Sol–gel synthesis of ZnO–SiO2 thin films: impact of ZnO contents on its photonic efficiency

Highly crystalline ZnO–SiO₂ films obtained by a sol–gel method at different ZnO contents were deposited on silicon substrate (P(100)) using spin coating process. The XRD results revealed that the strong ZnO(100) peak is grown with highly c-axis oriented film and the crystallinity is progressively improved with increasing ZnO contents. SEM micrographs of the films deposited on silicon substrate show a homogeneous and uniformity structure at different ZnO content. The prepared ZnO–SiO₂ films are compared with either a film prepared from a commercial photocatalysts Hombikat UV-100 or Pilkington Glass Activ? by the determination of their photonic efficiencies for degradation of methylene blue. The photocatalytic efficiency of the 10 wt% ZnO–SiO₂ film was found to be about four times higher than film prepared from UV-100 or Pilkington Glass Activ?. The photocatalytic efficiencies of ZnO–SiO₂ films are increased with increasing ZnO content from 1 wt% to 10 wt% ZnO and then decreased at 15 wt% ZnO. The order of photocatalytic efficiencies of ZnO–SiO₂ films at different ZnO content and commercial photocatalysts after 6 h illumination were as following: 10 wt% ZnO > 15 wt% ZnO > 1 wt% ZnO > as-prepared 10 wt% ZnO–SiO₂ film > UV-100 > Pilkington Glass Activ?, which suggested that the ZnO–SiO₂ films are photoactive than commercial photocatalysts. The improved efficiency and potentially the low-cost synthesis suggest that this material might be practically useful as a photocatalyst film.     

Preparation, characterization and photocatalytic performance of Mo-doped ZnO photocatalysts

A series of Mo-doped ZnO photocatalysts with different Mo-dopant concentrations have been prepared by a grinding-calcination method.The structure of these photocatalysts was characterized by a variety of methods,including N 2 physical adsorption,X-ray diffraction(XRD),scanning electron microscopy(SEM),Fourier transform infrared(FT-IR) spectroscopy,photoluminescence(PL) emission spectroscopy,and UV-vis diffuse reflectance spectroscopy(DRS).It was found that Mo 6+ could enter into the crystal lattice of ZnO due to the radius of Mo 6+(0.065 nm) being smaller than that of Zn 2+(0.083 nm).XRD results indicated that Mo 6+ suppressed the growth of ZnO crystals.The FT-IR spectroscopy results showed that the ZnO with 2 wt.% Mo-doping has a higher level of surface hydroxyl groups than pure ZnO.PL spectroscopy indicated that ZnO with 2 wt.% Mo-doping also exhibited the largest reduction in the intensity of the emission peak at 390 nm caused by the recombination of photogenerated hole-electron pairs.The activities of the Mo-doped ZnO photocatalysts were investigated in the photocatalytic degradation of acid orange II under UV light(λ = 365 nm) irradiation.It was found that ZnO with 2 wt.% Mo-doping showed much higher photocatalytic activity and stability than pure ZnO.The high photocatalytic performance of the Mo-doped ZnO can be attributed to a great improvement in the surface properties of ZnO,higher crystallinity and lower recombination rate of photogenerated hole-electron(e-/h+) pairs.Moreover,the undoped Mo species may exist in the form of MoO3 and form MoO3 /ZnO heterojunctions which further favors the separation of e-/h+ pairs.     

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.     

Photocatalytic activity of ZNO with different morphologies synthesized by a sonochemical method

Different morphologies of ZnO structures were successfully synthesized in precursor solutions with the pH of 8, 9, 10, 11, and 12 by a sonochemical method at room temperature. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR) and Raman spectroscopy. The photocatalytic activities of ZnO samples with different morphologies were evaluated via the degradation of methylene blue (C₁₆H₁₈ClN₃S). In this research, the flower-like ZnO sample of densely assembled nanoplates exhibited the highest photodegradation of 64% under UV light irradiation within 300 min.     

Photocatalytic activity of flower-like ZnO derived by a d-glucose-assisted sonochemical method

This work reports the preparation of flower-like ZnO for applications in the catalytic oxidation of methyl orange (MO) in aqueous solution. The wurtzite ZnO samples with flower-like morphologies were obtained via a d-glucose-assisted sonochemical method. Effects of the presence of glucose, sonication times (0, 10, and 20 min) and calcination temperatures (300, 400, and 500 °C) on the morphology of the catalysts were investigated. Results from this work suggest that d-glucose played an important role in the formation of flower-like morphologies and the sonication processes further enhanced the flower-like characteristic ordering. The majority of ZnO samples prepared in this work had rather high photocatalytic activity after 45 min, with MO degradation greater than 85 % of the initial concentration. These results suggest that the photocatalytic activity of ZnO after 45-min reaction time correlates well with the specific surface area, and the number of oxygen vacancies present in the materials. The solubility of flower-like ZnO samples in the dye solution was measured to be 19.2 ppb after 24-h reaction time.     

Visible light photocatalytic activity of BiVO4 particles with different morphologies

Bismuth vanadate (BiVO₄) particles with different morphologies were synthesized by a one-step hydrothermal process and their optical and photocatalytic properties were investigated. Their crystal structure and microstructures were characterized using X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). XRD patterns demonstrate that the as-prepared samples are monoclinic cell. FESEM shows that BiVO₄ crystals can be fabricated in different morphologies by simply manipulating the reaction parameters of hydrothermal process. The UV–visible diffuse reflectance spectra (UV–vis DRS) reveal that the band gaps of BiVO₄ photocatalysts are about 2.07–2.21 eV. The as-prepared BiVO₄ photocatalysts exhibit higher photocatalytic activities in the degradation of rhodamine B (Rh B) under visible light irradiation (λ > 420 nm) compared with traditional N-doped TiO₂ (N-TiO₂). Furthermore, wheat like BiVO₄ sample reveals the highest photocatalytic activity. Up to 100% Rh B is decolorized after visible light irradiation for 180 min. The reason for the difference in the photocatalytic activities for BiVO₄ samples obtained at different conditions were systematically studied based on their shape, size and the variation of local structure.     

Assessment of metal contamination in an urban drainage system (using water and tilapia, Oreochromis spp.) in view of human health effect. A case study of some selected communities in Cape Coast township in Ghana

This research work aimed at studying the metal content of water and tilapia fish sample, Oreochromis spp., from a wastewater-fed pond around the University of Cape Coast community using instrumental neutron activation analysis. The metals studied were Al, As, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, V and Zn. In the water samples the order of elemental concentrations at sampling point 1, in ??g/g, was K (75.96?±?0.92), Na (18.52?±?0.35), Al (6.00?±?0.89), Mn (3.28?±?0.44), As (3.08?±?0.40), Mg (1.56?±?0.17), Ca (0.70?±?0.08), Cu (0.54?±?0.08) and V (0.04?±?0.01). Co, Cr, Fe and Zn were below detection limits of INAA. The order of elemental concentrations in the water at point 2 was as follows: Na (4.99?±?0.14), K (4.82?±?0.89), Mn (4.40?±?0.53), Mg (2.92?±?0.37), Al (1.98?±?0.21), As (0.69?±?0.10), Ca (0.24?±?0.07) and V (0.23?±?0.06) with Co, Cr, Cu, Fe and Zn falling below the detection limit of INAA. The concentrations recorded for Al, As, Cu and Mn in the water samples were all above WHO permissible limits. The mean levels of heavy metals in the soft tissue of tilapia was of the order: K?>?Mg?>?Fe?>?Ca?>?Na?>?Al?>?Mn?>?Zn?>?V?>?Cu?>?Cr?>?Co. Arsenic was below detection limit. The transfer factor values calculated for the metals Al, Ca, K, Mg, Mn, Na and V were all greater than one indicating movement of metals from the water column to the tilapia species. The hazard index (HI) calculated for Al, Fe, Mn and V suggested possible occurrence of adverse health effects (HI?>?1) where as the HI value obtained for Cr, Cu and Zn (i.e., HI?<?1) suggested unlikely adverse effects occurring.     

Photodegradation of chlorophenolic compounds using zinc oxide as photocatalyst: experimental and theoretical studies

Zinc oxide nanoparticles were synthesized via the sol?Cgel method. The structures of the obtained nanoparticles were investigated by X-ray diffraction. The photocatalytic degradation of chlorophenolic compounds, namely 2-chlorophenol (CP), 2,4-dichlorophenol (DCP) and 2,4,6-trichlorophenol (TCP), was carried out using ZnO nanoparticles under solar intensity of 20?C26?W?m^?2. The photocatalytic degradation efficiency of TCP?<?DCP?<?CP was found. The adsorption energies of the chlorophenolic compounds with ZnO catalyst were calculated from quantum chemical molecular dynamic model and found to increase in the order of TCP?<?DCP?<?CP.     

CuO Quantum‐Dot‐Sensitized Mesoporous ZnO for Visible‐Light Photocatalysis

How to extend ultraviolet photocatalysts to the visible‐light region is a key challenge for solar‐driven photocatalysis. Herein, we show that ultraviolet ZnO photocatalysts can present high visible‐light photocatalytic activity when combined with CuO quantum dots (QDs; <3 nm). Theoretical analysis demonstrates that the quantum size effect plays a key role in the photoactivity of the CuO/ZnO composite. For CuO QDs smaller than 3 nm, the separated charges could transfer from CuO QDs to the conduction bands of ZnO due to quantum splitting of the CuO energy level and phonon compensation for the difference in the conduction band minimum of CuO and ZnO; however, this process would not occur with the disappearance of the quantum size effect. Further structural analysis demonstrates that interfacial charge separation and transfer between ZnO and CuO dominate the photocatalytic processes instead of a single CuO or ZnO surface. Compared with ZnO? noble metal structures (e.g., ZnO? Ag or ZnO? Au), these ZnO? CuO QD composites present wider absorption bands, higher visible photocatalytic efficiencies, and lower costs.     

可循环SERS基底ZnO/Ag纳米材料合成和表征

利用简易、绿色、一锅煮的水热法合成了花状氧化锌/银复合纳米材料。然后利用各种光谱和显微技术对复合物进行了表征,并讨论了其表面增强拉曼(SERS)性能和光催化性能。结果表明氢氧化钠的量对于这种复合纳米材料的形貌和性能具有重要的调节作用。和其他形貌的氧化锌/银复合纳米材料相比较,花状氧化锌/银复合纳米材料具有最佳的光催化性能。同时进一步以花状氧化锌/银复合纳米材料作为SERS基底研究其表面增强拉曼性能,结果表明这种复合材料同时具有很好的表面增强拉曼性能。光催化和表面增强拉曼结果表明这种花状氧化锌/银复合纳米材料有望在有机物检测中作为一种具有很好的可循环性的新表面增强拉曼基底材料。     

可循环SERS基底ZnO/Ag纳米材料合成和表征

利用简易、绿色、一锅煮的水热法合成了花状氧化锌/银复合纳米材料。然后利用各种光谱和显微技术对复合物进行了表征,并讨论了其表面增强拉曼（SERS）性能和光催化性能。结果表明氢氧化钠的量对于这种复合纳米材料的形貌和性能具有重要的调节作用。和其他形貌的氧化锌/银复合纳米材料相比较,花状氧化锌/银复合纳米材料具有最佳的光催化性能。同时进一步以花状氧化锌/银复合纳米材料作为SERS基底研究其表面增强拉曼性能,结果表明这种复合材料同时具有很好的表面增强拉曼性能。光催化和表面增强拉曼结果表明这种花状氧化锌/银复合纳米材料有望在有机物检测中作为一种具有很好的可循环性的新表面增强拉曼基底材料。     

Facile synthesis of core-shell ZnO/Cu<Subscript>2</Subscript>O heterojunction with enhanced visible light-driven photocatalytic performance

As p–n heterojunction photocatalysts usually possess dramatically improved photocatalytic activity than single photocatalysts, a novel ZnO/Cu₂O heterojunction was designed by a facile self-templating method in this study. The crystal structure, chemical composition, surface morphology, and optical property of ZnO/Cu₂O heterojunction were investigated to clarify the structure-property correlation. Scanning electron microscope and transmission electron microscope images proved the uniform core-shell submicrospheres of ZnO/Cu₂O, in which a three-dimensional flower-like ZnO core was coated by a shell comprised of Cu₂O nanoparticles. The photoresponse result showed that the band gap of the ZnO/Cu₂O core-shell submicrospheres became narrow, and the absorption edge shifted from the ultraviolet region (380?nm) to the visible region (500?nm) compared with the pure ZnO microflowers. For the degradation of Rhodamine B under visible light, the photocatalytic efficiency of ZnO/Cu₂O submicrospheres reached 96% within 40?min of reaction time, which was 3.8 times higher than that of pure ZnO microflowers and up to 4.5 times than that for pure Cu₂O nanoparticles. The remarkable visible light-driven photocatalytic performance is mainly attributed to the extended photoresponse range and effective separation of the photo-generated electron-hole pairs in the unique heterojunction.

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ZnO/Cu₂O core-shell microspheres for the degradation of RhB under visible light

     

Photobleaching of pollutant dye catalyzed by p-n junction ZnO-CuO photocatalyst under UV-visible light activation

The p-n junction ZnO/CuO nanocomposite photocatalysts are prepared via the copreripitation route. The detailed structural, compositional and optical characterization and physico-chemical properties of the obtained products are analyzed by X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), photoluminscience spectra (PL) and electron spin resonance (ESR) spin-trapping techniques. The experimental results showed that the absorption wavelength range of the ZnO/CuO nanocomposite was notably extended towards the visible-light region (400–500 nm). The photocataltic activity of the ZnO/CuO nanocomposite was evaluated based on the decomposition of by methyl orange (MeO) in aqueous solution under UV-vis light irradiation. The photocatalytic activity of ZnO/CuO nanocomposite is found much better than of bare ZnO photocatalyst under the identical conditions. Factors influencing photocatalytic activity and the mechanism of photocatalysis reaction were also addressed.     

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。     

Preparation and optical properties of high-quality oriented of Al and Er co-doped ZnO thin films

High-quality c-axis oriented Al and Er co-doped ZnO films were prepared on the quartz glasses by sol?Cgel method. In order to obtain the optimal processing parameters for the growth of the oriented film, an L₁₆ (4⁵) orthogonal experimental design was chosen. The experimental results show the rank of 5-factors as follows: Er at.%?>?the number of coating layer?>?annealing temperature?>?Al at.%?>?the concentration of the sol. The Al and Er co-doped film prepared using the optimal parameters exhibits the preferential orientation along the c-axis perpendicular to the substrate surface. In addition, the structural, morphological and optical properties of the films were studied by X-ray diffraction, scanning electron microscopy, and UV?Cvisible spectrophotometer, respectively. The photoluminescence spectra were also used to characterize the luminescence properties of the samples. It is found that when ZnO was co-doped with 7?% Al and 1.5?% Er, the blue emission centered at 465?nm disappears and the green emission centered at 547?nm increases with a blue shift, resulted from the rapid reducing of the interstitial Zn defect, and increasing of the oxygen defects and vacancies caused by Al³⁺ and Er³⁺ dopants.     

Trace metal accumulation in tissues of sole (Solea senegalensis) and the relationships with the abiotic environment

The distribution patterns and the organ-specific accumulation trends of 10 trace metals (iron, manganese, zinc, copper, chromium, nickel, cobalt, lead, cadmium and silver) and 4 major elements (sodium, potassium, calcium and magnesium) in 10 different tissues (heart, muscle, kidney, stomach, intestine, liver, gill, gonads, white skin and dark skin) of a benthic fish species (Solea senegalensis) from a densely populated coastal area affected by anthropogenic activities, the Bay of Cadiz (SW Spain), have been investigated. High variability of metal concentrations among tissues were found for Ca, Fe, Zn, Cu, Pb and Ag. Factor analysis was applied to study this variability. Five principal components were found explaining the 92.95% of the total variance and similarities in behavioural patterns of bioaccumulation were described. They associated Mg, Cr, Ni and Mn to intestine and stomach tissues (PC1), Ag, Cu and Cd to liver (PC2), Zn, K and Co to gonads (PC3), Na, Fe and Pb to gill, heart and kidney tissues (PC4) and Ca, Pb and Mn to gill and dark skin (PC5). The metallic concentration in the sediment and water was also studied. The pollution in this area was found moderate with outstanding values of Zn, Cu and Pb (average values of 139, 50.4 and 75.6?mg?kg^?1, respectively) in sediment and dissolved Cu (average value of 2.5?µg?L^?1). Metal bioconcentration trends followed the order Zn?>?Cu?>?Cd?>?Pb for dissolved metals in seawater, Cu?>?Zn?>?Cd?>?Pb?≈?Mn?>?Fe?≈?Ni?≈?Co for metals associated to particulate matter and Zn?≈?Cu?>?Cd?>?Mn?>?Co?≈?Fe?>?Ni?≈?Pb?>?Cr for metals in the sediment. Higher values were found for copper in liver, zinc in gonads and lead in gill, showing the relationship between biotic and abiotic environment. In addition, Cd bioconcentration factors were found high in liver and gill showing the sensitivity of sole to this metal even at low concentrations.     

形貌可控ZnO微纳米结构的水热合成及光催化性能

以乙醇胺为辅助溶剂,采用水热合成法,制备了花状、梭状和剑状的ZnO微纳米结构。采用扫描电镜(SEM)、X射线衍射(XRD)、光致发光光谱(PL)和拉曼光谱等测试手段对样品的形貌、结构、晶相等进行了表征。结果表明所有样品均为六方纤锌矿结构ZnO;其形貌和结晶度可通过改变物质的量的配比nZn2+/nOH-来调控。探讨了反应物配比对产物形貌结构的影响,乙醇胺对不同形貌ZnO的制备起到至关重要作用。以亚甲基蓝为目标降解物,采用紫外-可见吸收光谱(UV-Vis)并结合低温氮吸附-脱附比表面测试(BET),研究了花状、梭状和剑状ZnO的光催化活性。结果表明,与商用ZnO相比,制备的ZnO具有更好的光催化活性;样品催化活性与其比表面积不成正比,具有最小比表面积的花状ZnO拥有最好的光催化活性,这可能是由于其低的结晶度和特殊的花状形貌所致。     

形貌可控ZnO微纳米结构的水热合成及光催化性能

以乙醇胺为辅助溶剂,采用水热合成法,制备了花状、梭状和剑状的ZnO微纳米结构。采用扫描电镜（SEM）、Ｘ射线衍射（XRD）、光致发光光谱（PL）和拉曼光谱等测试手段对样品的形貌、结构、晶相等进行了表征。结果表明所有样品均为六方纤锌矿结构ZnO;其形貌和结晶度可通过改变物质的量的配比n_Zn²⁺/n_OH^-来调控。探讨了反应物配比对产物形貌结构的影响,乙醇胺对不同形貌ZnO的制备起到至关重要作用。以亚甲基蓝为目标降解物,采用紫外-可见吸收光谱（UV-Vis）并结合低温氮吸附-脱附比表面测试（BET）,研究了花状、梭状和剑状ZnO的光催化活性。结果表明,与商用ZnO相比,制备的ZnO具有更好的光催化活性;样品催化活性与其比表面积不成正比,具有最小比表面积的花状ZnO拥有最好的光催化活性,这可能是由于其低的结晶度和特殊的花状形貌所致。     

Physicochemical and photocatalytic properties of the ZnO particles synthesized by two different methods using three different precursors

ZnO particles with different morphological forms and various scale sizes were successfully synthesized as photocatalysts using two different methods (sol–gel and precipitation) and three precursors (zinc acetate dihydrate, zinc nitrate hexahydrate, and zinc sulfate heptahydrate). These materials were calcined at 500 °C for 3 h and characterized by various physicochemical techniques such as X-ray diffraction, Fourier transform infrared, transmission electron microscopy, S_BET, and UV–vis diffuse reflectance. The results showed that the crystalline structure, size, and morphology of the ZnO particles are strongly influenced by the preparation method and by the nature of the precursor used as reactant. The photocatalytic efficiency of the synthesized photocatalysts was evaluated by the photodegradation of methyl orange in aqueous solution under UV-A light. The results showed that the ZnO nanoparticles prepared the by sol–gel method from zinc acetate are more efficient than those prepared by the precipitation method.     

Elemental Analysis and Nutritional Value of Seaweed from the East Coast of KwaZulu-Natal,South Africa

Seaweed, biologically and phycologically referred to as algae, is classified as Rhodophyta (red), Chlorophyta (green), and Ochrophyta (brown). In this study, the concentrations of 13 elements (As, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Se, and Zn) were investigated for 14 seaweed species of varying classes (Amphiroa bowerbankii, Ceramium virgatum, Dichotomaria tenera, Ellisolandia (Coralline) elongata, Gelidium abbottiorum, Gracilaria canaliculata, Jania rubens, and Jania (Haliptylon) squamata of the Rhodophyta (red); Caulerpa filiformis, Codium capitatum, Halimeda cuneata, and Ulva rigida of the Chlorophyta (green); and Cystoseira myrica and Sargassum elegans of the Ochrophyta (brown) to determine the nutritional value of seaweed based on its medicinal properties, industrial importance, and natural abundance. The elemental distribution in seaweeds was in decreasing order of Ca?>?Mg?>?Fe?>?Cu?>?Mn?>?Zn?>?Cr?>?Co?>?Se?>?As?>?Pb?>?Ni?>?Cd. All edible species contained high levels of macro and microelements with the corali sp. accumulating high levels of Ca. Of the edible seaweeds characterized, only three (G. abbottiorum, E. (Coralline) elongate and C. virgatum) are suitable for human consumption due to high levels of As, Cd, and Pb present in the other species. These three species are also rich in essential nutrients, specifically C. virgatum, which is high in Cu and Se. Hierarchical cluster analysis showed a clear similarity in distribution of essential and toxic elements in similar classes of seaweed.