Hydrothermal synthesis and photocatalytic property of porous CuO hollow microspheres via PS latex as templates

Porous copper oxide (CuO) hollow microspheres have been fabricated through a simple hydrothermal method using PS latex as templates. The as-obtained samples were characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD) and Fourier transform infrared spectroscopy (FTIR). The influences of the mole ratio of Ethylenediamine (C₂H₈N₂) and copper acetate (Cu(Ac)₂·H₂O), hydrothermal temperature and time on the size and morphologies of the final products have been investigated. The possible formation mechanism of porous CuO hollow microspheres has been proposed and the specific surface area of the hollow microspheres with 81.71 m²/g is measured by BET method. The band gap value calculated from a UV–vis absorption spectrum of porous CuO hollow microspheres is 2.71 eV. The as-synthesized product exhibits high photocatalytic activity during the photodegradation of an organic dyestuff, rhodamine B (RhB), under UV-light illumination.     

Photocatalytic hydrogen production over CuO-modified titania

Efficient hydrogen production and decomposition of glycerol were achieved on CuO-modified titania (CuO-TiO(2)) photocatalysts in glycerol aqueous solutions. CuO clusters were deposited on the titania surface by impregnation of Degussa P25 TiO(2) powder (P25) with copper nitrate followed by calcination. The resulting CuO-TiO(2) composite photocatalysts were characterized by X-ray diffraction (XRD), UV-visible spectrophotometry, X-ray photoelectron spectroscopy (XPS), N(2) adsorption-desorption, transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. The low-power ultraviolet light emitting diodes (UV-LED) were used as the light source for photocatalytic H(2)-production reaction. A detailed study of CuO effect on the photocatalytic H(2)-production rates showed that CuO clusters can act as an effective co-catalyst enhancing photocatalytic activity of TiO(2). The optimal CuO content was found to be 1.3 wt.%, giving H(2)-production rate of 2061 μmolh(-1)g(-1) (corresponding to the apparent quantum efficiency (QE) of 13.4% at 365 nm), which exceeded the rate of pure TiO(2) by more than 129 times. The quantum size effect of CuO clusters is deemed to alter its energy levels of the conduction and valence band edges in the CuO-TiO(2) semiconductor systems, which favors the electron transfer and enhances the photocatalytic activity. This work shows not only the possibility of using CuO clusters as a substitute for noble metals in the photocatalytic H(2)-production but also demonstrates a new way for enhancing hydrogen production activity by quantum size effect.     

Facile synthesis of nanoscaled α-Fe2O3, CuO and CuO/Fe2O3 hybrid oxides and their electrocatalytic and photocatalytic properties

A facile and easily controlled route was designed to synthesize nano-structured Fe₂O₃, CuO, and CuO/Fe₂O₃ hybrid oxides with different Cu/Fe molar ratios via a hydrothermal procedure. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and field-emission scanning electron microscopy (FE-SEM). The results showed that the morphologies of the samples changed with different Cu/Fe ratios. The electrocatalytic properties of the samples modified on a glassy carbon electrode for p-nitrophenol reduction in a basic solution were investigated. The results indicated that CuO/Fe₂O₃ hybrids with lower Cu/Fe ratio exhibited higher electrocatalytic activity. The photocatalytic performances of the samples for methyl orange degradation with assistance of oxydol under irradiation of visible light were studied. The results revealed that CuO/Fe₂O₃ hybrids with higher Cu/Fe ratio showed efficient photocatalytic activity.      

Electrochemical synthesis of ZnO nanorods/porous silicon composites and their gas-sensing properties at room temperature

The zinc oxide (ZnO) nanorods with different aspect ratio (length/diameter) were grown directly on the porous silicon (PS) substrate through electrochemical synthesis. The obtained ZnO nanorods/PS products were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and gas-sensing test. Comparative study shows that the addition of nonionic polymer polyvinylpyrrolidone (PVP) into oxygenated zinc chloride electrolyte can modulate the crystal growth and the aspect ratio of ZnO nanorods from electrodeposition, thus, influence the gas-sensing properties of ZnO nanorods/PS composites. With appropriate amount of PVP in the electrolyte, the product possessing high-density and large aspect ratio ZnO nanorods has an obvious improvement of the NO₂-sensing performances with high sensitivity, fast response-recovery characteristic, and good repeatability and selectivity. The gas-sensing mechanism was discussed in the paper. The result indicated that the heterojunction effect of ZnO nanorods and PS may be responsible for the excellent gas-sensing properties.     

两步水热法合成Sn_2Nb_2O_7纳米晶及其高效可见光分解水制氢性能（英文）

铌基半导体光催化材料因其具有独特的晶体结构和能带结构在光催化分解水制氢领域受到科研工作者的高度关注.然而,大多数铌基半导体光催化剂仅能够在紫外光驱动下实现光催化分解水制氢,具有可见光响应的铌基半导体光催化剂不仅数量少而且活性较低,因此发展新型纳米铌基半导体光催化剂并实现其高效可见光催化分解水产氢具有重要的学术和实用意义.具有烧绿石构型的Sn_2Nb_2O_7材料由于具有较窄的禁带宽度(2.4 e V)和合适的导带和价带电势在可见光催化分解水制氢方面引起了科研人员广泛的兴趣.然而,目前报道的利用高温固相法制备的块体Sn_2Nb_2O_7材料由于颗粒尺寸较大和比表面积较小而导致光催化活性较差.因此,发展一种简便高效的制备方法实现纳米Sn_2Nb_2O_7材料的可控制备进而提高其可见光催化活性仍具有一定的挑战性.我们发展了一种简便的两步水热合成方法实现了Sn_2Nb_2O_7纳米晶的可控制备.扫描电镜和透射电镜测试结果表明,通过两步水热法得到的Sn_2Nb_2O_7纳米颗粒具有较好分散度,其平均颗粒尺寸为20 nm.X射线衍射测试结果也进一步证明,通过两步水热法可以实现Sn_2Nb_2O_7纳米晶的可控制备.比表面积测试结果表明,Sn_2Nb_2O_7纳米晶的比表面积约为52.2 m~2/g,远远大于固相法制备的块体Sn_2Nb_2O_7材料(2.3 m~2/g).大量研究表明,大的比表面积有利于半导体催化材料催化活性的提升.通过考查所制备的Sn_2Nb_2O_7纳米晶的可见光分解水制氢能力,对其催化性能进行了评价.研究结果表明,以乳酸为空穴消耗剂,负载0.3wt.%Pt纳米颗粒作为助催化剂的Sn_2Nb_2O_7纳米晶表现出优异的可见光催化分解水产氢性能,其产氢速率是块体Sn_2Nb_2O_7材料的5.5倍.Sn_2Nb_2O_7纳米晶可见光催化分解水产氢性能提高的主要原因是其具有高分散度的纳米颗粒、较大的比表面积和更正的价带电势.首先,颗粒尺寸的纳米化能够显著减小光生电子和空穴的迁移距离,实现光生载流子快速迁移到催化剂表面进而参与催化反应;其次,大的比表面积能够提供更多的催化活性位点,进而有利于催化活性的提高;最后,X射线光电子能谱测试表明,Sn_2Nb_2O_7纳米晶具有更正的价带电势,研究表明,价带电势越正,其光生空穴氧化能力越强.在光催化分解水制氢过程中,具有较强氧化能力的光生空穴通过与空穴牺牲剂乳酸快速反应而被消耗掉,抑制了光生电子与空穴的复合,进而导致其具有较高的光催化产氢活性.     

ZnO/BiOI微球的合成及其光催化性能

通过一步溶剂热法合成ZnO/BiOI纳米复合材料,在Bi（NO₃）₃·6H₂O、KI、ZnO和乙二醇（EG）溶剂中,制备出的样品尺寸和形貌采用X射线粉末衍射（XRD）、场发射扫描电镜（FESEM）、高分辨透射电镜（HRTEM）、紫外-可见漫反射光谱（DRS）、X射线光电子能谱（XPS）、N₂吸附-脱附等,对实验所得产物的组成、结构及光学性质等进行表征。以染料罗丹明B（RhB）水溶液和气态乙醛作为降解对象,采用BiOI、ZnO/BiOI和ZnO微纳材料作为光催化剂,通过对BiOI、ZnO/BiOI和ZnO微纳材料在可见光下光催化降解染料罗丹明B（RhB）水溶液和气态乙醛,结果表明多孔微纳材料的ZnO/BiOI具有更高的降解效率,实验表明多孔微纳材料的ZnO/BiOI具有更高的氧空位浓度,因此使其催化活性增强,讨论了其可能的催化活性机理。     

ZnO/BiOI微球的合成及其光催化性能

通过一步溶剂热法合成ZnO/BiOI纳米复合材料,在Bi（NO₃）₃·6H₂O、KI、ZnO和乙二醇（EG）溶剂中,制备出的样品尺寸和形貌采用X射线粉末衍射（XRD）、场发射扫描电镜（FESEM）、高分辨透射电镜（HRTEM）、紫外-可见漫反射光谱（DRS）、X射线光电子能谱（XPS）、N₂吸附-脱附等,对实验所得产物的组成、结构及光学性质等进行表征。以染料罗丹明B（RhB）水溶液和气态乙醛作为降解对象,采用BiOI、ZnO/BiOI和ZnO微纳材料作为光催化剂,通过对BiOI、ZnO/BiOI和ZnO微纳材料在可见光下光催化降解染料罗丹明B（RhB）水溶液和气态乙醛,结果表明多孔微纳材料的ZnO/BiOI具有更高的降解效率,实验表明多孔微纳材料的ZnO/BiOI具有更高的氧空位浓度,因此使其催化活性增强,讨论了其可能的催化活性机理。     

CdS-TiO2/累托石复合材料的制备及光催化性能

采用原位插层法制备了CdS-TiO2/累托石纳米复合材料. 以X射线粉未衍射、电镜、红外光谱、漫反射吸收光谱及液氮吸附比表面积测定等方法对其微结构和性能进行了分析与表征. 并以罗丹明B(RB)为模拟有机污染物, 对比研究了累托石、TiO2/累托石与CdS-TiO2/累托石的吸附和光催化性能. 结果表明, 与累托石相比, CdS-TiO2/累托石具有更复杂的多孔结构、更大的孔体积和比表面积以及更有效的光吸收能力; 该类复合材料表现出良好的吸附性能和光催化降解活性.     

Synthesis of Gd-N Codoped Porous TiO2 Photocatalyst and Its Enhanced Photocatalytic Activities

Visible-light-active Gd-N codoped porous TiO₂(Gd-N-TiO₂) photocatalyst was fabricated by an evapora-tion-induced self-assembly route using surfactants as structure-directed agents. As-prepared samples were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy(TEM), X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller(BET) method, and ultraviolet-visible absorption spectroscopy. The results indicated that synergistic reaction occurred when codoping with Gd³⁺ and N, which enhanced the light absorption properties of TiO₂. Irregular worm-like particles with wide interparticle spaces were clearly observed by TEM. The average particle size of Gd-N-TiO₂ decreased to ca. 8 nm because co-doping inhibited the particles growth significantly. Thus, the specific surface area of Gd-N-TiO₂(198.7 m²/g) was higher than that of Degussa P25 TiO₂(50 m²/g). Gd-N-TiO₂ exhibited a high photocatalytic activity toward methyl orange degradation under UV-Vis or visible-light irradiation. The Gd-N-TiO₂ catalyst also presented a stable performance without losing activity after four successive photocatalytic experiments. The facile synthesis and excellent activity of Gd-N-TiO₂ indicated its great potential as industrial catalysts for wastewater treatment.     

聚合物控制CuO纳米盘的液相生长

表面活性剂聚丙烯酰胺（PAM）的控制下,在温和的低温水溶液中,高产率的CuO纳米盘被合成。粉未衍射（XRD）,扫描电镜（SEM）,高分辨透射电子显微（HRTEM）对产物的形貌结构进行表征。研究了不同反应条件如温度、PAM浓度等对产物形貌与尺寸的影响。结果表明,CuO纳米盘为单晶结构,沿着（002）和（110）面生长。PAM对纳米盘的形成起到关键作用。典型的聚合物-晶体作用生长机理用来解释CuO纳米盘的形成。聚合物诱引晶体生长与调控纳米晶自组装将提供了一条有效的路径来合成具有复杂形貌与特殊结构的无机和无机-有机杂化材料。     

Improved visible light photocatalytic activity of sphere-like BiOBr hollow and porous structures synthesized via a reactable ionic liquid

BiOBr uniform flower-like hollow microsphere and porous nanosphere structures have been successfully synthesized through a one-pot EG-assisted solvothermal process in the presence of reactable ionic liquid 1-hexadecyl-3-methylimidazolium bromide ([C(16)mim]Br). The as-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) and diffuse reflectance spectroscopy (DRS). Possible formation mechanism for the growth of hollow microspheres was discussed. During the reactive process, ionic liquid [C(16)mim]Br played the role of solvent, reactant and template at the same time. Moreover, the photocatalytic activities of BiOBr flower-like hollow and porous structures were evaluated on the degradation of rhodamine B (RhB) under visible light irradiation. The results assumed that BiOBr porous nanospheres sample showed much higher photocatalytic activity than the conventionally prepared sample and TiO(2) (Degussa, P25). The relationship between the structure of the photocatalyst and the photocatalytic activities were also discussed in detail; it can be assumed that the enhanced photocatalytic activities of BiOBr materials could be ascribed to a synergistic effect, including high BET surface area, the energy band structure, the smaller particle size and light absorbance.     

Microwave-hydrothermal synthesis and photocatalytic properties of biomass charcoal/TiO2 nanocomposites

Biomass charcoal-doped titanium dioxide (C/TiO₂) composites were proposed by microwave-hydrothermal and calcination method using tetrabutyl titanate as the titanium source and lignin as the carbon source. TiO₂ crystals with different morphologies could be successfully adsorbed onto the surface of biomass charcoal. These products were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TG), derivative thermogravimetric (DTG), UV–vis diffuser flection spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FT-IR), and Brunauer–Emmett–Teller (BET). The photocatalytic activities of the as-obtained composites were checked under visible light irradiation. The results showed that both the microwave-hydrothermal temperature and time played an important role in the microstructure and photocatalytic activity of the samples. The rapid microwave-hydrothermal with the thermal post-treatment provides a promising route for the fabrication of biomass charcoal-doped nanocomposites materials.     

Dopant-stimulated CuO Nanofibers for Electro-oxidation and Determination of Glucose

We described the preparation of copper oxide composite nanofibers doped with carbon nanotubes (CuO/C-NFs) or nickel oxide(CuO/NiO-NFs) by electrospinning for direct glucose determination. The interest in exploring practical CuO/C-NFs and CuO/NiO-NFs electrode materials for sensor application was fascinated by the possibility of promoting electron transfer for kinetically unfavorable glucose oxidation reactions at a lower overpotential and thus improving the selectivity of the electrode for glucose in electroanalysis. The morphologies of CuO/C-NFs and CuO/NiO-NFs were characterized by scanning electron microscopy(SEM) and X-ray powder diffraction(XRD). The electrocatalytic performances of glucose were evaluated in detail by cyclic voltammetry(CV) and chronoamperometry. Facile charge transport, enhanced current response(at a lower overpotential of +0.35 V), improved stability and selectivity, as well as excellent resistance towards electrode fouling were observed at CuO/ C-NFs electrode in direct glucose electroanalysis. These merits are attributed to the highly porous three-dimensional network film structure of CuO/C-NFs electrode materials and the potential synergic catalytic effect of CuO and carbon nanotubes in composite nanofibers. This study may provide a new insight into metal oxide-based composite nanofibers obtained via electrospinning for fabricating novel and high performance sensors and devices.     

Facile synthesis of 3D flowerlike α-FeOOH architectures and their conversion into mesoporous α-Fe2O3 for gas-sensing application

We reported a facile and efficient solution-based route to prepare novel flowerlike α-FeOOH architectures without any template or surfactant. Scanning electron microscope (SEM) images reveal that leaf-like nanosheets with a thickness about 40 nm assembled into flowerlike superstructures. On the basis of time-dependent experiments, a multistage reaction mechanism for the formation of the flowerlike α-FeOOH was proposed. After heat treatment, the flowerlike α-FeOOH could be converted into corresponding mesoporous α-Fe₂O₃. Transmission electron microscopy (TEM) images and porosity analysis showed that the nanosheets have porous walls with a pore size of about 7 nm. As a demonstration of potential application for gas-sensing materials, the mesoporous α-Fe₂O₃ nanostructures exhibited short response/recovery time within 5/10 s, and low response concentration of 1 ppm toward acetone vapors. Large specific surface area and mesoporous structure should be beneficial for the sensing properties of α-Fe₂O₃.     

Room temperature electrochemical synthesis of CuO flower-like microspheres and their electrooxidative activity towards hydrogen peroxide

We describe a facile electrochemical route for the synthesis of CuO flower-like microspheres (CuO FMs) by anodic dissolution of bulk Cu in sodium hydroxide solution at room temperature and without heating. Scanning electron microscopy and X-ray diffraction revealed that the CuO FMs are phase-pure monoclinic crystallites and comprised of CuO nanoflakes. The concentration of NaOH has a large effect on the size of the CuO FMs. The possible formation mechanism is discussed. The CuO FMs are electrocatalytically active towards the oxidation of H₂O₂, and this has resulted in a sensor for H₂O₂. To our knowledge, this is the simplest way to obtain clean CuO FMs.

Facile large scale synthesis of CuCr2O4/CuO nanocomposite using MOF route for photocatalytic degradation of methylene blue and tetracycline under visible light

MIL-101(Cr) template method has been employed successfully to synthesize CuCr₂O₄/CuO composite. The synthesized sample was characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), high-resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy, N₂ adsorption–desorption isotherm (BET) analysis, and UV vis- diffuse reflectance spectroscopy (UV-DRS). The photocatalytic efficiency of the nanocomposite was evaluated towards the degradation of methylene blue (MB) dye and antibiotic tetracycline (TC) solution. The morphological studies confirmed that the CuO was uniformly dispersed on the CuCr₂O₄ matrix. The CuCr₂O₄/CuO nanocomposite showed high degradation efficiency of about 90% in the presence of H₂O₂ where the MB degradation reaction got completed in a mere 35 min and ~95% TC got degraded within 120 min.     

Construction of 3D hierarchical SnO2 microspheres from porous nanosheets towards NO decomposition

Three-dimensional (3D) hierarchical architectures are currently attracting worldwide interest owing to their fascinating morphology-dependent properties and potential applications. Herein we constructed SnO₂ microspheres with 3D hierarchical flower-like architectures self-assembled with porous SnS₂ nanosheets by a facile hydrothermal method with subsequent calcination. The chemical and physical properties as well as photocatalytic application of SnO₂ microspheres were investigated. The size and morphology were examined with scanning electron microscopy and transmission electron microscopy. The phase and crystalline structure were determined with powder X-ray diffraction. The UV–Vis absorption property was determined with UV–Vis diffuse reflectance. The photocatalytic activities were evaluated with nitrogen monoxide (NO) decomposition under UV–Vis light irradiation. The effects of calcination temperature on morphology and NO decomposition were also studied.     

A facile synthesis of hierarchical flower-like TiO2 with enhanced photocatalytic activity

The hierarchical flower-like TiO₂ has been achieved by using a simple solvothermal process without any surfactants or colloidal crystals as a template. The structures of the products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption–desorption analysis. The relationship between hierarchical structure and photocatalytic performance has been presented based on detailed characterizations. It was found that the hierarchical flower-like structure was a benefit for light absorption and significantly enhanced the photocatalytic activity.     

Synthesis,characterization and photocatalytic properties of CaNb2O6 with ellipsoid-like plate morphology

Ellipsoid-like two-dimensional (2D) plates of calcium niobate (CaNb₂O₆) were synthesized via the hydrothermal route without any surfactants or templates by controlling the reaction conditions, viz. the pH value, reaction time and temperature. The prepared powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), fluorescence spectroscopy, and diffuse reflectance UV–vis spectroscopy. It was found that the plates were consisted of uniaxially aligned nanorods and can absorb UV light with wavelengths of less than 340 nm. Compared with the powder of the same material prepared by the solid-state reaction method, the ellipsoid-like 2D plates exhibited a much lower room temperature luminescence intensity and higher photocatalytic activity for the degradation of Rhodamine B dye solution under UV light irradiation. The enhanced photocatalytic activity of the plates was assigned to their higher optical absorption capability, higher diffusion rate of charge carriers and higher surface area resulting from their reduced dimensionality.     

Facile Synthesis of Uniform Zinc-blende ZnS Nanospheres with Excellent Photocatalytic Activity toward Methylene Blue Degradation

Uniform and well-dispersed Zn S nanospheres have been successfully synthesized via a facile chemical route. The crystal structure, morphology, surface area and photocatalytic properties of the sample were characterized by powder X-ray diffraction(XRD), scanning electron microscopy(SEM), Brunauer-Emmett-Teller(BET) and ultraviolet-visible(UV-vis) spectrum. The results of characterizations indicate that the products are identified as mesoporous zinc-blende ZnS nanospheres with an average diameter of 200 nm, which are comprised of nanoparticles with the crystallite size of about 3.2 nm calculated by XRD. Very importantly, photocatalytic degradation of methylene blue(MB) shows that the as-prepared Zn S nanospheres exhibit excellent photocatalytic activity with nearly 100% of MB decomposed after UV-light irradiation for 25 min. The excellent photocatalytic activity of ZnS nanospheres can be ascribed to the large specific surface area and hierarchical mesoporous structure.