silicate through an ion-exchange resin bed, then coated with the precipitation from hydrolyzed butyl titanate in an ethanol-hexane mixture at a low pH value in the presence of poly(ethylene oxide) polyamine salt(PPA) at a high temperature of 90 ℃. In the second-step precipitating process, the spontaneously precipitated titania shell on the silica nuclei was stabilized in the suspension solution with the help of the adsorption of PPA on the particles. A possible precipitating mechanism was suggested. Furthermore, the amorphous titania shell could undergo crystallization from the amorphous to the anatase structure at a high temperature of 650 ℃, and a further phase transition from the anatase to the rutile structure in the different sintering processes at a rising temperature of 750 ℃.

Recent advances in non-metal doped titania for solar-driven photocatalytic/photoelectrochemical water-splitting

Photocatalytic (PC) / Photoelectrochemical (PEC) water splitting under solar light irradiation is considered as a prospective technique to support the sustainable and renewable H_(2) economy and to reach the ultime goal of carbon neutral. TiO_(2) based photocatalysts with high chemical stability and excellent photocatalytic properties have great potential for solar-to-H_(2) conversion. To conquer the challenges of the large band-gap and rapid recombination of photo generated electron-holepairs in TiO_(2), non-metal doping turns out to be economic, facile, and effective on boosting the visible light activity. The localized defect states such as oxygen vacancy and Ti^(3+) generated by non-metal doping are located in the band-gap of TiO_(2), which result in the reduction of band-gap, thus a red-shift of the absorption edge. The hetero doping atoms such as B^(3+), I^(7+), S^(4+)/S^(6+), P^(5+) can also act as electron donors or trap sites which facilitate the charge carrier separation and suppress the recombination of electron-hole pairs. In this comprehensive review, we present the most recent advances on non-metal doped TiO_(2) photocatalysts in terms of fundamental aspects, origin of visible light activity and the PC / PEC behaviours for water splitting. In particular, the characteristics of different non-metal elements (N, C, B, S, P, Halogens) as dopants are discussed in details focusing on the synthesis approaches, characterization as well as the efficiency of PC and PEC water splitting. The present review aims at guiding the readers who want quick access to helpful information about how to efficiently improve the performance of photocatalysts by simple doping strategies and could stimulate new intuitive into the new doping strategies.

Phenol photocatalytic degradation over mesoporous TUD-1-supported chromium oxide-doped titania photocatalyst

Mesoporous Technische Universiteit Delft（TUD-1）-supported chromium oxide-doped titania（Cr-TiO2） was developed as a promising photocatalyst for phenol photodegradation under visible light irradiation.Low-angle X-ray diffraction and Fourier transform infrared spectroscopy results confirmed the amorphous and mesoporous silicate framework of TUD-1 in TUD-1-supported Cr-TiO2.The mesostructure of TUD-1 was further verified via N2 adsorption-desorption analysis,which showed a type-IV isotherm with a narrow average pore size distribution of 3.9 nm and high surface area of 490 m^2/g.Transmission electron microscopy analysis results indicated that TUD-1-supported Cr-TiO2 contained nanoparticles and porous channels.An increase in band gap energy was observed after loading Cr-TiO2 into TUD-1.Compared with that of unsupported Cr-TiO2,TUD-1-supported Cr-TiO2 showed higher photocatalytic activity for phenol degradation under visible light irradiation.The TUD-1 supported Cr-TiO2 photocatalyst with a Si/Ti molar ratio of 30 exhibited the highest photodegradation of phenol（82%） of the prepared samples.The photodegradation of phenol by the supported catalyst followed the Langmuir adsorption isotherm with first-order kinetics.

Unexpectedly selective hydrogenation of phenylacetylene to styrene on titania supported platinum photocatalyst under 385 nm monochromatic light irradiation

Conversion of alkynes to alkenes by photocatalysis has inspired extensive interest but it is still challenging to obtain both high conversion and selectivity.Here we first demonstrate the photocatalytic conversion of phenylacetylene(PLE)to styrene(STE)with both high conversion and selectivity by using the titania(TiO2)supported platinum(Pt)as photocatalyst under 385 nm monochromatic light irradiation.It is demonstrated that the conversion rate of PLE is strongly dependent on the content of Pt cocatalyst loaded on the surface of TiO2.Based on our optimization,the conversion of PLE and the selectivity towards STE on the 1 wt%Pt/TiO2 photocatalyst can unexpectedly reach as high as 92.4%and 91.3%,respectively.The highly selective photocatalytic hydrogenation can well be extended to the conversion of other typical alkynes to alkenes,demonstrating the generality of selective hydrogenation of C≡C over the Pt/TiO2 photocatalyst.

Synthesis of Nanostructured Copper-doped Titania and Its Properties

Nanostructured pure-Ti O_2 and Cu3%-Ti O_2 were successfully synthesized via co-precipitation method. The X-ray diffraction(XRD) result proves that the synthesized sample were predominantly in anatase phase with size in the range of 8～16 nm, which are in good agreement with the transmission electron microscopy data. Owing to doping of copper, not only did the thermal stability of the Ti O_2 decrease, but also a significant decrease in its particle size and a shift of the adsorption edge to a higher wavelength region appear. The activity of both pure-Ti O_2 and Cu3%-doped Ti O_2 was tested to study their ability to decolorize congo red(CR) dye in aqueous solution. We observed that the CR dye was decolorized faster by Cu3%-Ti O_2 than pure-Ti O_2. Results of this study demonstrate a potential application of the synthesized sample for decolorizing dye pollutants from aqueous waste.

Superior performance of iridium supported on rutile titania for the catalytic decomposition of N_2O propellants

N2O is a promising green propellant and exhibits great potential for satellite propulsion systems. It is difficult for catalytic decomposition, which is an important way to initiate the propulsion process, to occur at temperatures below 600 °C due to the high activation energy of N2O. In this work, we report an Ir supported on rutile TiO2（Ir/r-TiO2） catalyst which exhibits a fairly high activity for high-concentration N2O decomposition. HAADF-STEM, H2-TPR, and XPS results indicate that highly dispersed Ir particles and improved oxygen mobility on the Ir/r-TiO2 could facilitate the decompo-sition of N2O and desorption of the adsorbed oxygen. Bridge-bonded peroxide intermediates were observed with in-situ DRIFT and herein, a detailed decomposition route is proposed.

Cytocompatibility with osteogenic cells and enhanced in vivo anti-infection potential of quaternized chitosan-loaded titania nanotubes

Infection is one of the major causes of failure of orthopedic implants. Our previous study demonstrated that nanotube modification of the implant surface, together with nanotubes loaded with quaternized chitosan （hydroxypropyltrimethyl ammonium chloride chitosan, HACC）, could effectively inhibit bacterial adherence and biofilm formation in vitro. Therefore, the aim of this study was to further investigate the in vitro cytocompatibility with osteogenic cells and the in vivo anti-infection activity of titanium implants with HACC-loaded nanotubes （NT-H）. The titanium implant （Ti）, nanotubes without polymer loading （NT）, and nanotubes loaded with chitosan （NT-C） were fabricated and served as controls. Firstly, we evaluated the cytocompatibility of these specimens with human bone marrow-derived mesenchymal stem cells in vitro. The observation of cell attachment, proliferation, spreading, and viability in vitro showed that NT-H has improved osteogenic activity compared with Ti and NT-C. A prophylaxis rat model with implantation in the femoral medullary cavity and inoculation with methiciUin-resistant Staphylococcus aureus was established and evaluated by radiographical, microbiological, and histopathological assessments. Our in vivo study demonstrated that NT-H coatings exhibited significant anti-infection capability compared with the Ti and NT-C groups. In conclusion, HACC-loaded nanotubes fabricated on a titanium substrate show good compatibility with osteogenic cells and enhanced anti-infection ability in vivo, providing a good foundation for clinical application to combat orthopedic implant-associated infections.

Heterogeneous Photocatalytic Mineralization of Chlorobenzene by Paratungstate-loaded Titania Catalysts in an Aqueous Medium

Paratungstate-loaded titania catalysts were prepared %via% the addition of a series of aqueous solutions of paratungstate(denoted as W_ 7) into an isopropanol solution of Ti[OCH(CH_ 3)_ 2]_ 4 by means of the sol-gel method. The catalysts were characterized by EDX, BET, FTIR, UV-Vis DRS, XRD and the results indicate that such paratungstate-loaded catalysts maintained their heptatungstate structure in the anatase titania matrix up to 400 ℃. The catalysts were tested for the heterogeneous photodegradation of chlorobenzene in aqueous media and showed a better catalytic activity than P-25 TiO_ 2 because paratungstate can prevent the recombination of the holes and electrons produced during irradiation. Moreover, the paratungstate-loaded titania catalysts can resist the disaggregation during the photoirradiation and can be easily recycled from the aqueous suspensions after reactions.