Zn掺杂TiO2的光催化性能研究

以钛酸四丁酯为钛源,醋酸锌为锌源用溶胶凝胶法制备了不同比例Zn掺杂TiO2纳米颗粒,掺杂比例为0 at%~10 at%。用X射线衍射(XRD)、透射电镜(TEM)、能谱分析(EDS)、紫外可见光谱(UV-Vis)等研究手段对所制备的Zn掺杂TiO2纳米颗粒进行分析,并对样品的光催化活性进行了研究。结果显示400℃退火的样品均为锐钛矿相TiO2,没有ZnO的衍射峰出现,EDS分析结果显示Zn离子存在于TiO2中,说明Zn离子成功掺杂进入TiO2晶格。通过TEM图像和谢乐公式计算可知,Zn掺杂TiO2的平均晶粒尺寸为6~7 nm,掺杂比例为1%的样品光催化降解亚甲基蓝染料效果最好。

Synthesis and highly efficient photocatalytic activity of mixed oxides derived from ZnNiAl layered double hydroxides

ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.

Preparation and photocatalytic performance of porous ZnO microrods loaded with Ag

Porous silver-modified ZnO microrods photocatalysts were synthesized through direct thermal decomposition of the Ag-doped zinctartrate precursor,which was prepared by homogeneous precipitation method at 80 °C for 2 h.The obtained samples were characterized by XRD,FTIR,TG？DTA and UV-VIS absorption spectroscopy.The photocatalytic activity of the as-prepared porous Ag/ZnO microrods was tested with the photocatalytic degradation of methyl orange.The results indicate that doping Ag greatly improves the photocatalytic efficiency of ZnO and 3% Ag-doped（mole fraction） ZnO porous microrod photocatalyst exhibits the highest photocatalytic decolorization efficiency,leading to as much as 80% reduction of MO concentration in 120 min.Moreover,the 3% Ag-doped porous microrods also possess higher photocatalytic activity under the real sunlight irradiation.

Enhanced photocatalytic properties of hierarchical nanostructured TiO_2 spheres synthesized with titanium powders

Using Ti powder as reagent, TiO 2 nanoneedle/nanoribbon spheres were prepared via hydrothermal method in NaOH solution. The samples were characterized by field emission scanning electron microscopy （FESEM）, transmission electron microscopy （TEM） with selected area electron diffraction （SAED）, X-ray diffraction （XRD）, and UV-visible light absorption spectrum. The results indicate that the growth orientations of the crystals are influenced by the hydrothermal temperature and NaOH concentration. The diameter of the nanoneedle spheres and nanoribbon spheres （40 50 μm） are almost the same as that of Ti powders. TiO 2 nanoneedle/nanoribbon sphere powders are anatase after heat treatment at 450 °C for 1 h. Furthermore, methyl orange was used as a target molecule to estimate the photocatalytic activity of the specimens. Under the same testing conditions, the photocatalytic activities of the products decrease in the following order： TiO 2 nanoneedle sphere, TiO 2 nanoribbon sphere and P25.

Solvent-assisted synthesis of porous g-C_3N_4 with efficient visible-light photocatalvtic performance for NO removal

Graphitic carbon nitride（g-C3N4） with efficient photocatalytic activity was synthesized through thermal polymerization of thiourea with the addition of water（CN-W） or ethanol（CN-E） at 550 ℃for 2 h.The physicochemical properties of the g-C3N4 were investigated by X-ray diffraction,transmission electron microscopy,ultraviolet-visible spectroscopy,photoluminescence spectroscopy,diffuse-reflection spectroscopy,BET and BJH surface area characterization,and elemental analysis.The carbon content was found to have self-doped into the g-C3N4 matrix during the thermal polymerization of thiourea and ethanol.CN-W and CN-E showed considerably enhanced visible-light photocatalytic activity,with NO removal percentages of 37.2%and 48.3%,respectively.Compared with pure g-C3N4,both the short and long lifetimes of the charge carriers in CN-W and CN-E were found to be prolonged.The mechanism of improved visible-light photocatalytic activity was deduced.The present work may provide a facile route to optimize the microstructure of g-C3N4photocatalysts for high-performance environmental and energy applications.

Mesh-Like Bi2MoO6 with Enhanced and Stable Visible Light Photocatalytic Activity

Mesh-like Bi2MoO6 product was successfully synthesized by a hydrothermal method without using any surfactant or template. The pH value played an important role in the formation of this morphology. The as-prepared mesh-like Bi2MoO6 sample exhibited excellent visible-light-driven photocatalytic e ciency. The photocatalytic activity of the mesh-like Bi2MoO6 sample was much higher than that of bulk Bi2MoO6 sample prepared by solid-state reac-tion. Di erence in the photocatalytic activities of the mesh-like Bi2MoO6 sample and bulk Bi2MoO6 sample was further investigated.

Fabrication and photocatalytic properties of Cu_2S/T-ZnO_w heterostructures via simple polyol process

The Cu2S/tetrapod-like ZnO whisker（T-ZnOw） heterostructures were successfully synthesized via a simple polyol process employing the poly（vinyl pyrrolidone）（PVP） as a surfactant.The as-prepared heterostructures were characterized by X-ray diffraction（XRD）,field emission scanning electron microscopy（FESEM）,X-ray photoelectron spectroscopy（XPS） and Fourier transform infrared（FTIR）.The photocatalytic properties of Cu2S/T-ZnOw nanocomposites synthesized with different PVP concentrations were evaluated by photodegradation of methyl orange（MO） under UV irradiation.The results show that the Cu2S/T-ZnOw nanocomposites exhibit remarkable improved photocatalytic property compared with the pure T-ZnOw.The sample prepared with 3.0 g/L PVP shows an excellent photocatalytic property and the highest photodegradation rate of MO is 97% after UV irradiation for 120 min.Besides,the photocatalytic activity of the photocatalyst has no evident decrease even after four cycles,which demonstrates that the Cu2S/T-ZnOw photocatalyst exhibits an excellent photostability.Moreover,the photocatalytic mechanism of the Cu2S/T-ZnOw nanocomposites was also discussed.

Fabrication and Photocatalysis of TiO2 Flower-like Nanostructures

TiO2 nanostructures were fabricated by a reaction of Ti foils in H2O2 solution at mild temperature, Porous TiO2 nanostructurcs, well adhered to Ti foil surfaces, were formed at 80 ℃ in 10 rain, and then flower- like and rod nanostructures formed in succession after a longer reaction time. Samples prepared at 80 ℃ for 4 h arc amorphous, and anatase-dominated crystal phase emerged in the sample prepared for as long as 10 h. Almost pure anatase phase were obtained in TiO2 nanostructures by annealing the samples at a temperature of 300 ℃. Photoeatalysis of the TiO2 nanostructures was characterized by the degradation of RhB dye molecules in an aqueous solution exposed to ultraviolet light. Results show a 7 cm^2 annealed TiO2 flower-like nanostrueture having the degradation rate of RhB as fast as 29.8 times that of the dye solution exposed to ultraviolet light alone.

Facile preparation of sepiolite@LDH composites for the visible-light degradation of organic dyes

Sepiolite@LDH(Sep@LDH)composites were designed and prepared based on the assembly of layered double hydroxides(LDH)on acidified sepiolites(Sep)for the simultaneous photocatalytic degradation of methyl orange(MO)and methylene blue(MB).The structure,morphology,texture,optical properties,and photocatalytic performance of the prepared Sep@LDH were studied in detail.Among the Sep@LDH composites,Sep4@LDH(4.0 g Sep)exhibited the highest photocatalytic activity under visible‐light irradiation,which could be attributed to its large surface area,high crystallinity,and plentiful active sites on its surface.The photodegradation of the dyes followed a pseudo first‐order kinetic model(Langmuir‐Hinshelwood model),indicating that the copious and homogeneous active sites on the surface of the composites contributed to the high photocatalytic activity.The photodegradation mechanism was studied by examining the active species(^-OH,h+,and·O2^-anions)using appropriate scavengers.It was found that·OH radicals played a critical role in the photocatalytic process of MO and MB,where the generation of·OH radicals occurred on the electron/hole(e^-/h+)pairs on the surface of the Sep@LDH composites.

Influence of Ag on photocatalytic performance of Ag/ZnO nanosheet photocatalysts

Ag/ZnO nanosheet composites were prepared by zinc nitrate, sodium hydroxide and silver nitrate via a simple hydrothermal method. The crystal structure, morphology, optical property and photocatalytic performance were studied by means of XRD, SEM, HRTEM, XPS, and PL methods. It is found that both the pure ZnO and composite Ag/ZnO samples have the same morphology of nanosheet. The interaction of spherical Ag particles with ZnO matrix in the Ag/ZnO sample leads to an increase in photocatalytic efficiency for the possible increase of concentration of surface hydroxyl and the photo-induced electrons and holes. The addition of Ag can reduce the recombination rate of photo-generated carriers and the sample with addition of 3 at% Ag to ZnO exhibits the best photocatalytic activity with the degradation rate up to 95% within 15 min.

Preparation and Photocatalytic Properties of Magnetically Separable TiO_2 Supported on Nickel Ferrite

A magnetically separable photocatalyst TiO2/SiO2/NiFe2O4 （TSN） with a typical ferromagnetic hysteresis was prepared by a liquid catalytic phase transfer method. When the intensity of applied magnetic field weakened to zero, the remnant magnetism of the prepared photocatalyst faded to zero. The photocatalytst can be separated from water when an external magnetic field is added and redispersed into aqueous solution after the external magnetic field is eliminated, that makes the photocatalysts promising for wastewater treatment. Transmission electron microscope （TEM） and X-ray diffractometer （XRD） were used to characterize the structure of the photocatalyst indicating that the magnetic SiOffNiFe204 （SN） particle was compactly enveloped by P-25 titania and Tit2 shell was formed. The magnetic composite showed high photocatalytic activity for the degradation of methyl orange in water. A thin SiO2 layer between NiFe2O4 and TiO2 shell prevented effectively the leakage of charges from TiO2 particles to NiFe2O4, which gave rise to the increase in photocatalytic activity. Moreover, the experiment on recycled use of TSN demonstrated a good repeatability of the photocatalytic activity.

Design of metal-organic frameworks(MOFs)-based photocatalyst for solar fuel production and photo-degradation of pollutants

Metal organic frameworks(MOFs)is a research hotspot in the solar fuel production and photo-degradation of pollutants field due to high surface area,rich metal/organic species,large pore volume,and adjustability of structures and compositions.Therefore,in this review,we first summarized the design factors of photocatalytic materials based on MOF from the perspective of"star"MOF.The modification strategies of MOFs-based photocatalysts were discussed to improve its photocatalytic activity and specific applications were summarized as well,including photocatalytic CO_(2)reduction,photocatalytic water splitting and photo-degradation of pollutants.Finally,the advantages and disadvantages of MOFs-based photocatalysts were discussed,the current challenges were highlighted,and suggestions for future research directions were proposed.

Structure,morphology and opto-magnetic properties of Bi_2MoO_6 nano-photocatalyst synthesized by sol-gel method

Bismuth molybdate （Bi2MoO6） nano-particles （NPs） were synthesized using bismuth nitrate, ammonium molybdate, citric acid and ethyl cellulose by a simple sol-gel method. The structure, morphology, opto-magnetic and photocatalytic properties of the obtained powder were characterized by X-ray diffraction （XRD）, Fourier transform infrared （FT-IR） spectra, high resolution scanning electron microscopy （HRSEM）, energy dispersive X-ray （EDX）, ultraviolet-visible diffuse reflectance spectra （DRS）, photoluminescence （PL） spectra and vibrating sample magnetometer （VSM） techniques. The XRD, FT-IR and EDX results indicate that the resultant powder is pure and single phase crystalline Bi2MoO6 with orthorhombic structure. The HRSEM image shows that the morphology of obtained powder consists with well defined nano-particles structure. The VSM results show superparamagnetic behavior of the obtained nano-particles. The photocatalytic activity of Bi2MoO6 nano-particles was performed. The addition of TiO2 catalyst enhances the photocatalytic activity of Bi2MoO6 nano-particles. The catalysts Bi2MoO6, TiO2 and mixed oxide catalyst Bi2MoO6-TiO2 nano-composites （NCs） were tested for the photocatalytic degradation （PCD） of 4-chlorophenol （4-CP）. It is found that the PCD efficiency of Bi2MoO6-TiO2 NCs is higher than that of pure Bi2MoO6 and TiO2 catalysts.

Low-cost and efficient visible-light-driven CaMg(CO_3)_2@Ag_2CO_3 microspheres fabricated via an ion exchange route

CaMg(CO3)2microspheres were prepared and used as hard templates to fabricate a series of CaMg(CO3)2@Ag2CO3composite microspheres via a fast and low‐cost ion exchange process.The effects of ion exchange time and temperature on the physicochemical properties and photocatalytic activities of the composite microspheres were studied through photocatalytic degradation of Acid Orange II under xenon lamp irradiation.The obtained samples were analyzed by X‐ray diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,UV‐vis diffuse reflectance spectroscopy,N2physical adsorption,and photocurrent tests.The CaMg(CO3)2@Ag2CO3sample with the highest activity was obtained with an ion exchange time of4h and temperature of40°C.The degradation rate of Acid Orange II by this sample reached83.3%after15min of light irradiation,and the sample also performed well in phenol degradation.The CaMg(CO3)2@Ag2CO3produced under these ion exchange conditions showed a well‐ordered hierarchical morphology with small particle sizes,which was beneficial to light absorption and the transfer of photoelectrons(e-)and holes(h+)to the catalyst surface.Moreover,the separation of photogenerated carriers over the composites was greatly improved relative to bare CaMg(CO3)2.Despite the very low content of Ag2CO3(2.56%),excellent photocatalytic performance was obtained over the CaMg(CO3)2@Ag2CO3microspheres.

Photocatalytic degradation of textile dyeing wastewater through microwave synthesized Zr-AC,Ni-AC and Zn-AC

The novel zirconium oxide, nickel oxide and zinc oxide nanoparticles supported activated carbons（Zr-AC, Ni-AC, Zn-AC） were successfully fabricated through microwave irradiation method. The synthesized nanoparticles were characterized using XRD, HR-SEM, XPS and BET. The optical properties of Zr-AC, Ni-AC and Zn-AC composites were investigated using UV–Vis diffuse reflectance spectroscopy. The photocatalytic efficiency was verified in the degradation of textile dyeing wastewater（TDW） in UV light irradiation. The chemical oxygen demand（COD） of TDW was observed at regular intervals to calculate the removal rate of COD. Zn-AC composites showed impressive photocatalytic enrichment, which can be ascribed to the enhanced absorbance in the UV light region, the effective adsorptive capacity to dye molecules, the assisted charge transfer and the inhibited recombination of electron-hole pairs. The maximum TDW degradation（82% COD removal） was achieved with Zn-AC. A possible synergy mechanism on the surface of Zn-AC was also designed. Zn-AC could be reused five times without exceptional loss of its activity.

Synthesis of NiMoO_4 nanoparticles by sol-gel method and their structural,morphological,optical,magnetic and photocatlytic properties

Nickel molybdate(NiMoO4)nanoparticles(NPs)were synthesized by sol-gel method.Utilizing water as solvent providescrystalline nanostructures.These nanocrystals were structurally characterized by X-ray diffraction,energy dispersive X-ray analysis(EDX),and Fourier transform infrared spectra.Compositional stoichiometry was confirmed by EDX technique.The size and shapewere observed by scanning electron microscopy(SEM)and transmission electron microscope(TEM).It was found that the obtainedNPs were pure and single phase crystalline with monoclinic structure.The optical properties were studied by ultraviolet-visiblediffuse reflectance spectroscopy(UV-Vis-DRS)and photoluminescence(PL)measurements at room temperature.The magneticproperties were studied by vibrating sample magnetometer(VSM)and results showed superparamagnetic behavior of the obtainednanoparticles.Photocatalytic activity of NiMoO4was studied.The photocatalytic activity of NiMoO4was enhanced with the additionof TiO2.The catalysts NiMoO4,TiO2and NiMoO4-TiO2nanocomposites(NC)were tested for photocatalytic degradation(PCD)of4-chlorophenol(4-CP).It was found that PCD efficiency of NiMoO4-TiO2NC was higher than that of pure NiMoO4and TiO2.

Enhanced Photocatalytic Properties of Silver Oxide Loaded Bismuth Vanadate

In this work, BiV04 powders were synthesized by a sol-gel method, and the BiV04 gels with different calcination temperature were investigated by X-ray diffraction （XRD）. Absorption range and band gap energy, which are respon- sible for the observed photocatalyst behavior, were investigated by UV/vis diffuse reflectance spectroscopy （DRS） for pure and silver oxide loaded BiV04. Pbotocatalytic properties of the prepared samples were examined by studying the degradation of the methyl orange. When using NaCI02 as an electron acceptor, the possible photocatalytic mech- anism has been discussed by photocatalytic reactions. With the help of electron acceptor, the results show clearly that the BiV04 loaded silver oxide exhibited superior photocatalytic activity in simulated dye wastewater treatment.

Photogenerated carrier transfer mechanism and photocatalysis properties of TiO_2 sensitized by Zn(Ⅱ) phthalocyanine

The Zn(Ⅱ) phthalocyanine sensitized TiO2(ZnPc-TiO2) nanoparticles were prepared by hydrothermal method via impregnation with ZnPc.The as-prepared photocatalysts were characterized by X-ray diffractometry(XRD) and diffuse reflectance spectroscopy(DRS),and the surface photovoltage spectroscopy(SPS) and photocatalytic degradation of rhodamine B(RhB) were studied under illuminating.The experimental results indicate that TiO2 sensitized by ZnPc extends its absorption band into the visible region effectively,and the sensitized TiO2 has higher activity than TiO2(Degussa P-25) under the simulated solar light and the visible light.Based on the DRS and SPS results,the mechanism about the photogenerated carrier transfer between TiO2 and ZnPc is proposed.At a lower ZnPc content(≤0.20 μmol/g),ZnPc monomer acts as the electron donor,which provides the photoinduced electrons to the conduction band of TiO2.These photoinduced electrons can transfer to molecular oxygen(O2),leading to the formation of active species,such as superoxide/hydroxide radicals and singlet oxygen,which is beneficial to the photocatalytic reaction.While at a higher ZnPc content(>0.20 μmol/g),the formation of ZnPc dimer results in the decrease of photocatalytic activities of ZnPc-TiO2 photocatalyst.

Synthesis and Photocatalytic Property of ZnO/TiO2 Inverse Opals Films with Controllable Composition and Topology

A novel method to fabricate composition- （IO） films using a positive sacrificial ZnO and topology-controlled ZnO/TiO2 inverse opals IO template has been developed. This method includes a two-step process, preparation of ZnO IO by a simple electrochemical deposition using a self-assembly polystyrene colloidal crystal template and preparation of ZnO/TiO2 IO by a liquid phase deposition （LPD） process at room temperature. The composition and topology of ZnO/TiO2 IO can be easily controlled by changing the duration of the LPD. After 20 min LPD process, a ZnO/TiO2 composite IO with non-close-packed face-centered cubic air sphere array was obtained. Prolonging the duration to 60 min, a pure TiO2 IO （TIO-LPD60） with obviously thickened walls was formed. The formation mechanism for the compositional and topological variation was discussed. A preliminary study on UV photocatalytic property of the samples for degradation of methylene blue reveals that the composition and topology significantly influenced the photocatalytic activity of the IO film. The ZnO/TiO2 composite IO demonstrates a higher degree of activity than both pure ZnO and pure TiO2 IO, although they have a similar IO wall thickness. Moreover, with increasing IO wall thickness from -52 nm to -90 nm, TIO-LPD60 exhibits the highest level of photocatalytic performance.

Improvement of visible light-induced photocatalytic performance by Cr-doped SrTiO_3-carbon nitride intercalation compound (CNIC) composite

Novel organic-inorganic composite photocatalyst offers new opportunities in the practical applications of photocatalysis. Novel visible light-induced Cr-doped Sr Ti O3–carbon nitride intercalation compound(CNIC) composite photocatalysts were synthesized. The composite photocatalyst was characterized by X-ray diffraction(XRD), field-emission scanning electron microscopy(FESEM), high-resolution transmission electron microscopy(HRTEM), Fourier transform infrared(FT-IR) spectroscopy, UV-vis diffuse reflection spectroscopy, photoluminescence(PL) spectroscopy, and BET surface area analyzer. The photocatalytic oxidation ability of the novel composite photocatalyst was evaluated using methyl orange(MO) as a target pollutant. The photocatalysts exhibited a significantly enhanced photocatalytic performance in degrading MO. For maximizing the photodegradation activity of the composite photocatalysts, the optimal CNIC content was determined. The improved photocatalytic activity of the as-prepared Cr-doped Sr Ti O3–CNIC composite photocatalyst may be attributed to the enhancement of photo-generated electron–hole separations at the interface.