Fe-Ni 共掺杂 ZnO 的制备及其光催化降解甲基橙活性

 采用溶液法制备了 Fe-Ni 共掺杂 ZnO 光催化剂, 并运用 X 射线衍射、扫描电镜和原子发射光谱等对催化剂进行了表征. 以甲基橙 (MO) 为模型污染物, 评价了样品的光催化活性, 考察了甲基橙初始浓度及其 pH 值, 以及催化剂用量等对光催化反应性能的影响. 结果表明, Fe-Ni 共掺杂降低了 ZnO 的结晶度, 并促进了晶粒的长大. 光催化降解反应表明, Fe-Ni 共掺杂显著提高了 ZnO 光催化降解甲基橙的活性, 当催化剂用量为 0.6 g/L, 经 120 min 紫外光照射时, 可使甲基橙溶液 (10 mg/L) 降解率达到 93.5%. 关键词：铁; 镍; 共掺杂; 氧化锌; 光催化; 甲基橙; 降解     

MOF-derived hollow NiO–ZnO composite micropolyhedra and their application in catalytic thermal decomposition of ammonium perchlorate

Ni(II)-doped Zn-based coordination polymer particles (Ni(II)-doped Zn-CPPs) with controllable shape and size were successfully synthesized by solvothermal method, which further transformed to porous ZnO–NiO composite micropolyhedra without significant alterations in shape by calcination in air. Those products were characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), infrared spectroscopy (IR) and gas adsorption measurements. The catalytic activity of ZnO–NiO composites for the thermal decomposition of ammonium perchlorate (AP) was investigated. The result shows that all ZnO–NiO composites efficiently catalyzed the thermal decomposition of AP, and NiO–ZnO composite hollow octahedrons have the highest catalytic efficiency compared with that of most materials reported to now, indicating that porous ZnO–NiO composite micropolyhedra could be a promising candidate material for application in AP-based propellant.     

NiO@ZnO heterostructured nanotubes: coelectrospinning fabrication, characterization, and highly enhanced gas sensing properties

Novel NiO@ZnO heterostructured nanotubes (NTs) were fabricated by the coelectrospinning method, consisting of external hexagonal ZnO shell and internal cubic NiO NTs. They are carefully investigated by scanning electron microscopy, transmission electron microscopy, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy mapping, X-ray diffraction, and X-ray photoelectron spectroscopy techniques. A reasonable formation mechanism of the hierarchical NiO@ZnO NTs is proposed, which is discussed from the view of degradation temperature of different polymers and the amount of inorganic salts. They were then explored for fabrication of H(2)S gas sensors. The gas sensing test reveals that compared with the pure ZnO, NiO, and the ZnO-NiO mixed gas sensors, hierarchical gas sensor exhibits highly improved sensing performances to dilute hydrogen sulfide (H(2)S) gas. The response of the optimum NiO@ZnO NTs sensor to 50 ppm H(2)S increases as high as 2.7-23.7 times compared to the other sensors, whereas the response and recovery times also become shorter considerably. These enhanced gas sensing properties are closely related to the change of nanostructure and activity of ZnO and NiO nanocrystals as well as combination of homo- and heterointerfaces in the optimum gas sensor, which are confirmed by a series of well-designed experiments.     

多孔微球镍锌复合型吸附剂反应吸附脱硫性能研究

考察了葡萄糖量对氧化锌微球形貌的影响,分别采用等体积浸渍法和水热法制备含Ni质量分数为5%的NiO/ZnO微球吸附剂,使用N2吸附-脱附、扫描电子显微镜(SEM)、X射线衍射(XRD)等手段对NiO/ZnO微球吸附剂进行结构和形貌分析,并研究了制备方法对NiO/ZnO微球吸附剂物化性质的影响,再将其经H2还原后制得Ni/ZnO微球吸附剂,在模型汽油中使用噻吩作为含硫化合物,通过固定床反应器进行反应吸附脱硫性能研究。实验表明,与等体积浸渍法制备的负载型NiO/ZnO微球吸附剂相比,水热法制备的复合型NiO-ZnO微球吸附剂的比表面积和孔体积分别高达(40.45 m~2/g)和(0.096 cm~3/g),还原后所得复合型Ni-ZnO微球吸附剂具有更好的脱硫活性,在吸附温度350℃、压力1.0 M Pa、进料液体积空速6 h-1及氢气与模拟油体积比为60的条件下,可以将模拟油中的硫质量含量从1.5×10~(-4)降至10-5以下。并且拥有很好的再生能力,经过多次再生后仍保持很高的脱硫率,具有潜在的工业应用价值。     

Surface-interface investigations of an ultrathin pulsed laser deposited NiO/ZnO bilayer structure

We hereby report detailed structural and morphological studies for an ultrathin NiO/ZnO bilayer structure grown on sapphire (001) substrate using pulsed laser deposition technique. The combined X-ray reflectivity (XRR) and grazing incidence X-ray fluorescence (GIXRF) studies revealed formation of a low-density defective ZnO interfacial layer of thickness ~32 Å at the ZnO/sapphire interface prior to growth of main ZnO layer. Our results further indicate that the variation of electron density across the NiO/ZnO bilayer structure is smooth and we do not observe presence of any interface layer between them. X-ray diffraction measurements show that deposited ZnO layer is epitaxial in nature whereas NiO is highly oriented along (100) direction. The angle dependent X-ray absorption near edge fine structure (XANES) measurements at Ni–K edge has been utilized to determine depth-resolved oxidation state of Ni and the results have been correlated with the depth-resolved electron density of NiO layer. The method described here offers nondestructive determination of the microstructural parameters as well as depth-resolved mapping of oxidation state of a thin film-based heterojunction device. It extends several advantages over destructive methods which are abundantly reported in literature.     

Room temperature solution-phase synthesis of flower-like nanostructures of [Ni3(BTC)2·12H2O] and their conversion to porous NiO

Hierarchical flower-like architectures of[Ni₃（BTC）₂·12H₂O]（BTC³=benzene-1,3,5-tricarboxylate） were successfully prepared by a simple solution-phase method under mild conditions without any template or surfactant.Phase-pure porous NiO nanocrystals were obtained by annealing the Ni-BTC complex without significant alteration in morphology.The product was characterized by X-ray diffraction techniques,field-emission scanning electron microscopy（FESEM）.transmission electron microscopy（TEM） and high-resolution TEM（HRTEM）.The catalytic effect of the NiO product was investigated on the thermal decomposition of ammonium perchlorate（AP） and it was found that the annealed NiO product has higher catalytic activity than the commercial NiO.     

Effect of electron beam irradiation on CO2 reforming of methane over Ni/Al2O3 catalysts

The effect of electron beam irradiation on the CO₂ reforming of methane over Ni/Al₂O₃ was investigated. The conversion rate of CO₂ and CH₄ forming H₂ and CO using various catalysts irradiated with an absorbed dose greater than 2 MGy was 5–10% higher than when using an untreated catalyst. The Ni/O ratio on the catalyst surface increased after treatment with an electron beam, and was more prominent for catalysts with a higher Ni content. As such, based on XRD and XPS measurements, electron beam treatment was found to result in either the desorption of oxygen from NiO or the removal of OH groups from the outermost surface layer of the catalyst. In addition, the concentration of active sites, such as Ni²⁺ and NiO, or surface defects was also found to increase with the absorbed radiation dose, thereby increasing the conversion rate.     

A Systematic Study of ZnO/CuO Core/Shell Nanostructures Pegylated by Microwave Assistant Reverse Micelles (RM) Method

In this work we synthesized ZnO/CuO nanostructures pegylated by simple and fast microwave method assistant reverse micelles, Reverse micelles protocol creates many advantages in stability, particle size control, morphology, density, loading level, distribution, uniformity, charge and purification. Based on the statistical results ZnO/CuO nanostructures placed in the hydrophilic substrate. The effect of microwave and concentration of surfactant on the surface area, pore diameter and pore volume of the final product was systematically studied using Taguchi technique. ZnO/CuO core/shell pegylated nanostructures, indicating a ZnO as core and CuO as shell and continuous micelles chains around this structures. Products were characterized by UV–Vis spectra, X-ray diffraction, scanning electron microscopy, Dynamic light scattering, Energy-dispersive X-ray spectroscopy, transmission electron microscopy and nitrogen adsorption (i.e. Brunauer–Emmett–Teller surface area analysis).     

ITO和ZnO基底对电化学沉积氧化亚铜薄膜的形貌、结构的影响及作用机制

采用电化学恒电位沉积方法在ITO导电玻璃上和在ZnO薄膜上沉积氧化亚铜(Cu₂O),并通过X射线衍射(XRD)和扫描电镜(SEM)对晶体的微观结构和表面形貌进行了分析.在ZnO基底上沉积得到了纳米级的Cu₂O粒子并且具有明显择优取向,而在ITO导电玻璃上仅得到粒径为2—5μm的Cu₂O粒子,没有明显的择优取向.对薄膜的生长机理进行了讨论.     

微波辅助合成石墨烯/氧化镍复合材料及其表征

本文通过微波辅助的方法,快速而有效地在热膨胀石墨烯(RG)的缺陷上原位合成氧化镍纳米颗粒,形成石墨烯/氧化镍复合材料(RG/NiO)。利用X-射线衍射(XRD),拉曼光谱(Raman),傅里叶变换红外(FTIR),扫描电镜(SEM),透射电镜(TEM),热重-差热(TGA-DSC)对所制备样品的结构、形貌和NiO含量在复合材料中的含量进行表征。结果表明,热膨胀石墨烯层数约7~8层,层间距约为0.35nm,缺陷多,在水热和微波处理后抗氧化性明显变差。复合材料中氧化镍颗粒平均粒径为25nm,均匀而密集地分散在石墨烯平面上,同时在复合材料中的含量为19.8%。     

Preparation,characterization and activity evaluation of p–n junction photocatalyst p-NiO/n-ZnO

In this paper, p–n junction photocatalyst NiO/ZnO was prepared by the sol–gel method using Ni (NO₃)₂ and zinc acetate as the raw materials. The structural and optical properties of the p–n junction photocatalyst NiO/ZnO were characterized by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) analysis, UV–Vis diffuse reflection spectrum (DRS) and the fluorescence emission spectra. The photocatalytic activity of the photocatalyst was evaluated by photocatalytic reduction of Cr₂O₇ ²⁻ and photocatalytic oxidation of methyl orange (MO). The results showed that the photocatalytic activity of the p–n junction photocatalyst NiO/ZnO is much higher than that of ZnO on the photocatalytic reduction of Cr₂O₇ ²⁻. However, the photocatalytic activity of the photocatalyst is much lower than that of ZnO on the photocatalytic oxidation of methyl orange. Namely, the p–n junction photocatalyst NiO/ZnO has higher photocatalytic reduction activity, but lower photocatalytic oxidation activity. The heat treatment condition also influences the photocatalytic activity strongly, and the best preparation condition is about 400 °C for 2 h. Effect of the heat treatment condition on the photocatalytic activity of the photocatalyst was also investigated. The mechanisms of influence on the photocatalytic activity were discussed by the p–n junction principle.     

Controllable synthesis of nickel hydroxide and porous nickel oxide nanostructures with different morphologies

Alpha-Ni(OH)(2) nanobelts, nanowires, short nanowires, and beta-Ni(OH)(2) nanoplates have been successfully prepared in high yields and purities by a convenient hydrothermal method under mild conditions from very simple systems composed only of NaOH, NiSO(4), and water. It has been found that the ratio of NaOH to NiSO(4) not only affects the morphology of the Ni(OH)(2) nanostructures, but also determines whether the product is of the alpha- or beta-crystal phase. A notable finding is that porous NiO nanobelts were produced after exposure of the Ni(OH)(2) products to an electron beam for several minutes during transmission electron microscopy (TEM) observations. Another unusual feature is that rectangular nanoplates with many gaps were obtained. Furthermore, porous NiO nanobelts, nanowires, and nanoplates could also be obtained by annealing the as-prepared Ni(OH)(2) products. A sequence of dissolution, recrystallization, and oriented attachment-assisted self-assembly of nanowires into nanobelts is proposed as a plausible mechanistic interpretation for the formation of the observed structures. The method presented here possesses several advantages, including high yields, high purities, low cost, and environmental benignity. It might feasibly be scaled-up for industrial mass production.     

Synthesis of mesoporous NiO with crystalline walls by a simple sol–gel route

Mesoporous NiO particles with crystalline walls were prepared by a simple sol-gel technique. X-ray diffraction (XRD), N₂ adsorption–desorption, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) have been used to investigate the mesoporous NiO particles. The as-prepared mesoporous NiO possessed narrow pore in the range of mesopores and was stable up to 700 ^oC. Various characterization results showed that the mesostructure was formed through the aggregation of nanocrystals and stearic acid in the precursor played an important role in formation of the final mesoporous structures. Mesoporous Ni particles have also been successfully synthesized by reduction of the obtained mesoporous NiO at 700 ^oC for 30 min.     

微波辅助合成石墨烯/氧化镍复合材料及其表征

本文通过微波辅助的方法,快速而有效地在热膨胀石墨烯(RG)的缺陷上原位合成氧化镍纳米颗粒,形成石墨烯/氧化镍复合材料(RG/NiO)。利用X-射线衍射(XRD),拉曼光谱(Raman),傅里叶变换红外(FTIR),扫描电镜(SEM),透射电镜(TEM),热重-差热(TGA-DSC)对所制备样品的结构、形貌和NiO在复合材料中的含量进行表征。结果表明,热膨胀石墨烯层数约7~8层,层间距约为0.35 nm,缺陷多,在水热和微波处理后抗氧化性明显变差。复合材料中氧化镍颗粒平均粒径为25 nm,均匀而密集地分散在石墨烯平面上,同时在复合材料中的含量为19.8%。     

La~2NiO~4催化制备纳米碳管

制备了四方结构复合氧化物La~2NiO~4,并以其为催化剂前体,甲烷和一氧化碳为碳,合成出大量高纯度的纳米碳管。XRD结果表明La~2NiO~4经还原后,在La~2O~3的隔离作用下Ni晶粒实现纳米级均匀分散。利用TEM,HRTEM,SEM,XRD,Raman等手段对所制备的纳米碳管进行了观察和表征。所制备的纳米碳管管径均匀、石墨化程度较高,该法制备纳米碳管工艺简单、产量较高,产品易于纯化。     

Facile synthesis of spray pyrolyzed ZnO/NiO nanocomposites thin films

Abstract

This study reviews ZnO, NiO, and ZnO/NiO nanocomposites thin films deposition using the Spray Pyrolysis Technique (S.P.T). The thin films were deposited onto ordinary glass substrates heated at 500?°C from aqueous solutions of zinc chloride and nickel chloride precursors dissolved in distilled water. The structural, morphological, and optical properties of the ZnO, NiO, and ZnO/NiO thin films have been studied by X-ray diffraction, scanning electron microscopy, Raman spectroscopies, and so on. The optical band gaps are 3.3 and 3.5?eV for ZnO and NiO thin films, respectively obtained by UV–Vis spectroscopy. However, the optical band gaps of ZnO/NiO nanocomposites thin films, are noticeable out of the range (3.4–3.64?eV).     

Controllable Synthesis and Optical Properties of Connected Zinc Oxide Nanoparticles

Connected zinc oxide (ZnO) nanoparticles are successfully synthesized by a simple solution‐based chemical route that uses evaporation and concentration technology. The influences of processing parameters, especially the evaporation and concentration time on the size and morphology of the nanoparticles, have been investigated by transmission electron microscopy (TEM) and high‐resolution TEM (HRTEM). The structure and optical properties are systematically characterized by X‐ray diffraction (XRD), UV/Vis spectrophotometery, and fluorescence spectroscopy (FL). It is found that the average diameter and morphology are strongly affected by the evaporation and concentration time. Additionally, the formation mechanism of the nanoparticles is also discussed. The studies revealed that the evaporation and concentration are important aggregation or nucleation processes for ZnO growth, which leads to the macro‐differences in morphology. These results provide some insight into the growth mechanism of ZnO nanostructures. The synthetic strategy developed in this study may also be extended to the preparation of other nanomaterials and promising applications in various fields of nanotechnology.     

同轴静电纺丝技术制备ZnO@CeO2纳米电缆

采用同轴静电纺丝技术,以硝酸铈、硝酸锌、聚乙烯吡咯烷酮、N,N-二甲基甲酰胺、甘油和氯仿为原料,制备了ZnO@CeO2 同轴纳米电缆。用差热–热重分析、X射线衍射、扫描电镜、透射电镜和能谱仪对样品进行了表征。结果表明,所得到的产物为ZnO@CeO2同轴纳米电缆,以晶态CeO2为壳层,晶态ZnO为芯层,电缆直径约90 nm,芯层直径约60 nm,壳层厚度约15 nm,电缆长度>300 μm,对其形成机理进行了分析。     

Growth and morphological studies of NiO/CuO/ZnO based nanostructured thin films for photovoltaic applications

At present, inorganic semiconducting materials are the most economical and viable source for the renewable energy industry. The present work deals with the morphological and optical characterization of copper oxide (CuO) and zinc oxide (ZnO) thin films fabricated by layer by layer deposition on nickel oxide (NiO) coated indium tin oxide (ITO) glass by solution processing methods, mainly chemical bath deposition (CBD) and hydrothermal deposition (HTD) processes at room temperature. As a whole, the above inorganic composite materials (NiO/CuO/ZnO) can be applied in photovoltaic cells. An attempt has been made to study structural, morphological and absorption characteristics of NiO/CuO/ZnO heterojunction using state of the art techniques like X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV spectroscopy. The energy band gaps of CuO and ZnO have also been calculated and discussed based on the UV spectroscopy measurements.     

Ni/MgO-Al2O3催化剂上高温焦油组分的催化转化

采用分步浸渍法制备了MgO-Al2O3负载的Ni基催化剂, 并运用N2吸附、载射线衍射(XRD)、透射电子显微镜(TEM)等手段进行表征. 该催化剂用于甲苯或萘为焦油模拟化合物的高温焦炉煤气(COG)的常压加氢裂解反应, 并考察了H2浓度、H2S对催化剂活性的影响. 结果表明: 催化剂还原后, 表面形成均匀分散、直径为8-14 nm的金属Ni纳米颗粒; 在较低的水碳摩尔比(nH2O/nC=0.28)时, 甲苯就能完全转化并选择性地加氢裂解形成CH4, 测试的时间内(480 min), 催化剂没有明显的失活和积炭现象, 显示出好的反应活性、稳定性和耐硫能力. 制得的Ni/MgO-Al2O3催化剂有望应用于较低水含量(10%-15%(φ, 体积分数))的高温焦炉煤气中焦油的直接转化.