Synthesis and photocatalytic activity of cobalt oxide doped ZnFe2O4-Fe2O3-ZnO mixed oxides

Novel cobalt oxide doped ZnFe₂O₄-Fe₂O₃-ZnO mixed oxides with the Zn/Fe molar ratio of 1/2 were synthesized with a citric acid complex method. The effects of cobalt oxide and calcination temperature on phase composition and photocatalytic activity of the mixed oxides were investigated. X-ray diffraction (XRD) analysis revealed that there were mainly ZnFe₂O₄, α-Fe₂O₃, amorphous ZnO and Fe₂O₃ in the 6 mol% cobalt oxide doped products calcined at 500 °C. 5-10 mol% cobalt oxide doping could significantly enhance the formation of ZnFe₂O₄ and altered the phase composition of the mixed oxides. Experimental results showed that cobalt oxide doping could remarkably improve the photocatalytic activity of the mixed oxides for phenol degradation. The 6 mol% cobalt oxide doped mixed oxides calcined at 500 °C exhibited better photocatalytic activity as compared with other samples.     

Growth and structure characterization of epitaxial Bi2Sr2Co2Oy thermoelectric thin films on LaAlO3 (001)

Epitaxial Bi₂Sr₂Co₂O_y thin films with excellent c-axis and ab-plane alignments have been grown on (001) LaAlO₃ substrates by chemical solution deposition using metal acetates as starting materials. Microstructure studies show that the resulting Bi₂Sr₂Co₂O_y films have a well-ordered layer structure with a flat and clear interface with the substrate. Scanning electron microscopy of the films reveals a step-terrace surface structure without any microcracks and pores. At room temperature, the epitaxial Bi₂Sr₂Co₂O_y films exhibit a resistivity of about 2 mΩ cm and a seebeck coefficient of about 115 μV/K comparable to those of single crystals.     

Influence of calcination temperature on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol–gel-combustion processing

The detailed preparation process of Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ phosphor powders with red long afterglow by sol–gel-combustion method in the reducing atmosphere is reported. X-ray diffraction, scanning electron microscopy and photoluminescence spectroscopy are used to investigate the effects of synthesis temperature on the crystal characteristics, morphology and luminescent properties of the as-synthesized Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors. The results reveal that Sr₃Al₂O₆ crystallizes completely when the combustion ash is sintered at 1200 °C. The excitation and the emission spectra indicate that the excitation broad-band lies chiefly in visible range and the phosphor powders emit strong light at 618 nm under the excitation of 472 nm. The light intensity and the light-lasting time of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors are increased when increasing the calcination temperatures from 1050 to 1200 °C. The afterglow of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors sintered at 1200 °C lasts for over 600 s when the excited source is cut off. The red emission mechanism is discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions.     

Preparation and characterization of Sr4Al2O7:Eu, Eu phosphors

A new composition of red strontium aluminate phosphor (Sr₄Al₂O₇:Eu³⁺, Eu²⁺) is synthesized using a solid state reaction method in air and in a reducing atmosphere. The investigation of firing temperature indicates that a single phase of Sr₄Al₂O₇ is formed when the firing temperature is higher than 1300 °C and that a Sr₃Al₂O₆ phase is formed as the main peak below 1300 °C. The effects of firing temperature and doping concentration on luminescent properties are investigated. Sr₄Al₂O₇ phosphors exhibit the typical red luminescent properties of Eu³⁺ and Eu²⁺. A comparison photoluminescence study with Sr₃Al₂O₆ phosphor shows that Sr₄Al₂O₇ has higher emission intensity than Sr₃Al₂O₆ as a result of the higher optimum doping concentration of Sr₄Al₂O₇ phosphor.     

A citrate complex process to prepare nanocrystalline PbBi2Nb2O9 at a low temperature

PbBi₂Nb₂O₉ nanocrystals with a perovskite-type structure were successfully synthesized at a relative low temperature via a citrate complex method. Metal ions were dispersed by citric acid in ethanol and ethylene glycol solvent, and then reacted with NH₄H₂[NbO(C₂O₄)₃·3H₂O] to form the gel. XRD results showed that pure PbBi₂Nb₂O₉ nanocrystals could be obtained after calcined treatment of xerogel at 800 °C. The average particles size was 57 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that the sintering process led to the agglomeration of the nanoparticles. The photocatalytic test showed that the sample prepared by the citrate complex method exhibited a higher photocatalytic activity than that of the sample prepared by the solid-state reaction.     

Ferroelectric Bi3.25La0.75Ti3O12 thin films on a conductive Sr4Ru2O9 electrode obtained by pulsed laser deposition

Strontium ruthenate and Bi_3.25La_0.75Ti₃O₁₂ (BLT) layers were grown on Si(100) substrate using pulsed laser deposition technique. Starting from a Sr₂RuO₄ target, we obtained single phase films composed of Sr₄Ru₂O₉; on these strontium ruthenate electrodes, textured and non-textured BLT were grown at 700 °C. Structural characterizations of these double layers were done by X-ray diffraction, scanning electron microscopy, normal and high-resolution transmission electron microscopy. The Van der Pauw's resistivity measurements indicate that Sr₄Ru₂O₉ can be used as a back electrode. The temperature dependence of the resistivity at low temperatures is , which corresponds to a variable-range hopping mechanism.     

等离子体电解氧化法制备多孔TiO2/V2O5复合物膜层及其增强光催化产氢活性

较差的光催化产氢效率极大地阻碍了TiO₂光催化剂的工业化应用。为此,本文在含有NH₄VO₃的磷酸盐溶液中,采用等离子体电解氧化(PEO)法制备了多孔TiO₂/V₂O₅复合膜光催化剂,通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射(XRD)、X射线光电子谱(XPS)和紫外可见漫反射光谱(UV-Vis DRS)对其组成、结构及光吸收性质进行了表征,并采用气相色谱评价了薄膜催化剂的光催化产氢性能,研究了电解液中NH₄VO₃含量对膜的结构、组成和光催化产氢性能的影响。结果表明:复合膜催化剂主要由锐钛矿和金红石型TiO₂组成,具有微孔结构,V₂O₅主要以无定形形式存在于膜中,与TiO₂有很强的相互作用,影响TiO₂的晶面间距。研究发现,元素V抑制了TiO₂的结晶和金红石型TiO₂的形成,扩大了薄膜的光学吸收范围。针对Na₂S+ Na₂SO₃溶液中的光催化产氢性能的研究显示,在质量浓度为1 g/L NH₄VO₃的电解液中制备的TiO₂/V₂O₅薄膜的光催化活性最高,优于近年来报道的其他光催化剂。光催化重复实验表明,该复合膜催化剂具有较高的稳定性和较为恒定的光催化活性。     

微结构对Bi_2Sr_2Co_2O_y化合物电性能的影响

通过溶胶-凝胶法制备单相Bi2Sr2Co2Oy化合物,通过添加PEG20000和超声分散对化合物粉体微结构进行调控,采用SPS烧结得到了致密的块体.探索了微结构对Bi2Sr2Co2Oy化合物电性能的影响规律.结果表明,添加PEG20000和超声分散可以明显降低Bi2Sr2Co2Oy化合物粉体的晶粒尺寸,使烧结块体的晶粒尺寸大幅度减小,从而显著提高材料的电性能.温度为873K时,添加PEG20000并超声处理所制备样品烧结块体获得了最高ZT值0.041.     

Sr3.5Mg0.5Si3O8Cl4: Eu bluish-green-emitting phosphor for NUV-based LED

Sr₄Si₃O₈Cl₄:Eu²⁺ and Sr_3.5Mg_0.5Si₃O₈Cl₄:Eu²⁺ phosphors were prepared by a conventional solid state reaction (SS). Excited by 370 nm near-ultraviolet light, the phosphors show an efficient bluish-green wide-band emission centering at 484 nm, which originates from the 4f5d¹ → 4f⁷ transition of Eu²⁺ ion. The excitation spectra of the phosphors are a broad band extending from 250 nm to 400 nm. Mg²⁺-codoping greatly enhances the bluish-green emission of the phosphors. An LED was fabricated by coating the Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ phosphor onto an ~ 370 nm-emitting InGaN chip. The LED exhibits bright bluish-green emission under a forward bias of 20 mA. The results indicate that Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ is a candidate as a bluish-green component for fabrication of NUV-based white LEDs.     

Nanosized BiVO4 with high visible-light-induced photocatalytic activity: Ultrasonic-assisted synthesis and protective effect of surfactant

Nanosized BiVO₄ with high visible-light-induced photocatalytic activity was successfully synthesized via ultrasonic-assisted method with polyethylene glycol (PEG). The BiVO₄ sample prepared under ultrasonic irradiation with 1 g PEG for 30 min was consisted of small nanoparticles with the size of ca. 60 nm. The effects of ultrasonic irradiation and surfactant were investigated. The nanosized BiVO₄ exhibited excellent visible-light-driven photocatalytic efficiency for degrading organic dye, which was increased to nearly 12 times than that of the products prepared by traditional solid-state reaction. Besides decoloring, the reduction of chemical oxygen demand (COD) concentration was also observed in the degradation of organic dye, further demonstrating the photocatalytic performance of BiVO₄. After five recycles, the catalyst did not exhibit any significant loss of photocatalytic activity, confirming the photocatalyst is essentially stable. Close investigation revealed that the crystal size, BET surface area, and appropriate band gap of the as-prepared BiVO₄ could improve the photocatalytic activities.     

Photocatalytic degradation of RhB over MgFe2O4/TiO2 composite materials

MgFe₂O₄/TiO₂ (MFO/TiO₂) composite photocatalysts were successfully synthesized using a mixing-annealing method. The synthesized composites exhibited significantly higher photocatalytic activity than a naked semiconductor in the photodegradation of Rhodamine B. Under UV and visible light irradiation, the optimal percentages of doped MgFe₂O₄ (MFO) were 2 wt.% and 3 wt.%, respectively. The effects of calcination temperature on photocatalytic activity were also investigated. The origin of the high level of activity was discussed based on the results of X-ray diffraction, UV-vis diffuse reflection spectroscopy, scanning electron microscopy, transmission electron microscopy, and nitrogen physical adsorption. The enhanced activity of the catalysts was mainly attributed to the synergetic effect between the two semiconductors, the band potential of which matched suitably.     

Synthesis,Characterization and Photocatalytic Activity of TiO_2 Film/Bi_2O_3 Microgrid Heterojunction

TiO2 film modified by Bi2O3 microgrid array was successfully fabricated by using a microsphere lithography method.The structure and morphology of TiO2 film,Bi2O3 film and TiO2 film/Bi2O3 microgrid heterojunction were characterized through X-ray diffraction,atomic force microscopy and scanning electron microscopy.The optical transmittance spectra and the photocatalytic degradation capacity of these samples to rhodamine B were determined via ultraviolet-visible spectroscopy.The results indicated that the coupled system showed higher photocatalytic activity than pure TiO2 and Bi2O3 films under xenon lamp irradiation.The enhancement of the photocatalytic activity was ascribed to the special structure,which could improve the separation of photo-generated electrons and holes,enlarge the surface area and extend the response range of TiO2 film from ultraviolet to visible region.     

Influence of excitation wavelengths on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol-gel-combustion processing

Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ red-emitting long afterglow phosphor was synthesized by sol-gel-combustion methods using Sr(NO₃)₂, Al(NO₃)₃·9H₂O, Eu₂O₃, Dy₂O₃, H₃BO₃ and C₆H₈O₇·H₂O as raw materials. The crystalline structure of the phosphors were characterized by X-ray diffraction, luminescent properties of phosphors were analyzed by fluorescence spectrophotometer. The effect of excitation wavelengths on the luminescent properties of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors was discussed. The emission peak of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor lays at 516 nm under the excitation of 360 nm, and at 612 nm under the excitation of 468 nm. The results reveal that the Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor will emit a yellow-green light upon UV illumination, and a bright red light upon visible light illumination. The emission mechanism was discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions in Sr₃Al₂O₆. The afterglow time of (Sr_0.94Eu_0.03Dy_0.03)₃ Al₂O₆ phosphors lasts for over 600s after the excited source was cut off.     

Investigations of Bi substitution in NdBa2Cu3Oy

Attempts to substitute Bi for Nd in orthorhombic NdBa₂Cu₃O _y , prepared in air or oxygen at about 950°C led instead to formation of Ba₂NdBiO₆, a new cubic compound witha=0.8703 nm. The possibility was then explored of preparing superconducting (Nd_1–x Bi _x )Ba₂Cu₃O _y , by first forming the tetragonal phase at 880–950°C in nitrogen or argon followed by reheating in oxygen or air at 250–500°C in order to insert the additional oxygen required to yield the orthorhombic form while avoiding oxidation of Bi³⁺ to Bi⁵⁺. X-ray diffraction studies, electrical conductivity measurements, and thermogravimetric analysis of products indicate that Bi does not enter the NdBa₂Cu₃O _y , lattice in either the tetragonal or the orthorhombic phase. Ba₂NdBiO₆ clearly forms on reheating in oxygen or air even at low temperatures, and evidence is presented that a poorly crystallized oxygen-deficient form of this compound is already present prior to the reheating.     

HREM surface profile images of Bi2Sr2CaCu2O8

Surface profile images of Bi₂Sr₂CaCu₂O₈ have been obtained using high-resolution electron microscopy. The cleaved (001) surface of the crystals terminates with a single Bi-O atomic layer. The modulated structure developed in this surface atomic layer was observed directly. The (hk0) surfaces were found to decompose in air into an amorphous coating layer. This coating layer was unlikely recrystallized into the original structure under electron beam irradiation. The amorphous layer on the (hk0) surface formed in pure Ar atmosphere was relatively thin and could be recrystallized into some secondary phases in which a Bi loss was observed. The original (001) surface might also be covered by an amorphous-like layer. This disordered layer could be recrystallized under electron beam irradiation into BiSr₂Ca₂Cu₃O₉, BiSr₂CuO₅, etc. which intergrow with the parent crystal perfectly on the (001) planes.The author thanks the EPSRC for financial support.     

Bactericidal effect of blue LED light irradiated TiO2/Fe3O4 particles on fish pathogen in seawater

This study uses blue LED light (λ_max = 475 nm) activated TiO₂/Fe₃O₄ particles to evaluate the particles' photocatalytic activity efficiency and bactericidal effects in seawater of variable salinities. Different TiO₂ to Fe₃O₄ mole ratios have been synthesized using sol-gel method. The synthesized particles contain mainly anatase TiO₂, Fe₃O₄ and FeTiO₃. The study has identified TiO₂/Fe₃O₄'s bactericidal effect to marine fish pathogen (Photobacterium damselae subsp. piscicida BCRC17065) in seawater. The SEM photo reveals the surface destruction in bacteria incubated with blue LED irradiated TiO₂/Fe₃O₄. The result of this study indicates that 1) TiO₂/Fe₃O₄ acquires photocatalytic activities in both the freshwater and the seawater via blue LED irradiation, 2) higher photocatalytic activities appear in solutions of higher TiO₂/Fe₃O₄ mole ratio, and 3) photocatalytic activity decreases as salinity increases. These results suggest that the energy saving blue LED light is a feasible light source to activate TiO₂/Fe₃O₄ photocatalytic activities in both freshwater and seawater.     

Investigations of chemical interaction between Bi-based 2212 and (RE)Ba2Cu3O7 high Tc superconducting materials

Composite materials have been synthesized by mixing 90% (or 95%) YBa₂Cu₃O₇ and 10% (or 5%) Bi₂Sr₂Ca₁Cu₂O₈ by weight, and firing at 900°C to promote grain growth by inducing a liquid phase (Bi₂Sr₂Ca₁Cu₂O₈) in the system. The influence of the amount of liquid phase on the X-ray diffraction data and electrical properties is reported. Energy dispersive X-ray (EDX) analyses are also reported. The YBiBa₂O₆ phase is formed during the heat treatment and introduces additional chemical heterogeneities at the grain boundaries. A previously reported 2212-related superconducting phase, Bi₂(Sr,Ba)₂(Ca,Y)Cu₂O_8+y, could also be formed during the synthesis process, and its effect on the electrical resistance versus temperature measurements is discussed. Attempts to substitute RE ions (Dy³⁺, Er³⁺, Ho³⁺) for Y³⁺ in YBiBa₂O₆ have been successful and are reported in an appendix section. X-ray diffraction data are also reported. EDX analyses have been performed specifically for a typical ErBiBa₂O₆ compound and reveal the presence of a new Er₂Ba₄O₇ phase.     

Superconductivity in epitaxial Bi2Sr2CuO6/Bi2Sr2CaCu2O8 superlattices: The superconducting behavior of ultrathin cuprate slabs

Utilizing atomic layer-by-layer molecular beam epitaxy (ALL-MBE), we have synthesized a series of high-quality superlattices in which ultrathin slabs (one-half unit cell thick) of the high-T _c superconductor Bi₂Sr₂CaCu₂O₈ alternate with up to five such layers of the low-T _c Bi₂Sr₂Cu₁O₆ phase. In all these superlattices we foundT _c to be essentially equal to that of the high-T _c Bi₂Sr₂CaCu₂O₈ phase itself, which indicates that this cuprate is a 2D superconductor insofar as the interslab coupling plays at best a secondary role. Furthermore, it is demonstrated thatT _c need not be reduced at heterostructure interfaces.     

Effect of chromium substitution on structure and magnetic properties of Bi2Fe4O9

Orthorhombic Bi₂Fe_4 − xCr_xO₉ (x = 0.0, 0.25, and 0.75) nanoplatelets were synthesized by a simple hydrothermal method. The structure, morphology, and magnetic properties of the obtained powders have been characterized. Calculation of the lattice parameters of Bi₂Fe_4 − xCr_xO₉, as well as bond lengths and angles, was carried out by X-ray diffraction Rietveld refinement. The volumes of the metal-oxygen tetrahedra and octahedra were calculated to be sequentially increasing as the Cr doping level increases. The samples undergo an antiferromagnetic transition at 250 ± 5 K. The magnetic moments of the samples increase with higher Cr doping level. The 3d electron spin state for Fe³⁺ in the as-prepared samples is different, which is possibly due to the distortion of Fe-O tetrahedra and octahedra in the crystal structure after chromium substitution.