10BaF2:NaF, Na3AlF6/TiO2 composite as a novel visible-light-driven photocatalyst based on upconversion emission

A rare-earth free upconversion luminescent material, 10BaF2：NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light （550 nm-610 nm） into ultraviolet light （290 nm 350 nm）, and two emission peaks at 304 nm and 324 nm are observed under the excitation of 583 nm at room temperature. Subsequently, 10BaF2：NaF, Na3AIF6/TiO2 composite photocatalyst is prepared and its catalytic activity is evaluated by the photocatalytic reduction of CO2 under visible light irradiation （λ〉 515 nm）. The results show that 10BaF2：NaF, Na3AIF6/TiO2 is a more effective photocatalyst for CO2 reduction than pure TiO2, their corresponding methanol yields are 179 and 0 μmol/g-cat under the same conditions. Additionally, the mechanism of photocatalytic reduction of CO2 on 10BaF2：NaF, Na3AIF6/TiO2 is proposed.     

The influence of interfacial barrier engineering on the resistance switching of In₂O₃:SnO₂/TiO₂/In₂O₃:SnO₂ device

The I–V characteristics of In2O3:SnO2/TiO2/In2O3:SnO2 junctions with different interfacial barriers are inves- tigated by comparing experiments. A two-step resistance switching process is found for samples with two interfacial barriers produced by specific thermal treatment on the interfaces. The nonsynchronous occurrence of conducting filament formation through the oxide bulk and the reduction in the interfacial barrier due to the migration of oxygen vacancies under the electric field is supposed to explain the two-step resistive switching process. The unique switching properties of the device, based on interfacial barrier engineering, could be exploited for novel applications in nonvolatile memory devices.     

The concentration quenching and crystallographic sites of Eu²⁺ in Ca₂BO₃Cl

A yellow phosphor, Ca2BO3 Cl:Eu2+ , is prepared by the high-temperature solid-state method. Under the condition of excitation sources ranging from ultraviolet to visible light, efficient yellow emission can be observed. The emission spectrum shows an asymmetrical single intensive band centred at 573 nm, which corresponds to the 4f 6 5d 1 →4f 7 transition of Eu2+ . Eu2+ ions occupy two types of Ca2+ sites in the Ca2BO3 Cl lattice and form two corresponding emission centres, respectively, which lead to the asymmetrical emission of Eu2+ in Ca2 BO 3 Cl. The emission intensity of Eu2+ in Ca2BO3 Cl is influenced by the Eu2+ doping concentration. Concentration quenching is discovered, and its mechanism is verified to be a dipole–dipole interaction. The value of the critical transfer distance is calculated to be 2.166 nm, which is in good agreement with the 2.120 nm value derived from the experimental data.     

Assembly,characterization, and photocatalytic activities of TiO<Subscript>2</Subscript> nanotubes/CdS quantum dots nanocomposites

The semiconductor quantum dots (QDs) can be very efficient to tune the response of photocatalyst of TiO₂ to visible light. In this study, CdS QDs formed in situ with about 8 nm have been successfully deposited onto the surfaces of TiO₂ nanotubes (TNTs) to form TNTs/CdS QDs nanocomposites by use of a simple bifunctional organic linker, thiolactic acid. The diffuse reflectance spectroscopy (DRS) spectra of as prepared samples showed that the absorption edge of the TNTs/CdS composite is extended to visible range, with absorption edge at 530 nm. The photocatalytic activity and stability of TNTs/CdS were also evaluated for the photodegradation of rhodamine B. The results showed that when TNTs/CdS QDs was used, photocatalytic degradation of RhB under visible light irradiation reached 91.6%, higher than 45.4 and 30.5% for P25 and TNTs, respectively. This study indicated that the TNTs/CdS QDs nanocomposites were superior catalysts for photodegradation under visible light irradiation compared with TNTs and P25 samples, which may find wide application as a powerful photocatalyst in environmental field.     

Ag负载WO3/TiO2光催化剂的合成及其催化性能

以钛酸丁酯、无水乙醇、钨酸铵为原料,采用溶胶-凝胶法合成了WO3/TiO2复合光催化剂;采用光还原技术制备了Ag负载WO3/TiO2光催化剂,借助X射线粉末衍射(XRD)和UV-Vis光谱等技术对样品的组成和光吸收性能进行了表征,并以罗丹明B为模型污染物考察样品的光催化活性。XRD分析表明,所得粉体均为锐钛矿型纳米TiO2,且与WO3复合后,纳米TiO2特征衍射峰宽化,强度降低;UV-Vis光谱分析表明,载银使得催化剂在400—700nm的可见光区域对光响应,且在紫外光区吸收显著增强,对光具有更高的利用率;以罗丹明B为降解物的光催化实验表明,WO3复合对纳米TiO2光催化活性有显著的影响,而载Ag后其光催化活性进一步提高,将该光催化剂用于炼油厂废水的处理,效果较好。     

离子液体辅助N,S,F共掺杂纳米TiO2的制备与表征

以TiCl4、硫脲和离子液体([C6mim]+[BF4]-)为原料,采用微波催化水解法合成掺杂的纳米TiO2前驱体,在NH3/N2气氛中经程序升温煅烧处理制得N,S,F共掺杂TiO2光催化剂(N—S—F—TiO2)。采用X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis/DRS)等对该光催化剂的结构和性能进行表征。结果表明,该光催化剂为锐钛矿晶型,具有较高的纯度和结晶度,掺杂在TiO2晶体中形成Ti—O—N键,Ti—O—S键,Ti—S键,而F以TiOF2形态掺杂。在可见光区400～550nm具有强吸收,且在600～800nm出现一个较强的吸收带。实验表明,使用[C6mim]+[BF4]-与H2O的体积比为5/95所制得的光催化剂对甲基橙降解的催化活性最高,可见光照射200min降解率达95%。多掺杂的协同效应使得N—S—F—TiO2具有对可见光的强烈吸收和较高的可见光催化活性。     

Diode-pumped laser and self-frequency-doubling properties of a Nd³⁺:Na₃La₉O₃(BO₃)₈ crystal

We report efficient, diode-pumped, self-frequency doubling (SFD) in the newly developed laser crystal Nd³⁺:Na₃La₉O₃(BO₃)₈ (Nd:NLBO). More than 730?mW of fundamental output power at 1072?nm was achieved with a slope efficiency of 16.2%. With incident pump power of 8?W, 29?mW of green cw laser emission at 536?nm was observed with proper phase matching. This initial performance and the good optical properties of the crystalline host are encouraging for the development of a high power diode-pumped SFD visible light laser source.     

A facile in situ solvothermal method for two-dimensional layered g-C<Subscript>3</Subscript>N<Subscript>4</Subscript>/SnS<Subscript>2</Subscript> p-n heterojunction composites with efficient visible-light photocatalytic activity

To overcome the fast recombination rate of electron-hole pairs of individual SnS₂, p-n heterojunction g-C₃N₄/SnS₂ composites were fabricated as high-efficiency visible-light photocatalyst to photodegradate the organic dye MB. The morphologies, structures, compositions, and photocatalytic properties were characterized. The SnS₂ shows two-dimensional layer structure with an average thickness of 20 nm and diameter size of about 2 μm, and the g-C₃N₄ nanoflakes were uniformly deposited on the surface of SnS₂ nanosheets. In comparison with the bare g-C₃N₄ and SnS₂, the composites show improved photocatalytic activity under visible light, which is sensitive to the content of g-C₃N₄. In particular, the 15% g-C₃N₄/SnS₂ composites exhibit the highest photocatalytic activity and outstanding reusability, which can degrade 88.01% MB after only 1 h in the visible light (λ?>?420 nm) range. The g-C₃N₄/SnS₂ heterojunction composites show outstanding reusability after four times cycling experiments. The improved photocatalytic activities of composites are attributed to abundant active species, increased charge separation, and decreased electron-hole pair recombination, which originated from the large specific surface area and efficient interfacial transport of photo-induced charge carriers between SnS₂ and g-C₃N₄. These results suggest that the two-dimensional layered g-C₃N₄/SnS₂ p-n heterojunction composites are promised to be a high-efficiency visible-light photocatalyst.     

Spectroscopic characterization of Yb:Sc₂O₃ transparent ceramics

Yb:Sc2O3 transparent ceramics are fabricated by a conventional ceramic process and sintering in H2 atmosphere. The room-temperature spectroscopic properties are investigated, and the Raman spectrum shows an obvious vibration characteristic band centred at 415 cm 1 . There are three broad absorption bands around 891, 937, and 971 nm, respectively. The strongest emission peak is centred at 1.04 μm with a broad bandwidth (11 nm) and an emission cross-section of 1.8×10 20 cm 2 . The gain coefficient implies a possible laser ability in a range from 990 nm to 1425 nm. The energy-level structure shows that Yb:Sc 2 O 3 ceramics have large Stark splitting at the ground state level due to their strong crystal field. All the results show that Yb:Sc2O3 transparent ceramics are a promising material for short pulse lasers.     

Preparation of N-doped TiO<Subscript>2</Subscript> photocatalyst by atmospheric pressure plasma process for VOCs decomposition under UV and visible light sources

The nitrogen doped (N-doped) titanium dioxide (TiO₂) photocatalyst was prepared by the atmospheric-pressure plasma-enhanced nanoparticles synthesis (APPENS) process operated under normal temperature, i.e. the dielectric barrier discharge plasma process. The N₂ carrier gas is dissociated in the AC powered nonthermal plasma environment and subsequently doped into the TiO₂ photocatalyst that was capable of being induced by visible light sources. The APPENS process for producing N-doped TiO₂ showed a higher film deposition rate in the range of 60–94 nm/min while consuming less power (<100 W) as compared to other plasma processes reported in literatures. And the photocatalytic activity of the N-doped TiO₂ photocatalyst was higher than the commercial ST01 and P25 photocatalysts in terms of toluene removals in a continuous flow reactor. The XPS measurement data indicated that the active N doping states exhibited N 1s binding energies were centered at 400 and 402 eV instead of the TiN binding at 396 eV commonly observed in the literature. The light absorption in the visible light range for N-doped TiO₂ was also confirmed by a clear red shift of the UV-visible spectra.     

CdS/TiO2/漂珠复合光催化剂制备及其降解高效氯氰菊酯研究

采用溶胶-凝胶-浸渍法制备了Cds/TiO2/漂珠复合光催化剂,通过SEM,XRD对其结构进行了表征.以高效氯氰菊酯(BEC)杀虫剂的光催化降解为模型反应,研究了CdS/TiO2/漂珠的光催化性能,探讨了影响催化剂活性的因素及采用太阳光作光源处理BEC的可行性.结果表明,CdS/TiO2/漂珠投加量为3 000mg·L-1,初始浓度为45 mg·L-1、初始pH为6.5,通气量为200 mL·min-1时间为60 min,BEC降解率分别为92.1%(125W高压汞灯)和79.3%(5 W紫外灯),采用太阳光照射300 min,BEC降解率可达93.4%.BEC的降解反应遵从L-H动力学模型,测得反应速率常数9.80 mg·(L·min)-1,吸附常数4.36×10-3 L·mg-1.     

Photodeposition of ultrathin MoS<Subscript>2</Subscript> nanosheets onto cubic CdS for efficient photocatalytic H<Subscript>2</Subscript> evolution

In this work, the photocatalyst composed of ultrathin MoS₂ nanosheets onto the surface of cubic CdS nanoparticles with an average diameter of 7~10 nm has been successfully fabricated through a facile and mild photodeposition route. The ultrathin MoS₂ nanosheets as a cocatalyst were demonstrated to greatly boost photocatalytic H₂ evolution over cubic CdS upon visible light irradiation. It was clearly revealed that both the cubic CdS substrate and structure of ultrathin MoS₂ nanosheets play critical roles in the observed efficient H₂ evolution. The cubic CdS offers a strong adherence for ultrathin MoS₂ nanosheets to form a well contact interface, across which the photogenerated charge transfer and charge separation are achieved. The ultrathin MoS₂ nanosheets introduce a high density of unsaturated active S atoms for H₂ evolution.     

Magnetically separable Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@C/BiOBr heterojunction for the enhanced visible light-driven photocatalytic performance

In this study, the magnetically recyclable Fe₃O₄@C/BiOBr heterojunction with enhanced visible light-driven photocatalytic ability was obtained by two-step solvothermal method. The phase, morphology, and structure of the samples were investigated by XRD, FESEM, HRTEM, and XPS. The Fe₃O₄@C/BiOBr heterojunction was composed of Fe₃O₄@C sphere and BiOBr microsphere with diameters of 200 nm and 1000 nm, respectively. The photocatalytic performance of Fe₃O₄@C/BiOBr composite for RhB was examined under visible light irradiation. The photocatalytic activity of Fe₃O₄@C/BiOBr composite was much higher than that of pure BiOBr and Fe₃O₄@C. After 35 min of irradiation, 97% of RhB could be removed with the Fe₃O₄@C/BiOBr photocatalyst. Based on radical trapping experiments of active species, the mechanism of enhanced photocatalytic performance was proposed. In addition, the superparamagnetic property of the photocatalyst not only allows its easy recyclability by an external magnetic field but also maintains high photocatalytic activity after five cyclic experiments.

Open image in new window

Graphical abstract ?

     

Calculations of the vibrational frequency and isotopic shift of UF₆ and U₂ F₆

Molecular structure, vibrational frequency and infrared intensity of UF 6 are investigated by using the revised Perdew-Burke-Enzerhof function with the triple-zeta polarized basis set. The calculation results are in good agreement with the experimental values and indicate the existence of a stable U2F6 molecule with a multiple bonded U2 unit. The calculation results also predict that the D3d symmetry of U2F6 is more stable than D3h . The optimized geometries, vibrational frequencies, and infrared intensities are also reported for U2F6 molecules in D3d symmetry. In addition, the isotopic shift of vibrational frequencies of the two molecules under isotopic substitution of uranium atom are also investigated with the same method. The U2F6 molecule is predicted to be better than UF6 for laser uranic isotope separation.     

Properties of a Si₂N molecule under an external electric field

In the present work,we adopt the ccsd/6-31g(d) method to optimize the ground state structure and calculate the vibrational frequency of the Si2N molecule.The calculated frequencies accord satisfactorily with the experimental values,which helps confirm the ground state structure of the molecule.In order to find how the external electric field affects the Si2N molecule,we use the density functional method B3P86/6-31g(d) to optimize the ground state structure and the time-dependent density functional theory TDDFT/6-31g(d) to study the absorption spectra,the excitation energies,the oscillator strengths,and the dipole moments of the Si2N molecule under different external electric fields.It is found that the absorption spectra,the excitation energies,the oscillator strengths,and the dipole moments of the Si2N molecule are affected by the external electric field.One of the valuable results is that the absorption spectra of the yellow and the blue-violet light of the Si2N molecule each have a red shift under the electric field.The luminescence mechanism in the visible light region of the Si2N molecule is also investigated and compared with the experimental data.     

RuO2/TiO2/漂珠复合光催化剂的制备及性能

"利用RuO2/TiO2前驱体溶胶,采用溶胶-凝胶-浸渍法在漂珠(FP)表面沉积RuO2/TiO2膜,经120 ℃干燥、500 ℃焙烧制备复合光催化剂RuO2/TiO2/FP,并通过SEM、XRD以及FT-IR分别对其结构进行了表征． 结果表明,RuO2/TiO2膜的平均厚度(三层)约1 1m,膜材料中TiO2主要呈现锐钛矿型结构,而RuO2是以非晶态高度分散在粒子表面．以高效氯氰菊酯杀虫剂的光催化降解为模型反应,研究了RuO2/TiO2/FP的光催化性能,探讨了影响催化剂活性的因素及采用太阳光做光源处理     

Tunable Ba_0.5 Sr_0.5 TiO₃ film bulk acoustic resonators using SiO₂ /Mo Bragg reflectors

Tunable and switchable Ba 0.5 Sr 0.5 TiO 3 film bulk acoustic resonators(FBARs) based on SiO 2 /Mo Bragg reflectors are explored,which can withstand high temperature for the deposition of Ba x Sr 1 x TiO 3(BST) films at 800 C.The dc bias-dependent resonance may be attributed to the piezoelectricity of the BST film induced by an electrostrictive effect.The series resonant frequency is strongly dc bias-dependent and shifts downwards with dc bias increasing,while the parallel resonant frequency is only weakly dc bias-dependent and slightly shifts upwards at low dc bias(< 45 V) while downwards at higher dc bias.The calculated relative tunability of shifts at series resonance frequency is around 2.3% and the electromechanical coupling coefficient is up to approximately 8.09% at 60-V dc bias,which can be comparable to AlN FBARs.This suggests that a high-quality tunable BST FBAR device can be achieved through the use of molybdenum(Mo) as the high acoustic impedance layer in a Bragg reflector,which not only provides excellent acoustic isolation from the substrate,but also improves the crystallinity of BST films withstanding higher deposition temperature.     

Transport properties of a binary mixture of CO₂-N₂ from the pair potential energy functions based on a semi-empirical inversion method

The potential energy surface of a CO 2 –N 2 mixture is determined by using an inversion method, together with a new collision integral correlation [J. Phys. Chem. Ref. Data 19 1179 (1990)]. With the new invert potential, the transport properties of CO2–N2 mixture are presented in a temperature range from 273.15 K to 3273.15 K at low density by employing the Chapman–Enskog scheme and the Wang Chang–Uhlenbeck–de Boer theory, consisting of a viscosity coefficient, a thermal conductivity coefficient, a binary diffusion coefficient, and a thermal diffusion factor. The accuracy of the predicted results is estimated to be 2% for viscosity, 5% for thermal conductivity, and 10% for binary diffusion coefficient.     

Photocatalytic ability of Bi<Subscript>6</Subscript>Ti<Subscript>3</Subscript>WO<Subscript>18</Subscript> nanoparticles with a mix-layered Aurivillius structure

Aurivillius phase layered perovskites Bi₆Ti₃WO₁₈ was prepared by the sol-gel citrate-complexation synthesis. The sample developed into the plate-like nanoparticles with the exposed (001) facets. The phase formation and structure have been verified via X-ray polycrystalline powder diffraction (XRD) Rietveld refinements. The nanoparticles were investigated via the measurements such as FE-SEM, TEM, EDS, and the surface analyses. UV–Vis absorption data revealed that the Aurivillius compound has a direct band characteristic with the band energy of 2.214 eV. The band structure of Bi₆Ti₃WO₁₈ nanoparticles was discussed on the base of the experiments and theoretical calculation. Bi³⁺-containing Aurivillius Bi₆Ti₃WO₁₈ shows efficient photocatalytic degradation for rhodamine B dye (RhB) with the visible light irradiation (λ?>?420 nm). Dynamic characteristic of the light-created excitons was measured by the luminescence and decay lifetime. The multivalent properties of W and Ti ions in the Aurivillius-like lattices of Bi₆Ti₃WO₁₈ photocatalyst were discussed.     

镶嵌Pt的二氧化钛纳米管的合成及其光催化性能研究

以金红石相二氧化钛(TiO₂)粉体为原料,采用水热法合成了二氧化钛纳米管(Titania nanotubes,简写为TNTs),然后把H₂PtCl₆的无水乙醇溶液引入到TNTs中,得到镶嵌Pt的二氧化钛纳米管(Pt/TNTs)。利用透射电镜(TEM)、X射线衍射(XRD)和紫外-可见光谱(UV-Vis)对产物进行了表征,并重点研究了Pt/TNTs的光催化性能。结果表明,有直径约为3 nm的 Pt纳米粒子插入到了TNTs中,且Pt粒子以Pt单质的形式存在。Pt/TNTs在可见光区域表现出较强的吸收,并且其起始吸收带边发生明显红移。紫外光催化降解甲基橙实验结果表明,金红石相TiO₂,TNTs和Pt/TNTs对甲基橙溶液的降解率分别达到46.8%, 57.2%和84.6%,Pt/TNTs的光催化活性较金红石相二氧化钛粉体和纯TNTs有显著的提高。