ZnO自组装薄膜的可控生长及其光催化性能

通过改变工艺参数, 制得了粒径可控的ZnO自组装薄膜. 该薄膜在可见光区域出现了光子带隙. 以染料甲基橙的光催化降解为模型评价了ZnO自组装薄膜的光催化活性. 利用X射线衍射仪(XRD)和扫描电子显微镜(SEM)表征了ZnO的晶体结构和微观形貌. 实验结果表明, ZnO自组装薄膜在太阳光照射下表现出良好的光催化性能, 其光催化活性随着ZnO颗粒粒径的减小而提高. ZnO自组装薄膜光催化降解甲基橙的反应符合一级反应动力学规律.     

Synthesis of an Ag–ZnO nanocomposite catalyst for visible light-assisted degradation of a textile dye in aqueous solution

The photocatalytic activity of silver-deposited ZnO in the photodegradation of methyl orange (MO) was investigated. The as-prepared photocatalysts were characterized by X-ray diffraction, UV–visible diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The results showed that the silver-deposited ZnO had a visible light plasmon absorption band. The photocatalytic degradation experiment revealed that the catalytic efficiency of the Ag–ZnO composite in the degradation of MO was greater than that of pure ZnO samples. This study shows that the degradation process is dominated by the Ag–ZnO photocatalytic system, complying with a pseudo-first-order rate law. Under the experimental conditions, approximately 65.0% dye removal was achieved within 100 min.     

A general approach for the growth of metal oxide nanorod arrays on graphene sheets and their applications

In the fabrication of flexible devices, highly ordered nanoscale texturing, such as semiconductor metal oxide nanorod arrays on flexible substrates, is critical for optimal performance. Use of transparent conducting films, metallic films, and polymer substrates is limited by mechanical brittleness, chemical and thermal instability, or low electrical conductivity, low melting point, and so on. A simple and general nanocrystal-seed-directed hydrothermal route has now been developed for large-scale growth of nanorod arrays of various semiconductor metal oxides (MO), including TiO(2), ZnO, MnO(2), CuO, and ZrO(2) on both sides of flexible graphene (G) sheets to form sandwichlike MO/G/MO heterostructures. The TiO(2)/G/TiO(2) heterostructures have much higher photocatalytic activity than TiO(2) nanorods, with a photocatalytic degradation rate of methylene blue that is four times faster than that of the TiO(2) nanorods, and are thus promising candidates for photocatalytic decontamination.     

Synthesis of Nano‐Sized Zinc Oxide Photocatalyst by Combustion Method

The objective of this research was to use combustion synthesis to create a nano‐sized ZnO photocatalyst using citric acid as the fuel and zinc nitrate as the oxidant. The starting materials were mixed in a stoichiometric ratio, and a slurry precursor with high homogeneity was formed. The precursor was ignited at room temperature, resulting in dry, loose, and voluminous ZnO powders. The powders, characterized by SEM, TEM and XRD, showed a particle size range of 40 to 80 nm with a wurtzite structure. The ZnO powders were introduced as a photocatalyst for the degradation of methyl orange, which was adopted as a model compound. UV light (6W) was used as the irradiation source to induce synthesized ZnO powders to perform catalytic activity. The photocatalytic reaction was executed in 40 mL of a 10 ppm methyl orange aqueous solution under 254 nm UV illumination. In this work, it was observed that both UV light and ZnO powders are needed for the photocatalytic reaction. In addition, it was found that increasing the amount of ZnO powder present in the MO (methyl orange‐C₁₄H₁₄N₃NaO₃S) solution did not correlate directly with an increase in photocatalytic ability. It was found that the scattering problem of UV light also needs to be considered. The optimized photocatalytic degradation ratio in this work reached 92.7%.     

Enhancement of oxygen vacancies and solar photocatalytic activity of zinc oxide by incorporation of nonmetal

B-doped ZnO and N-doped ZnO powders have been synthesized by mechanochemical method and characterized by TG-DTA, XRD, SEM-EDX, XPS, UV-visible and photoluminescence (PL) spectra. X-ray diffraction data suggests the hexagonal wurtzite structure for modified ZnO crystallites and the incorporation of nonmetal expands the lattice constants of ZnO. The room temperature PL spectra suggest more number of oxygen vacancies exist in nonmetal-doped ZnO than that of undoped zinc oxide. XPS analysis shows the substitution of some of the O atoms of ZnO by nonmetal atoms. Solar photocatalytic activity of B-doped ZnO, N-doped ZnO and undoped ZnO was compared by means of oxidative photocatalytic degradation (PCD) of Bisphenol A (BPA). B-doped ZnO showed better solar PCD efficiency as compare to N-doped ZnO and undoped ZnO. The PCD of BPA follows first order reaction kinetics. The detail mechanism of PCD of Bisphenol A was proposed with the identification of intermediates such as hydroquinone, benzene-1,2,4-triol and 4-(2-hydroxypropan-2-yl) phenol.     

Study on the photocatalytic degradation of methyl orange in water using Ag/ZnO as catalyst by liquid chromatography electrospray ionization ion-trap mass spectrometry

A nanocrystal catalyst Ag/ZnO was successfully synthesized using a simple solvothermal method in this study. This catalyst was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that this catalyst was composed of metallic Ag and ZnO. The photodegradation of methyl orange (MO) was investigated in aqueous suspension containing Ag/ZnO catalyst under UV irradiation. Liquid chromatography coupled with electrospray ionization ion-trap mass spectrometry was applied to the analysis of the samples coming from the photocatalytic degradation of MO. The experimental results showed that there were four intermediates existing in the photocatalytic reaction. MO could be mineralized in the Ag/ZnO suspension after 60 min illumination.     

Preparation of ZnO/GO composite material with highly photocatalytic performance via an improved two-step method

ZnO/graphene oxide(ZnO/GO) composite material,in which ZnO nanoparticles were densely coated on the GO nanosheets,was successfully prepared by an improved two-step method and characterized by IR, XRD,TEM,and UV-vis techniques.The improved photocatalytic property of the ZnO/GO composite material,evaluated by the photocatalytic degradation of methyl orange(MO) under UV irradiation,is ascribed to the intimate contact between ZnO and GO,the enhanced adsorption of MO,the quick electron transfer from excited ZnO particles to GO sheets and the activation of MO molecules viaπ-πinteraction between MO and GO.     

Biomineralization‐Inspired Preparation of Zinc Hydroxide Carbonate/Polymer Hybrids and Their Conversion into Zinc Oxide Thin‐Film Photocatalysts

The development of ZnO thin films has been achieved through the conversion of zinc hydroxide carbonate thin‐film crystals. Crystallization of this compound is induced by a biomineralization‐inspired method with polymer‐stabilized amorphous precursors. The crystals grow radially on polymer matrices, leading to the formation of zinc hydroxide carbonate/polymer thin‐film hybrids that fully cover the substrate. These hybrids are converted into ZnO and retain their thin‐film morphologies. The resultant ZnO thin films exhibit a preferential crystallographic orientation that is attributed to the alignment of zinc hydroxide carbonate crystals before conversion. In addition, a photocatalytic function of the ZnO thin films has been demonstrated by analyzing the oxidation reaction of 2‐propanol. The biomineralization‐inspired approach reported herein is a promising way to develop ZnO materials with controlled morphologies and structures for photocatalytic applications.     

Degradation of toluene gas at the surface of ZnO/SnO2 photocatalysts in a baffled bed reactor

To eliminate volatile organic compounds (VOCs) from contaminated air, a novel medium-scale baffled photocatalytic reactor was designed and fabricated, using immobilized ZnO/SnO₂ coupled oxide photocatalysts. Toluene was chosen as a representative pollutant of VOCs to investigate the degradation mechanism and the parameters affecting photocatalytic degradation efficiency. The preliminary experimental results indicate that the degradation efficiency of toluene increased with the increase of the light irradiation dosage, while it decreased with the increase of concentrations of toluene. The degradation efficiency increased rapidly with the increase of the relative humidity in a low humidity range from 0 to 35%, but decreased gradually in a high relative humidity (i.e., >35%). The optimum experimental conditions for toluene degradation is a toluene concentration of 106 mg m^?3, a relative humidity of 35%, and an illumination intensity of ca. 6 mW cm^?2 at the surface of ZnO/SnO₂ photocatalysts. The intermediates produced during the gaseous photocatalytic degradation process were identified using the GC–MS technique. Based on these identified intermediates, the photocatalytic mechanism of toluene into ZnO/SnO₂ coupled oxide catalyst was also deduced.     

Spherical Zinc Oxide Nano Particles from Zinc Acetate in the Precipitation Method

The liquid precipitation method using zinc acetate dihydrate was applied for the synthesis of uniform and spherical ZnO nanoparticles. The ultrafine zinc oxid was prepared in a water‐ethanol mixture solution. The solution containing zinc cation was soluble in water. The surface‐active agent triethanolamine (TEA) was soluble in ethanol. Then alkali precipitated by adding n‐propylamine. The spherical zinc oxide particle morphology was found to be highly dependent on the zinc salt concentration, ethanol‐water ratio, and the surface‐active agent additive. The process can produce white ZnO powder of 50–90 nm in size. The morphology of zinc oxide showed a powder shape by transmission electron microscopy (TEM), the crystallization phase structure of zinc oxide by X‐ray diffraction (XRD), and the zinc oxide remaining by using an organic analysis by infrared spectroscopy (IR).     

Zinc oxide prepared by homogeneous hydrolysis with thioacetamide, its destruction of warfare agents, and photocatalytic activity

Zinc sulfide (ZnS) nanoparticles were prepared by homogeneous hydrolysis of zinc sulfate and thioacetamide (TAA) at 80 degrees C. After annealing at a temperature above 400 degrees C in oxygen atmosphere, zinc oxide (ZnO) nanoparticles were obtained. The ZnS and ZnO nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and Brunauer-Emmett-Teller (BET)/Barrett-Joyner-Halenda (BJH) methods were used for surface area and porosity determination. The photocatalytic activity of as-prepared zinc oxide samples was determined by decomposition of Orange II dye in aqueous solution under UV irradiation of 365 nm wavelength. Synthesized ZnO were evaluated for their non-photochemical degradation ability of chemical warfare agents to nontoxic products.     

Photocatalytic activities of multilayered ZnO-based thin films prepared by sol–gel route: effect of SnO2 heterojunction layer

In present study, ZnO/SnO₂/ZnO/SnO₂/ZnO multi–layer, ZnO/SnO₂/ZnO triple layer and ZnO single layer films have been deposited on glass substrate by sol–gel dip–coating technique. The structural and optical properties of thin films have been investigated by X-ray diffractometer, UV–visible, photoluminescence spectroscopies and scanning electron microscopy. The structural analysis reveals structural inhomogeneities and different crystallite growth processes as function of number of deposited layers. A comparison between photocatalytic activity of zinc oxide samples toward photodegradation of phenol, 4-aminophenol and 4-nitrophenol has been performed under UV light irradiation. Experiments were conducted to study the effects of operational parameters on the degradation rate. Pseudo-first-order photodegradation kinetics was observed on all films and the reaction constants were determined. The results showed that the photocatalytic activity of ZnO multi–layer film was superior to that of the ZnO single- and triple-layer films. Differences in film efficiencies can be attributed to differences in crystallinity, surface morphology, defect concentration of oxygen vacancy and to presence of SnO₂ sublayer that may act as trap for electrons generated in the ZnO layer thus preventing electron–hole recombination. The results reveal that SnO₂ hetrojunction layers improve crystalline quality, optical and photocatalytic properties of ZnO multilayered films.     

钒酸银/氧化石墨烯复合物的制备和可见光催化性能

通过改进Hummers法制备了氧化石墨烯(GO),采用液相沉淀法合成了Ag₃VO₄/GO复合物,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和紫外-可见(UV-Vis)漫反射光谱等技术手段对样品进行了测试表征;并在可见光辐射下(λ≥420 nm)考察了复合物催化剂中GO含量对Ag₃VO₄光催化降解甲基橙溶液(MO)的性能影响。 结果表明,掺杂质量分数2%的GO复合物光催化活性提高最显著,30 min内对MO的降解率可达到89%以上,是纯Ag₃VO₄光催化活性的3倍。     

Crystallization and Reduction of Sol-Gel-Derived Zinc Oxide Films by Irradiation with Ultraviolet Lamp

Structural changes in sol-gel films with photo-irradiation were investigated using zinc oxide (ZnO) derived from zinc acetate. The exposure of the films to an ultraviolet lamp induced hexagonal ZnO crystals in a relatively dense amorphous structure. On the other hand, the formation of zinc metal was found in a porous gel film. The photo-induced crystallization and reduction are ascribed to the electronic excitation in the metastable non-crystalline states.     

WO3纳米颗粒修饰ZnO纳米管的光催化性能

二甲四氯钠(MCPA-Na)是一种广泛用于牧场和果园的除草剂,但由于其生物降解性极低,已成为地下水和浅水中的主要污染物.研究发现,半导体可以有效地辅助降解转化危险化学品.ZnO纳米管因其中空结构和较大的比表面积,而在光催化降解有机物方面备受关注.但是,ZnO只能吸收紫外光,如果将其与窄带隙半导体进行复合,可以有效降低带隙,增强其在可见光区域的光吸收,表现出更好的光催化性能.WO3是一种具有稳定物理化学性质及耐光腐蚀窄带隙半导体.采用WO3修饰ZnO纳米管,能扩展ZnO吸收光的范围以及提高ZnO纳米管的耐光腐蚀性能.本文首先通过电化学合成的方法制备了ZnO纳米管,然后按照不同的W/Zn摩尔比将(NH4)6H2W12O40·XH2O滴加在纳米管表面,并在450 ℃下退火2 h制得ZnO-WO3纳米管阵列.研究了不同WO3含量的ZnO-WO3纳米管光催化降解MCPA-Na性能,并且通过X射线光电子能谱(XPS)、傅里叶红外光谱仪(FTIR)、紫外可见光谱(UV-Vis)和光致发光光谱(PL)等手段研究了复合WO3纳米颗粒后ZnO纳米管半导体光催化性能提高的原因.XPS结果表明,W元素在ZnO-WO3纳米管阵列中以W6+的形式存在.FTIR结果表明,复合WO3后的ZnO-WO3复合半导体上比纯ZnO纳米管表面具有更多的OH-基团.由于OH-可以捕获光生空穴,并转化为具有反应活性的●OH自由基,因此复合WO3能在一定程度上提高ZnO纳米管的光催化活性.UV-Vis结果表明,WO3的复合使得光谱发生明显红移,但随着WO3含量的增加,ZnO-WO3的吸光度明显增加.另外,PL结果表明,适当的复合WO3可以抑制光生电子-空穴的复合.这是因为W6+和晶格氧的相互作用产生了较高不饱和键和表面缺陷,而表面缺陷可以作为光生载流子的陷阱,促进了光生电子和空穴的分离,因而光催化性能提高.在模拟太阳光下研究了不同WO3含量的ZnO纳米管对光催化降解MCPA-Na溶液的性能.发现W/Zn摩尔比为3%的ZnO-WO3样品表现出最好的光催化活性,200 min内其降解率为98.5%.与纯ZnO纳米管相比,其光催化循环性能也有所提高.利用Mott-Schottky测试方法并结合UV-vis结果,我们计算得到不同WO3含量的ZnO-WO3复合半导体导带价带位置.由于WO3导带位置和价带位置都比ZnO的更高,WO3上产生的光生电子会向ZnO的导带移动,而ZnO光生空穴向WO3的价带移动,从而促使光生电子和空穴的分离,提高了光催化性能.但是如果WO3复合的量太大,则在ZnO纳米管上分散性不好,反而成为光生空穴和电子复合中心,导致其光催化活性降低.     

Co doped ZnO nanowires as visible light photocatalysts

High aspect ratio cobalt doped ZnO nanowires showing strong photocatalytic activity and moderate ferromagnetic behaviour were successfully synthesized using a solvothermal method and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), vibrating sample magnetometry (VSM) and UV–visible absorption spectroscopy. The photocatalytic activities evaluated for visible light driven degradation of an aqueous methylene orange (MO) solution were higher than for Co doped ZnO nanoparticles at the same doping level and synthesized by the same synthesis route. The rate constant for MO visible light photocatalytic degradation was 1.9·10⁻³ min⁻¹ in case of nanoparticles and 4.2·10⁻³ min⁻¹ in case of nanowires. We observe strongly enhanced visible light photocatalytic activity for moderate Co doping levels, with an optimum at a composition of Zn_0.95Co_0.05O. The enhanced photocatalytic activities of Co doped ZnO nanowires were attributed to the combined effects of enhanced visible light absorption at the Co sites in ZnO nanowires, and improved separation efficiency of photogenerated charge carriers at optimal Co doping.     

Wettability and photodegradation activity of sol–gel dip-coated zinc oxide films

The hydrophilic characteristics of zinc oxide combined with the electronic properties of this width band gap semi-conductor were used to produce transparent, anti fog and photocatalytic porous films by using a simple sol?Cgel dip-coating process. The observed values of contact angles (near to 10°) and calculated spreading coefficients (close to zero) indicate that sol?Cgel dip-coated ZnO porous films show excellent wettability. The photocatalytic behavior of these films measured from methylene blue degradation is dependent on the film thickness in agreement with wettability results; as the film thickness increases from 0.1?±?0.05 to 0.5?±?0.05 the photocatalytic reaction rate constant increases from 0.9?×?10^?3 to 5.5?×?10^?3 min^?1.     

特殊形貌的ZnO晶体：水热法生长及光催化性能

采用水热法制得了微米棒状的ZnO结构,并通过改变降温冷却方式得到了锥形管状的ZnO结构。以染料甲基橙的光催化降解为模型评价了ZnO的光催化活性。利用XRD和SEM表征了ZnO的晶体结构和微观形貌。结果表明,所得的ZnO晶体在高压汞灯照射下表现出良好的光催化性能,且ZnO锥形管的光催化活性优于微米棒。ZnO晶体光催化降解甲基橙的反应符合一级反应动力学规律。探讨了ZnO锥形管的形成机理以及光催化降解甲基橙的作用机理。     

Two-Dimensional (2D) Porous Zinc Oxides Derived from the Coordination Polymer via Chemical-Assisted Phase Transition

Two-dimensional (2D) porous zinc oxides (ZnO) were successfully prepared via chemical treatment and thermal annealing of coordination polymers (CPs) precursors consisting of Zn(II) ion and fumarate ligand. The morphology, crystalline phase, chemical state, and surface area of the resultant ZnO were characterized. It is experimentally discovered that the crystal phase of the CP bearing Zn(II) ions is transformed to the zinc hydroxide crystal phase by chemical treatment using ammonia water. The prepared CP-derived porous 2D ZnO exhibited enhanced photocatalytic efficiency for dye degradation under black-light irradiation (365 nm) compared to CP-derived non-porous ZnO without a chemical-assisted phase transition process.     

碳纳米管/氧化锌纳米复合材料的制备及其形貌控制

0引言碳纳米管(CNT)优良的力学、电学、热学性能使其在材料、储能、传感等许多领域都有广泛的应用前景,近年来,以碳纳米管为载体制备的纳米复合材料因其独特的应用潜力而受到广泛关注:彭峰等[1]用FeSO4-H2O2体系修饰碳纳米管,成功地制备了由碳纳米管负载的Fe2O3催化剂;Chen等[2]用溶胶凝胶法制备了CNT/SnO复合材料,作为Li离子电池阴极材料,测试表明它的电化学性能比单独的CNT和SnO材料都有所增强;Jitianu等[3]用溶胶凝胶和水热方法得到不同形貌的TiO2/CNT复合结构,这种新型的纳米复合材料在光催化方面有着重要的应用前景。纳米Z…