Mesoporous TiO2 microparticles formed by the oriented attachment of nanocrystals： A super-durable anode material for sodium-ion batteries

Spindle-shaped anatase TiO2 secondary particles were successfully fabricated via the oriented attachment of primary nanocrystals. By adjusting the concentration of tetrabutyl titanate, the size of the TiO2 nanocrystals and particles could be controlled, resulting in pore evolution. Pores for the random aggregation of secondary particles gradually transformed to nanopores originating from the oriented attachment of the primary nanocrystals, resulting in an excellent micro/nanostructure that increased the performance of a sodium-ion battery. The mesoporous TiO2 microparticle anode, with its unique combination of nanocrystals and uniform nanopores, displays super durability （95 mAh/g after 11,000 cycles at I C）, high initial efficiency （61.4%）, and excellent rate performance （265 and 77 mAh/g at 0.1 and 20 C, respectively）. In particular, at slow discharge （0.1 C） and fast charge （5, 50, and 100 C） rates, the anatase TiO2 shows remarkable initial charge capacities of 200, 119, and 56 mAh/g, corresponding to 172, 127, and 56 mAh/g, after 150 cycles, respectively, thus meeting the requirements for fast energy storage. This excellent performance can be attributed to the stability of the material and its high ionic conductivity, resulting from the stable architecture with a mesoporous microstructure and without the random aggregation of secondary particles. A fundamental understanding of the pore structure and controllable pore construction has been proven to be effective in increasing the rate capability and durability of nanostructured electrode materials.

Template-free synthesis of core-shell Fe_(3)O_(4)@MoS_(2)@mesoporous TiO_(2) magnetic photocatalyst for wastewater treatment

TiO_(2)is the dominant and most widely researched photocatalyst for environmental remediation,however,the drawbacks,such as only responding to UV light(<5%of sunlight),low charge separation efficiency,and difficulties in recycling,have severely hindered its practical application.Herein,we synthesized magnetically separable Fe_(3)O_(4)@MoS_(2)@mesoporous TiO_(2)(FMmT)photocatalysts via a simple,green,and template-free solvothermal method combined with ultrasonic hydrolysis.It is found that FMmT possesses a high specific surface area(55.09 m2·g−1),enhanced visible-light responsiveness(~521 nm),and remarkable photogenerated charge separation efficiency.In addition,the photocatalytic degradation efficiencies of FMmT for methylene blue(MB),rhodamine B(RhB),and tetracycline(TC)are 99.4%,98.5%,and 89.3%within 300 min,respectively.The corresponding degradation rates are 4.5,4.3,and 3.1 times higher than those of pure TiO_(2)separately.Owing to the high saturation magnetization(43.1 A·m^(2)·kg^(−1)),FMmT can achieve effective recycling with an applied magnetic field.The improved photocatalytic activity is closely related to the effective transport of photogenerated electrons by the active interlayer MoS_(2) and the electron–hole separation caused by the MoS_(2)@TiO_(2)heterojunction.Meanwhile,the excellent light-harvesting ability and abundant reactive sites of the mesoporous TiO_(2)shell further boost the photocatalytic efficiency of FMmT.This work provides a new approach and some experimental basis for the design and performance improvement of magnetic photocatalysts by innovatively incorporating MoS2 as the active interlayer and integrating it with a mesoporous shell.

Defect-enhanced photocatalytic removal of dimethylarsinic acid over mixed-phase mesoporous TiO2

Much attention has been paid to the pollutant dimethylarsenic acid(DMA),because of its high toxicity even at very low doses.Although TiO2 photocatalytic oxidation(PCO)is one of the few effective methods for treating DMA-containing water,the efficient decomposition of DMA and simultaneous removal of toxic arsenic species remains a significant but challenging task.Here,defective mesoporous TiO2 with mixed-phase structure was synthesized and used as both photocatalyst and adsorbent for DMA removal.Due to the reduced band-gap and enhanced separation of photogenerated charge carriers,the oxygen-deficient TiO2 nanostructures exhibited 4.2 times higher PCO efficiency than commercial TiO2(P25).More importantly,the high surface area of the mesoporous TiO2 provided sufficient active sites for in-situ adsorption and reaction,resulting in the efficient removal of as-formed As(V).Combining the experimental and characterization results,the different roles of reactive species during PCO reactions were clarified.In the presence of hole(h+)as the dominant oxidation species,DMA was demethylated and transformed into MMA.Thereafter,MMA was subsequently reduced to As(Ⅲ)by photo-generated electrons.Superoxide radicals(O2·-)played a significant role in oxidizing As(Ⅲ)into As(Ⅴ),which was finally adsorptively removed by the mesoporous TiO2.

MESOPOROUS TIO_2 NANO-SPHERES: ELECTROSPRAY COMBINED SOL-GEL FABRICATION AND APPLICATION TO ORGANIC PHOSPHORUS DEGRADATION

In this work, electrospray technique combined sol-gel method was used to prepare porous TiO2 film. X-ray Photoelectron Spectroscopy (XPS), X-Ray Diffraction (XRD), and Scanning Electron Microscope (SEM) analyses were conducted to examine the chemical composition, phase structure, and surface morphology of the sprayed TiO2 film. After calcined at 450℃ in air atmosphere for 2 h, mesoporous TiO2 nano-spheres clusters were formed on the surface of silicon wafer and the average size of nano-spheres was 250 nm. Ti presented as Ti 4+ oxidation state in TiO2 film, and the TiO2 film exhibited the anatase phase. The sprayed porous TiO2 films were employed as photocatalyst to degrade organic phosphorus in water samples. Compared with the TiO2 film prepared by Sol-Gel spin-coating method, the porous TiO2 film deposited by electrospray combined sol-gel method showed higher photocatalytic activity.

Plasmonic Au Decorated Single-crystal-like TiO2-NaYF4 Mesoporous Microspheres for Enhanced Broadband Photocatalysis

Single-crystal-like TiO2 mesoporous microspheres have been reported with high photocatalytic activity under ultraviolet light （UV light） because of their high specific surface areas and single-crystal-like channel walls. In this work, plasmonic gold nanoparticles （Au NPs） and fl-NaYF4： Yb3＋, Er3＋ upconversion nanoparticles （UCNPs） were composited with single-crystal-like TiO2 mesoporous microspheres through a series of facile approaches, aiming at broadening response region of solar light from UV to visible and near infrared light and enhancing the photocata- lyric activity further. The structure was rationally designed by modifying the pore size of TiO2 mesoporous micro- spheres so as to anchor plasmonic Au NPs, and covering β-NaYF4： Yb3＋, Er3＋ with SiO2 in order to embed UCNPs into TiO2 mesoporous microspheres via hydrophilic interaction. This work studied the attribution of Au NPs and UCNPs to photocatalysis and found out that combining Au NPs and certain amount of UCNPs with single-crystal- like TiO2 mesoporous microspheres in a monolithic architecture would bring enhanced broadband photocatalytic activity under simulated solar light. Consequently, the composite photocatalyts containing 150 mg UCNPs showed a significant enhancement in reaction rate, which was 36.02% higher than commercial P25 and 85.09% higher than pure TiO2 mesoporous microspheres under simulated solar light.

Synthesis of Mesoporous Anatase TiO2 Sphere with High Surface Area and Enhanced Photocatalytic Activity

Mesoporous anatase TiO2 spheres with high surface area（119 m^2g^（-1）） were successfully synthesized via a facile and green template-free method. The prepared TiO2 was characterized by X-ray diffraction（XRD）,N2 adsorption, scanning electron microscopy（SEM）, transmission electron microscopy（TEM） and UV–vis absorbance spectra. It was found that the prepared TiO2 is characterized by pure anatase phase, which shows uniform spheres and has a typical mesostructure with a high specific surface area and a large pore volume. The effects of complexant（acetylacetone） amount, crystallization temperature and calcination temperature were also investigated. Based on the results, a sketch for the preparation of mesoporous TiO2 was proposed. First, complex formed between tetrabutyl titanate and acetylacetone in ethanol. After introduction of aqueous of ammonia sulfate and urea, hydrolysis of tetrabutyl titanate would occur slowly,and sol of TiO2 was formed. Then, crystallization proceeded under hydrothermal conditions. Calcination process favored the formation of bigger TiO2 crystal through combining of the small crystals in TiO2.This led to the formation of bigger mesopores between TiO2 crystals. Photocatalytic activity of the prepared TiO2 was evaluated by decomposition of methyl orange.

Photocatalytic parameters and kinetic study for degradation of dichlorophenol-indophenol (DCPIP) dye using highly active mesoporous TiO_2 nanoparticles

Highly active mesoporous TiO_2 of about 6 nm crystal size and 280.7 m^2/g specific surface areas has been successfully synthesized via controlled hydrolysis of titanium butoxide at acidic medium. It was characterized by means of XRD（X-ray diffraction）, SEM（scanning electron microscopy）, TEM（transmission electron microscopy）, FT-IR（Fourier transform infrared spectroscopy）, TGA（thermogravimetric analysis）, DSC（differential scanning calorimetry） and BET（Brunauer–Emmett–Teller） surface area. The degradation of dichlorophenol-indophenol（DCPIP） under ultraviolet（UV） light was studied to evaluate the photocatalytic activity of samples. The effects of different parameters and kinetics were investigated. Accordingly, a complete degradation of DCPIP dye was achieved by applying the optimal operational conditions of 1 g/L of catalyst, 10 mg/L of DCPIP, pH of 3 and the temperature at 25 ± 3°C after 3 min under UV irradiation. Meanwhile, the Langmuir–Hinshelwood kinetic model described the variations in pure photocatalytic branch in consistent with a first order power law model.The results proved that the prepared TiO_2 nanoparticle has a photocatalytic activity significantly better than Degussa P-25.

Stepwise construction of Pt decorated oxygen-deficient mesoporous titania microspheres with core-shell structure and magnetic separability for efficient visible-light photocatalysis

Solid photocatalysts with high specific surface area,superior photoactivity and ease of recycling are highly desired in chemical process,water treatment and so on.In this study,a facile stepwise sol-gel coating approach was utilized to synthesize Pt decorated oxygen-deficient mesoporous titania microspheres with core-shell structure and convenient magnetic separability(denoted as Fe3 O4@-SiO2@Pt/mTiO2-x).These photocatalysts consist of magnetic Fe3 O4 cores,nonporous insulating SiO2 middle layer and mesoporous anatase TiO2-x shell decorated by Pt nanoparticles(~3.5 nm)through wet impregnation and H2 reduction.As a result of high activity of oxygen-deficiency of black TiO2-x by H2 reduction and efficient inhibition of electron-hole recombination by Pt nanoparticles,the rationally designed core-shell Fe3 O4@SiO2@Pt/mTiO2-x photocatalysts exhibit superior photocatalytic performance in rhodamine B(RhB)degradation under visible light irradiation,with more than 98%of RhB degraded within 50 min.These core-shell structured photocatalysts show excellent recyclability under the assistance of magnetic separation with well-retained photocatalytic performance even after running five cycles.This stepwise synthesis method paves the way for the rational design of a high-efficiency recyclable heterogeneous catalyst,including photocatalysts,for various applications.

Template-free synthesis of carbon doped TiO_2 mesoporous microplates for enhanced visible light photodegradation

报道了一种在乙酸蒸汽中蒸发有机钛源(Ti(i-Pr O)_4),无模版合成碳掺杂介孔Ti O_2微板块的方法.该微板块由纳米晶组成,具有统一的介孔结构和微米级厚度.制备过程的副产有机物经炭化后对Ti O_2形成了表面和/或间隙碳掺杂,特别是源于乙酸的羧基最终与Ti O_2形成双齿螯合结构,强吸电子特性使羧基在价带边引入了带尾,导致Ti O_2带隙大幅减小(1.84 e V).独特的形貌和显著缩减的带隙,使该Ti O_2微板块显示出较高的可见光苯酚降解活性和优良的固-液分离性能.

Tricrystalline TiO_2 with enhanced photocatalytic activity and durability for removing volatile organic compounds from indoor air

It is important to develop efficient and economic techniques for removing volatile organic compounds（VOCs） in indoor air. Heterogeneous Ti O2-based semiconductors are a promising technology for achieving this goal. Anatase/brookite/rutile tricrystalline Ti O2 with mesoporous structure was synthesized by a low-temperature hydrothermal route in the presence of HNO3.The obtained samples were characterized by X-ray diffraction and N2 adsorption-desorption isotherm. The photocatalytic activity was evaluated by photocatalytic decomposition of toluene in air under UV light illumination. The results show that tricrystalline Ti O2 exhibited higher photocatalytic activity and durability toward gaseous toluene than bicrystalline Ti O2,due to the synergistic effects of high surface area, uniform mesoporous structure and junctions among mixed phases. The tricrystalline Ti O2 prepared at R HNO3= 0.8, containing80.7% anatase, 15.6% brookite and 3.7% rutile, exhibited the highest photocatalytic activity,about 3.85-fold higher than that of P25. The high activity did not significantly degrade even after five reuse cycles. In conclusion, it is expected that our study regarding gas-phase degradation of toluene over tricrystalline Ti O2 will enrich the chemistry of the Ti O2-based materials as photocatalysts for environmental remediation and stimulate further research interest on this intriguing topic.

Performance of CdS/CdSe/ZnS quantum dot-sensitized TiO_2 mesopores for solar cells

We prepare CdS/CdSe/ZnS thin films by successive ionic layer adsorption and reaction method. Results show a wider photoresponse range of TiO2 mesopores from the ultraviolet region to the visible light region. Sequentially assembled CdS/CdSe/ZnS quantum and photocurrent efficiency. A high efficiency of dots exhibit significantly improved light-harvesting ability 1.059354% is obtained.