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 D...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.展开更多
Mesoporous TiO2 （m-TiO2） nanoparticles were used to prepare the porous film electrodes for dye-sensitized solar cells, and a second metal oxide （MgO, ZnO, A1203, or NiO） modifi- cation was carried out by dipping t...Mesoporous TiO2 （m-TiO2） nanoparticles were used to prepare the porous film electrodes for dye-sensitized solar cells, and a second metal oxide （MgO, ZnO, A1203, or NiO） modifi- cation was carried out by dipping the m-TiO2 electrode into their respective nitrate solution followed by annealing at 500 ℃. Experimental results indicated that the above second metal oxide modifications on m-TiO2 electrode are shown in all cases to act as barrier layer for the interracial charge transfer processes, but film electron transport and interfacial charge recombination characteristics under applied bias voltage were dependent significantly on the existing states and kinds of these second metal oxides. Those changes based on sec- ond metal oxide modifications showed good correlation with the current-voltage analyses of dye-sensitized solar cell, and all modifications were found to increase the open-circuit photo- voltage in various degrees, while the MgO, ZnO, and NiO modifications result in 23%, 13%, and 6% improvement in cell conversion efficiency, respectively. The above observations indi- cate that controlling the charge transport and recombination is very important to improve the photovoltaic performance of TiO2-based solar cell.展开更多
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 nanocrystal...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.展开更多
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 a...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.展开更多
Ordered mesoporous Fe/TiO2 was prepared by an evaporation-induced self-assembly method. The iron ions were in situ embedded in the pore wall of the TiO2 framework. The catalyst has excellent light-assisted Fenton cata...Ordered mesoporous Fe/TiO2 was prepared by an evaporation-induced self-assembly method. The iron ions were in situ embedded in the pore wall of the TiO2 framework. The catalyst has excellent light-assisted Fenton catalytic performance under UV and visible light irradiation. X-ray diffraction and transmission electron microscopy results showed that the TiO2 samples have an ordered two-dimensional hexagonal pore structure and an anatase phase structure with high crystallinity. The ordered pore structure of the TiO2 photocatalyst with a large specific surface area is beneficial to mass transfer and light harvesting. Furthermore, iron ions can be controlled by embedding them into the TiO2 framework to prevent iron ion loss and inactivation. After five cycles, the reaction rate of the ordered mesoporous Fe/TiO2 remained unchanged, indicating that the material has stable performance and broad application prospects for the purification of environmental pollutants.展开更多
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 difficult...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.展开更多
The mesoporous Ti O2 has been synthesized by evaporation induced self assembly(EISA) method. The thermogravimetric/differential scanning calorimetric(TG/DSC), X-ray diffraction(XRD), high-resolution transmission elect...The mesoporous Ti O2 has been synthesized by evaporation induced self assembly(EISA) method. The thermogravimetric/differential scanning calorimetric(TG/DSC), X-ray diffraction(XRD), high-resolution transmission electron microscopy(HR-TEM) and N2 adsorption desorption and adsorption are used to study the effects of the synthesized process condition on the microstructure of the as-synthesized mesoporous Ti O2. The photocatalytic performances of as-synthesized samples are evaluated by the degradation of the formaldehyde under ultraviolet light irradiations. The results demonstrate that the as-synthesized mesoporous Ti O2 are anatase with the uniform size about 20-40 nm. The sample is prepared using cetyltrimethyl ammonium bromide(CTAB) as the template with average pore size distribution of 8.12 nm, specific surface area of 68.47 m2/g and pore volume of 0.213 m L/g. The samples show decomposition of formaldehyde 95.8% under ultraviolet light irradiations for 90 min. These results provide a basic experimental process for preparation mesoporous Ti O2, which will posses a broad prospect in terms of the applications in improving indoor air quality.展开更多
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 approa...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.展开更多
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 ...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.展开更多
Mesoporous TiO_2-B/anatase microparticles have been in-situ synthesized from K_2Ti_2O_5 without template.The TiO_2-B phase around the particle surface accelerates the diffusion of charges through the interface,while t...Mesoporous TiO_2-B/anatase microparticles have been in-situ synthesized from K_2Ti_2O_5 without template.The TiO_2-B phase around the particle surface accelerates the diffusion of charges through the interface,while the anatase phase in the core maintains the capacity stability.The heterojunction interface between the main polymorph of anatase and the trace of TiO_2-B exhibits promising lithium ion battery performance.This trace of 5%(by mass) TiO_2-B determined by Raman spectra brings the first discharge capacity of this material to 247 mA · h ·g^(-1),giving 20%improvement compared to the anatase counterpart Stability testing at 1 C reveals that the capacity maintains at 171 mA·h·^(-1),which is better than 162 mA·h·g^(-1) for single phase anatase or 159 mA·h·g^(-1) for TiO_2-B.The mesoporous TiO_2-B/anatase rnicroparticles also show superior rate performance with 100 mA·h·g^(-1) at 40 C,increased by nearly 25%as compared to pure anatase.This opens a possibility of a general design route,which can be applied to other metal oxide electrode materials for rechargeable batteries and supercapacitors.展开更多
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 ...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.展开更多
Small Ag clusters confined in the channels of ordered mesoporous anatase TiO2 have been fabricated via a vacuum-assisted wet-impregnation method, utilizing well-ordered mesoporous anatase TiO2 with high thermal stabil...Small Ag clusters confined in the channels of ordered mesoporous anatase TiO2 have been fabricated via a vacuum-assisted wet-impregnation method, utilizing well-ordered mesoporous anatase TiO2 with high thermal stability as the host. The composites have been characterized in detail by X-ray diffraction, X-ray photoelectron spectroscopy X-ray absorption fine structure （XAFS） spectroscopy, N2 adsorption, UV-visible diffuse reflectance spectroscopy and transmission electron microscopy. The results indicate that small Ag clusters are formed and uniformly confined in the channels of mesoporous TiO2 with an obvious confinement effect. The presence of strong AgO interactions involving the Ag clusters in intimate contact with the pore walls of mesoporous TiO2 is confirmed by XAFS analysis, and favors the separation of photogenerated electron-hole pairs, as shown by steady-state surface photovoltage spectroscopy and transient-state surface photovoltage measurements. The ordered mesoporous Ag/TiO2 composites exhibit excellent solar-light-driven photocatalytic performance for the degradation of phenol. This is attributed to the synergistic effects between the small Ag clusters acting as traps to effectively capture the photogenerated electrons, and the surface plasmon resonance of the Ag clusters promoting the absorption of visible light. This study clearly demonstrates the high-efficiency utilization of noble metals in the fabrication of high-performance solar-light-driven photocatalysts.展开更多
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. ...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.展开更多
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 w...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.展开更多
Mesoporous TiO2microsphere(MTM)was synthesized via a simple solution route and then mixed with commercial TiO2(P25)to form highly homogeneous and stable TiO2colloid by simple hydrothermal treatment.The TiO2colloid was...Mesoporous TiO2microsphere(MTM)was synthesized via a simple solution route and then mixed with commercial TiO2(P25)to form highly homogeneous and stable TiO2colloid by simple hydrothermal treatment.The TiO2colloid was coated onto the plastic conductive substrate to prepare mesoporous TiO2film for flexible dye-sensitized solar cells(DSSCs)by low-temperature heat treatment.The influence of MTM content on the physicochemical properties of the flexible TiO2film was characterized by scanning electron microscope,transmission electron microscopy,X-ray diffraction,energy-dispersive X-ray spectrometer,N2adsorption-desorption isotherms,UV–vis absorption and diffuse reflectance spectra.It is revealed that with increasing the MTM content,the dye-loading capability of TiO2film and light-harvesting efficiency of flexible DSSCs are improved due to MTM having high surface area and acting as a light scattering center,respectively,resulting in the enhancement of photocurrent of flexible DSSCs.However,more and larger cracks having negative effect on the performances of flexible DSSCs are formed simultaneously.Under the optimal condition with MTM content of 20%,a flexible DSSC with overall light-to-electric energy conversion efficiency of 2.74%is achieved under a simulated solar light irradiation of 100 mW cm 2(AM 1.5),with 26%improvement in comparison with DSSCs based on P25 alone.展开更多
Several mesoporous TiO2 （MT） materials were synthesized under different conditions following a hydrothermal procedure using poly（ethylene-glycol）- block-poly（propylene-glycol）-block-poly（ethylene-glycol） （P12...Several mesoporous TiO2 （MT） materials were synthesized under different conditions following a hydrothermal procedure using poly（ethylene-glycol）- block-poly（propylene-glycol）-block-poly（ethylene-glycol） （P123） as the template and titanium isopropoxide as the titanium source. The molar ratios of Ti/P123, and the pH values of the reaction solution in an autoclave were investigated. Various techniques such as Brunauer-Emmett-Teller （BET）, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, laser Raman spectrometry （LRS）, scanning electron microscopy （SEM）, and high-resolution transmission electron microscopy （HRTEM） were used to characterize the products. Then, these materials were assembled into dye-sensitized solar cells （DSSCs）. Analysis of the J-V curves and electrochemical impedance spectroscopy （EIS） were applied to characterize the cells. The results indicated that the specific surface area and crystalline structure of these materials provide the possibility of high photocurrent for the cells, and that the structural characteristics of the specimens led to increased electron transfer resistance of the cells, which was beneficial for the improvement of the photovoltage of the DSSCs. The highest photoelectric conversion efficiency of the cells involving MT materials reached 8.33%, which, compared with that of P25- based solar cell （5.88%）, increased by 41.7%.展开更多
Titanium dioxide(Ti O_2) is widely employed as a solid photocatalyst for solar energy conversion and environmental remediation. The ability to construct porous Ti O_2 with controlled particle size and narrowed bandgap...Titanium dioxide(Ti O_2) is widely employed as a solid photocatalyst for solar energy conversion and environmental remediation. The ability to construct porous Ti O_2 with controlled particle size and narrowed bandgap is an essential requirement for the design of highly efficient and recyclable photocatalysts. Here, we report a templatefree acetic acid induced method for the synthesis of visiblelight responsive carbon-doped Ti O_2 microplates with high crystallinity and mesoporous structure. It is shown that the electron-withdrawing bidentate carboxylate ligands derived from acetic acid can narrow the bandgap of Ti O_2(1.84 e V)substantially. Moreover, the resultant microplate photocatalysts exhibit excellent photocatalytic efficiency and solid–liquid separation performance, which will be beneficial for future industrial applications.展开更多
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. Sequenti...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.展开更多
基金supported by the National Natural Science Foundation of China(Nos.51678556 and 51578531)the National Key Research&Development Program of China(No.2016YFC0400806)
文摘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.
文摘Mesoporous TiO2 （m-TiO2） nanoparticles were used to prepare the porous film electrodes for dye-sensitized solar cells, and a second metal oxide （MgO, ZnO, A1203, or NiO） modifi- cation was carried out by dipping the m-TiO2 electrode into their respective nitrate solution followed by annealing at 500 ℃. Experimental results indicated that the above second metal oxide modifications on m-TiO2 electrode are shown in all cases to act as barrier layer for the interracial charge transfer processes, but film electron transport and interfacial charge recombination characteristics under applied bias voltage were dependent significantly on the existing states and kinds of these second metal oxides. Those changes based on sec- ond metal oxide modifications showed good correlation with the current-voltage analyses of dye-sensitized solar cell, and all modifications were found to increase the open-circuit photo- voltage in various degrees, while the MgO, ZnO, and NiO modifications result in 23%, 13%, and 6% improvement in cell conversion efficiency, respectively. The above observations indi- cate that controlling the charge transport and recombination is very important to improve the photovoltaic performance of TiO2-based solar cell.
文摘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.
基金supported by the National Natural Science Foundation of China (Nos. 21206150, U1304209 and U1204215)the Foundation for University Young Key Teacher by Henan Province (No. 2014GGJS-005)
文摘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.
基金supported by the National Natural Science Foundation of China(21876114,21761142011,51572174)Shanghai Government(17SG44)+2 种基金International Joint Laboratory on Resource Chemistry(IJLRC)Ministry of Education of China(PCSIRT_IRT_16R49)supported by The Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning and Shuguang Research Program of Shanghai Education Committee~~
文摘Ordered mesoporous Fe/TiO2 was prepared by an evaporation-induced self-assembly method. The iron ions were in situ embedded in the pore wall of the TiO2 framework. The catalyst has excellent light-assisted Fenton catalytic performance under UV and visible light irradiation. X-ray diffraction and transmission electron microscopy results showed that the TiO2 samples have an ordered two-dimensional hexagonal pore structure and an anatase phase structure with high crystallinity. The ordered pore structure of the TiO2 photocatalyst with a large specific surface area is beneficial to mass transfer and light harvesting. Furthermore, iron ions can be controlled by embedding them into the TiO2 framework to prevent iron ion loss and inactivation. After five cycles, the reaction rate of the ordered mesoporous Fe/TiO2 remained unchanged, indicating that the material has stable performance and broad application prospects for the purification of environmental pollutants.
基金financially supported by the National Key R & D Projects (Nos. 2021YFC1910504, 2019YFC1907101, 2019YFC1907103, and 2017YFB0702304)the Key R & D Project in Ningxia Hui Autonomous Region, China (No. 2020BCE01001)+6 种基金the Key and Normal Projects National Natural Science Foundation of China (Nos. U2002212 and 51672024)the Xijiang Innovation and Entrepreneurship Team (No. 2017A0109004)the Fundamental Research Funds for the Central Universities (Nos. FRF-BD-20-24A, FRF-TP-20-031A1, FRF-IC-19-017Z, FRF-GF-19-032B, and 06500141)the Integration of Green Key Process Systems MIIT, Natural Science Foundation of Beijing Municipality (No. 2214073)the Guangdong Basic and Applied Research Foundation, China (No. 2020A1515110408)the Foshan Science and Technology Innovation Special Foundation, China (No. BK21BE002)the Postdoctor Research Foundation of Shunde Graduate School of University of Science and Technology Beijing (No. 2020BH004)
文摘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.
基金Projects(51102026,51272032) supported by the Program for the National Natural Science Foundation of ChinaProject(11A014) supported by the Scientific Research Fund of Hunan Provincial Education DepartmentProject supported by the Aid Program for Science and Technology Innovative Research Team in Higher Educational Instituions of Hunan Province,China
文摘The mesoporous Ti O2 has been synthesized by evaporation induced self assembly(EISA) method. The thermogravimetric/differential scanning calorimetric(TG/DSC), X-ray diffraction(XRD), high-resolution transmission electron microscopy(HR-TEM) and N2 adsorption desorption and adsorption are used to study the effects of the synthesized process condition on the microstructure of the as-synthesized mesoporous Ti O2. The photocatalytic performances of as-synthesized samples are evaluated by the degradation of the formaldehyde under ultraviolet light irradiations. The results demonstrate that the as-synthesized mesoporous Ti O2 are anatase with the uniform size about 20-40 nm. The sample is prepared using cetyltrimethyl ammonium bromide(CTAB) as the template with average pore size distribution of 8.12 nm, specific surface area of 68.47 m2/g and pore volume of 0.213 m L/g. The samples show decomposition of formaldehyde 95.8% under ultraviolet light irradiations for 90 min. These results provide a basic experimental process for preparation mesoporous Ti O2, which will posses a broad prospect in terms of the applications in improving indoor air quality.
基金supported by the National Natural Science Foundation of China(Nos.51372041,51422202,21673048,21875044,51822202 and 51772050)Key Basic Research Program of Science and Technology Commission of Shanghai Municipality(No.17JC1400100)+1 种基金Youth Top-notch Talent Support Program of China,Shanghai Rising-Star Program(No.18QA1400100)DHU Distinguished Young Professor Program。
文摘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.
基金funded by the Science and Technology Development Fund (STDF), Ministry of Scientific Research (No. 1414, "Quantum Dots Nanomaterials Dye Sensitized Solar Cells")
文摘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.
基金Supported by the Program for Changjiang Scholars and Innovative Research Team in University(PCSIRT 0732)the National Natural Science Foundation of China(21136004,20736002,21176113,20876073)+2 种基金NSFC-RGC(20731160614)China Postdoctoral Science Foundation(20110491407)the National Basic Research Program of China(2009CB623407,2009CB219902 and 2009CB226103)
文摘Mesoporous TiO_2-B/anatase microparticles have been in-situ synthesized from K_2Ti_2O_5 without template.The TiO_2-B phase around the particle surface accelerates the diffusion of charges through the interface,while the anatase phase in the core maintains the capacity stability.The heterojunction interface between the main polymorph of anatase and the trace of TiO_2-B exhibits promising lithium ion battery performance.This trace of 5%(by mass) TiO_2-B determined by Raman spectra brings the first discharge capacity of this material to 247 mA · h ·g^(-1),giving 20%improvement compared to the anatase counterpart Stability testing at 1 C reveals that the capacity maintains at 171 mA·h·^(-1),which is better than 162 mA·h·g^(-1) for single phase anatase or 159 mA·h·g^(-1) for TiO_2-B.The mesoporous TiO_2-B/anatase rnicroparticles also show superior rate performance with 100 mA·h·g^(-1) at 40 C,increased by nearly 25%as compared to pure anatase.This opens a possibility of a general design route,which can be applied to other metal oxide electrode materials for rechargeable batteries and supercapacitors.
基金Supported by the National Basic Research Program of China (No. 2009CB320300)National Natural Science Foundation of China (No. 61072023)National High Technology Research and Development Programs (No.2012AA040506, No. 2012AA101608)
文摘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.
文摘Small Ag clusters confined in the channels of ordered mesoporous anatase TiO2 have been fabricated via a vacuum-assisted wet-impregnation method, utilizing well-ordered mesoporous anatase TiO2 with high thermal stability as the host. The composites have been characterized in detail by X-ray diffraction, X-ray photoelectron spectroscopy X-ray absorption fine structure （XAFS） spectroscopy, N2 adsorption, UV-visible diffuse reflectance spectroscopy and transmission electron microscopy. The results indicate that small Ag clusters are formed and uniformly confined in the channels of mesoporous TiO2 with an obvious confinement effect. The presence of strong AgO interactions involving the Ag clusters in intimate contact with the pore walls of mesoporous TiO2 is confirmed by XAFS analysis, and favors the separation of photogenerated electron-hole pairs, as shown by steady-state surface photovoltage spectroscopy and transient-state surface photovoltage measurements. The ordered mesoporous Ag/TiO2 composites exhibit excellent solar-light-driven photocatalytic performance for the degradation of phenol. This is attributed to the synergistic effects between the small Ag clusters acting as traps to effectively capture the photogenerated electrons, and the surface plasmon resonance of the Ag clusters promoting the absorption of visible light. This study clearly demonstrates the high-efficiency utilization of noble metals in the fabrication of high-performance solar-light-driven photocatalysts.
基金supported by grants from the National High Technology Research and Development Program (863) of China (Nos. 2010AA064902 and 2012AA062702)the Key Innovation Team for Science and Technology of Zhejiang Province (No. 2009R50047)
文摘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.
基金This work is supported by the National Natural Science Foundation of China （Nos. 21236003, 21322607, 21406072, 21471056, 21676093 and 91534202）, Shanghai Educational Development Foundation （No. 14CG29）, the Basic Research Program of Shanghai （No. 14JCI406402）, China Postdoctoral Science Foundation （Nos. 2014M560307, 2014M561497, 2015T80408）, and the Fundamental Research Funds for the Central Universities.
文摘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.
基金supported financially by the National High Technology Research and Development Program of China(2009AA03Z217)the National Natural Science Foundation of China(90922028)+1 种基金the Key Project of Chinese Ministry of Education(211204)the Fund of Fujian Provincial Key Laboratory of Nanomaterials(NM10-5)
文摘Mesoporous TiO2microsphere(MTM)was synthesized via a simple solution route and then mixed with commercial TiO2(P25)to form highly homogeneous and stable TiO2colloid by simple hydrothermal treatment.The TiO2colloid was coated onto the plastic conductive substrate to prepare mesoporous TiO2film for flexible dye-sensitized solar cells(DSSCs)by low-temperature heat treatment.The influence of MTM content on the physicochemical properties of the flexible TiO2film was characterized by scanning electron microscope,transmission electron microscopy,X-ray diffraction,energy-dispersive X-ray spectrometer,N2adsorption-desorption isotherms,UV–vis absorption and diffuse reflectance spectra.It is revealed that with increasing the MTM content,the dye-loading capability of TiO2film and light-harvesting efficiency of flexible DSSCs are improved due to MTM having high surface area and acting as a light scattering center,respectively,resulting in the enhancement of photocurrent of flexible DSSCs.However,more and larger cracks having negative effect on the performances of flexible DSSCs are formed simultaneously.Under the optimal condition with MTM content of 20%,a flexible DSSC with overall light-to-electric energy conversion efficiency of 2.74%is achieved under a simulated solar light irradiation of 100 mW cm 2(AM 1.5),with 26%improvement in comparison with DSSCs based on P25 alone.
文摘Several mesoporous TiO2 （MT） materials were synthesized under different conditions following a hydrothermal procedure using poly（ethylene-glycol）- block-poly（propylene-glycol）-block-poly（ethylene-glycol） （P123） as the template and titanium isopropoxide as the titanium source. The molar ratios of Ti/P123, and the pH values of the reaction solution in an autoclave were investigated. Various techniques such as Brunauer-Emmett-Teller （BET）, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, laser Raman spectrometry （LRS）, scanning electron microscopy （SEM）, and high-resolution transmission electron microscopy （HRTEM） were used to characterize the products. Then, these materials were assembled into dye-sensitized solar cells （DSSCs）. Analysis of the J-V curves and electrochemical impedance spectroscopy （EIS） were applied to characterize the cells. The results indicated that the specific surface area and crystalline structure of these materials provide the possibility of high photocurrent for the cells, and that the structural characteristics of the specimens led to increased electron transfer resistance of the cells, which was beneficial for the improvement of the photovoltage of the DSSCs. The highest photoelectric conversion efficiency of the cells involving MT materials reached 8.33%, which, compared with that of P25- based solar cell （5.88%）, increased by 41.7%.
基金supported by the National Natural Science Foundation of China(20966006)the Natural Science Foundation of the Inner Mongolia Autonomous Region(2014MS0218)the Program for Innovative Research Team in Universities of Inner Mongolia Autonomous Region(NMGIRT-A1603)
文摘Titanium dioxide(Ti O_2) is widely employed as a solid photocatalyst for solar energy conversion and environmental remediation. The ability to construct porous Ti O_2 with controlled particle size and narrowed bandgap is an essential requirement for the design of highly efficient and recyclable photocatalysts. Here, we report a templatefree acetic acid induced method for the synthesis of visiblelight responsive carbon-doped Ti O_2 microplates with high crystallinity and mesoporous structure. It is shown that the electron-withdrawing bidentate carboxylate ligands derived from acetic acid can narrow the bandgap of Ti O_2(1.84 e V)substantially. Moreover, the resultant microplate photocatalysts exhibit excellent photocatalytic efficiency and solid–liquid separation performance, which will be beneficial for future industrial applications.
基金supported by the University of Science of Ho Chi Munh City and Dongthap University
文摘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.
