Preparation of ZnO nanoparticle‐reinforced polyamide 6 composite by in situ‐coproduced method and their properties

Polyamide 6/ZnO nanocomposites (noted as PA6/ZnO) were prepared by an in situ co‐producing method, during which Zn₂(OH)₂CO₃ decomposed into nano‐ZnO in the process of the opening‐ring polymerization of caprolactam at high temperature. Transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry were used to analyze the size and dispersive properties of nano‐ZnO, the crystallization and melting properties, the thermal properties, and crystal structure of PA6/ZnO composite, respectively. The results showed that the nano‐ZnO derived from Zn₂(OH)₂CO₃ via in situ polymerization of PA6‐ZnO was uniformly dispersed in PA6 matrix. However, the overall nano‐ZnO crystallization rate and crystal size in the PA6 matrix were hindered by the bulky PA6 molecular chains. The mechanical properties were evaluated using universal tensile and impact testing instruments. The results revealed that PA6/ZnO composite with 0.2% nano‐ZnO content possessed excellent tensile strength, enhanced by 75% in comparison with the pure PA6. The nano‐ZnO had little influence on the impact strength of PA6. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 165–170     

Fabrication,characterization and exploration of cobalt (II) ion doped,modified zinc oxide thick film sensor for gas sensing characteristics of some pernicious gases

The present research deals with the synthesis of zinc oxide (ZnO) nanoparticles by the co-precipitation (CPT) method. The CPT method was successfully utilized for the synthesis of ZnO nanoparticles. The structural properties of undoped ZnO and cobalt doped ZnO were confirmed by employing an X-ray diffraction (XRD) study, from which the average particle size for each prepared material was calculated from the Debye Scherer formula. The average particle size confirms the nano range fabrication of undoped and cobalt doped ZnO material. The surface characteristics, morphology, texture, and porosity properties of undoped ZnO and cobalt doped ZnO were investigated from scanning electron microscopy (SEM). The elemental composition was investigated from energy dispersive spectroscopy (EDS). The High-resolution transmission electron microscopy (HRTEM) results revealed the hexagonal phase of prepared material. Furthermore, the undoped ZnO and 5% cobalt doped ZnO gas sensors prepared by screen printing technology were utilized for gas sensing purposes for testing the gases like H₂S, NO₂, SO₂, and methanol. For the gases examined, the cobalt modified ZnO sensor proved to be quite effective, especially for H₂S and NO₂ gas vapors. The Co²⁺ doped ZnO sensor showed 70.12% sensitivity for H₂S gas at 150 ⁰C and 68.75% gas response for NO₂ gas vapors at 120 ⁰C. In addition, the cobalt modified sensor was also investigated for reusability test to get concrete gas response results with the time interval of 15 days. In conclusion, it can be mentioned that the cobalt doped ZnO thick film sensor is a promising sensor for H₂S and NO₂ gas vapors.     

Synthesis and Characterization of TiO2 Doped ZnO Microtubes

The TiO₂-doped ZnO microtubes have been successfully fabricated via a wet chemicalmethod, using zinc chloride and titanium sulphate as the starting materials. The as-synthesized products were characterized by X-ray diffraction, field emission scanning electronmicroscopy and room temperature photoluminescence measurement. The photocatalytic ac-tivity in degrading methyl orange was measured with a UV-Vis spectrophotometer. The pure ZnO microtubes exhibit an exact hexangular hollow structure with a diameter of about 700 nm, a length of 3 μm and a wall thickness of about 40 nm. The TiO₂-doped ZnO microtubes with TiO₂/ZnO ratio less than 5% have the same dimension with the pure ZnO microtubes, a smooth column shape, not a hexangular structure. The growth of ZnO may be inhibited by the more Ti⁴⁺ doped into ZnO structure to achieve a small dimension or a multiphase. The crystallinity of ZnO microtubes decreases with increasing TiO₂ content, and then a multiphase containing ZnO, Ti₃O₅ and TiO occur when the TiO₂/ZnO ratio is more than 5%. The UV emission intensity of the TiO₂-doped ZnO obviously increases and then tends to decrease with TiO₂/ZnO ratio increasing. The photocatalytic properties of the TiO₂-doped ZnO microtubes are very effcient in degrading organic dyes of methyl orange and are well identical with its PL properties and the crystallinity.     

Electrical-optical properties of nanofiber ZnO film grown by sol gel method and fabrication of ZnO/p-Si heterojunction

Electrical and optical properties of the ZnO film prepared by sol-gel dip coating were investigated and ZnO film was deposited onto p-type silicon to obtain Ag/ZnO/p-Si heterojunction diode. Two dimensional atomic force microscopy images indicate that the ZnO film is formed from the fibers consisted from nanoparticles with grain size of 250-350 nm. The electrical conductivity mechanism of the ZnO film was varied from extrinsic to intrinsic conductivity. The calculated optical band gap of the ZnO film was found to be 3.22 eV. The Ag/ZnO/p-Si diode exhibit a non-linear behavior with ideality factor of n = 4.17 and barrier height of ?_B = 0.79 eV. The electrical properties of the Ag/ZnO/p-Si diode were investigated by current-voltage, capacitance-voltage-frequency and conductance-voltage-frequency measurements.     

Hierarchically Structure SnO2/ZnO Nanocomposites: Preparation,Growth Mechanism and Gas Sensing Property

SnO₂/ZnO nanocomposite was synthesized from mixed ethanol and water systems and the ethanol-sensing properties of sensors based on SnO₂/ZnO were investigated. The structure and morphology of the products was characterized by x-ray diffraction (XRD) and a field emission scanning electron microscope (FE-SEM). The results showed that the diameter of the liked pine needle SnO₂ was about 40 nm with a length about 300 nm, which are uniformly dispersed on the surface of the ZnO nanosheets. The growth process of the SnO₂/ZnO nanocomposite was discussed. The results of gas sensing properties of SnO₂/ZnO nanocomposite sensor showed high and quick response to ethanol vapor at 5.0 v. This sensor showed the advantages of high selectivity, strong stability, and prompt response/recovery characteristics in detecting ethanol vapor at 5.0 v.     

Metal oxide-modified ZnO/SiO <Subscript>2</Subscript> catalysts for cyclo-dehydrogenation of ethylenediamine with propyleneglycol to 2-methylpyrazine

Metal oxide-modified ZnO /SiO2 catalysts were studied for the cyclo-dehydrogenation of ethylenediamine with propyleneglycol to 2-methylpyrazine at 633 K. The ZnO/SiO₂ catalyst showed fairly good ethylenediamine conversion and quantitative propyleneglycol conversion with about 60 mol% of 2-methylpyrazine selectivity, which is due to the existence of large amount of unconverted intermediate, 2-methylpiperazine. Metal oxide (CuO, NiO, Co₃O₄)-modified ZnO/SiO₂ catalysts were prepared to facilitate the dehydrogenation of 2-methylpiperazine to 2-methylpyrazine. About 82 mol% of 2-methylpyrazine selectivity was achieved on CuO and Co₃O₄ modified ZnO/SiO₂ catalysts, with significant increases of pyrazine selectivity. The catalytic properties of the metal oxidemodified ZnO/SiO₂ catalysts, pretreated with hydrogen gas as in the cyclo-dehydrogenation, were compared using the well-known probe reaction, the dehydrogenation/ dehydration of cyclohexanol to cyclohexanone or phenol/cyclohexene. The selectivities of pyrazine in the cyclo-dehydrogenation on the metal oxide-modified ZnO/SiO₂ catalysts were correlated with the phenol selectivities of the probe reaction. It is proposed that the metallic site of catalyst is responsible for the formation of pyrazine from ethylenediamine dimerization. The improved 2-methylpyrazine yield on CuO/ZnO/SiO₂ catalyst was explained by the proper adjustment of catalytic properties, which could be differentiated by the phenol selectivity in the cyclohexanol probe reaction. Thus, the large enhancement of 2-methylpiperazine dehydrogenation to 2-methylpyrazine and the suppression of excess pyrazine formation are supposed to occur on the metallic Cu formed in situ during the reaction during the cyclo-dehydrogenation of ethylenediamine with propyleneglycol.     

In2O3/ZnO heterostructured nanotubes: electrospinning fabrication,characterization, and highly enhanced photocatalytic properties

In₂O₃/ZnO heterostructured nanotubes with cubic In₂O₃ and hexagonal ZnO were successfully synthesized via the combination of electrospinning and calcination process. The as-prepared materials are investigated by using thermogravimetric and differential scanning calorimetry, fourier transform infrared spectroscope, X-ray diffraction, scanning electron microscope and high-resolution transmission electron microscope techniques. The formation mechanism of In₂O₃/ZnO heterostructured nanotubes based on the kinetics of phase separation which results from the decomposition of polyvinyl pyrrolidone during the calcination process is also discussed in detail. The photocatalytic degradation tests reveal that In₂O₃/ZnO heterostructured nanotubes exhibit the highly improved photocatalytic properties compared with the single-component ZnO and In₂O₃ materials.     

Electrical,optical and photocatalytic properties of Ti-loaded ZnO/ZnO and Ti-loaded ZnO nanospheres

Ti-loaded ZnO and Ti-loaded ZnO/ZnO nanoparticles have been synthesized by sol–gel method and analyzed for photocatalyst application. The phase confirmation was analyzed by powder XRD and surface morphology with HR-SEM and EDAX spectrum. The particle size measured using HR-TEM and SAED pattern confirms the crystalline nature of Ti-loaded ZnO and Ti-loaded ZnO/ZnO nanoparticles. The optical properties were studied with UV–visible diffuse reflectance spectra. The DRS of Ti-loaded ZnO/ZnO nanoparticles are similar to those of pristine ZnO nanoparticles. The KM plots show both the synthesized Ti-loaded ZnO/ZnO and Ti-loaded ZnO exhibit in UV-A region. The electric properties are studied with impedance analyzer, and the results show the charge-transfer resistance of Ti-loaded ZnO/ZnO is larger than that of Ti-loaded ZnO nanoparticles. The photocatalytic activity was studied with methylene blue dye and phenol degradation by Ti-loaded ZnO/ZnO, Ti-loaded ZnO, TiO₂ and ZnO nanoparticles. The photocatalytic activity of Ti-loaded ZnO/ZnO nanospheres is slightly higher than that of other nanoparticles, which shows that they have excellent application as photocatalyst.     

Degradation products formed during UV exposure of polyethylene-ZnO nano-composites

Photodegradation of low density polyethylene (LDPE) containing nano-particulate ZnO has been studied using FTIR to follow the development of oxidation products in the polymer film and to monitor carbon dioxide evolved as a principal product of oxidation. The degradation behaviour of ZnO-free LDPE has been compared with that of compounds containing 0.25% and 0.75% ZnO and these results are compared with those obtained using similar films containing nano-particulate TiO₂. Under UV exposure, the presence of ZnO accelerated the development of carbonyl groups and CO₂ production. The carbonyl group development was more rapid when TiO₂ was used whereas ZnO caused greater CO₂ generation. Carbonyl group development seemed to correlate better with the reduction in mechanical properties whereas CO₂ generation correlated better with weight change measurements. The influence of ZnO on the oxidation pathways in LDPE is discussed; it is proposed that photo-oxidation is relatively much more likely to occur at terminal sites (rather than at pendent sites) when ZnO is present.     

Application of ZnO nanoparticles to enhance the antimicrobial activity and ultraviolet protective property of bamboo pulp fabric

Hyperbranched polymer HSDA was synthesized from methyl acrylate, tetraethylenepentamine, and dodecanoic acid by melt polycondensation. ZnO nanoparticle colloidal solution was prepared in one step by mixing Zn(NO₃)₂ and HSDA aqueous solution under hydrothermal condition. The results of transmission electron microscopy and ultraviolet–visible (UV–Vis) spectroscopy indicated that ZnO nanoparticles were formed in colloidal solution. Bamboo pulp fabric was treated with ZnO nanoparticle colloidal solution by an impregnation method to provide the bamboo pulp fabric with antibacterial and UV protective properties. The whiteness, antibacterial activity, UV protective property, and washing durability of the ZnO nanoparticle-treated fabrics were determined. The results indicated that the bamboo pulp fabric treated with ZnO nanoparticles showed good UV protective properties and its ultraviolet protection factor (UPF) can reach 90.38. The UPF value of treated fabric drops to 70.42 after washing for 20 times, but it retains good UV protective properties. The ZnO nanoparticle-treated fabric showed 99.91 % bacterial reduction of Staphylococcus aureus and 99.97 % bacterial reduction of Escherichia coli. The fabric retained over 98.93 % reduction level even after being exposed to 20 consecutive home-laundering conditions. In addition, the results of scanning electron microscopy and X-ray spectroscopy confirmed that ZnO nanoparticles were fixed and well dispersed on bamboo pulp fabric.     

RF magnetron sputtering of ZnO and Al-doped ZnO films from ceramic and nanopowder targets: a comparative study

Undoped zinc oxide (ZnO) and aluminium-doped zinc oxide (ZAO) thin films have been prepared on glass substrates by RF magnetron sputtering from ceramic and nanopowder targets at room temperature (RT). The effects of target nature on the properties of the films have been studied. The X-ray diffraction (XRD) patterns show that ZnO and Al-doped ZnO thin films are highly textured along the c-axis perpendicular to the surface of the substrate from either nanopowder or ceramic targets. From the SEM images, it appears that the surface morphologies of ZAO films exhibit difference from that of undoped ZnO films. All films exhibit a transmittance higher than 80% in the visible region. The optical band gap (E_g) of ZnO and ZAO films obtained from nanopowder target is higher than those prepared using ceramic target. In two cases, Al-doping leads to a larger optical band gap (E_g) of the films.     

Optical,magnetic and photocatalytic properties of magnetically separable Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>-doped ZnO and pristine ZnO nanospheres

This work focussed on the optical, magnetic and photocatalytic properties of sol–gel-synthesized Fe₃O₄-doped ZnO nanospheres and was compared with pristine ZnO nanospheres. The crystalline phase of Fe₃O₄-doped ZnO nanospheres was studied with X-ray diffraction analysis and was well matched with standard pattern. Surface morphology was studied with HR-SEM images and EDAX spectrum. Furthermore, elemental mapping analysis was carried out to confirm the presence of Fe₃O₄ phase in Fe₃O₄-doped ZnO nanospheres. FT-Raman spectral studies show that a strong intense peak at 670 cm^?1 indicates the presence of Fe₃O₄ in Fe₃O₄-doped ZnO nanospheres. The mean crystallite size of Fe₃O₄-doped ZnO nanospheres was 34 nm as calculated by Debye–Scherrer’s formula which confirmed with HR-TEM image. The SAED pattern shows the presence of (100), (101), (102) and (202) of ZnO phase and (400) of Fe₃O₄ phase, confirming the crystalline nature of Fe₃O₄-doped ZnO nanospheres. The vibrating sample magnetometer (VSM) result shows that Fe₃O₄-doped ZnO nanospheres possess superparamagnetic nature and the composite nanospheres are magnetically separable. The optical properties have been studied by diffuse reflectance spectroscopy and time-resolved photoluminescence spectra. Implantation of Fe₃O₄ in ZnO nanospheres modifies the UV absorption edge, and it displays near-band gap emission and deep-level emission. The photocatalytic activity of Fe₃O₄-doped ZnO nanospheres studied against rhodamine B dye is found higher than that of pristine ZnO nanospheres which shows that Fe₃O₄-doped ZnO nanospheres are a promising photocatalyst.     

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.     

The study of electronic and optical properties of ZnO/MoS2 and its vacancy heterostructures by first principles

Based on the first principles calculation, the effects of vacancies on the structural, electronic and optical properties of ZnO/MoS₂ heterostructure are investigated in this work. The results show that vacancies could exist stably in the heterojunctions and cause a significant decrease in bandgap. ZnO/MoS₂ with an O vacancy maintains semiconductor property with a bandgap of 0.119 eV, while heterostructure with a Zn vacancy exhibits metallic characteristic. Furthermore, the absorption capability of defective heterojunctions has been extended to infrared light region with obvious redshift. To sum up, vacancy engineering effectively changes the electronic and optical properties of ZnO/MoS₂ heterostructure, which provides a feasible approach for adjusting the optoelectronic properties of two-dimensional heterostructures and broadening their application in functional nanoelectronic and optoelectronic devices.     

Some clues about the interphase reaction between ZnO and MnO2 oxides

Raman spectroscopy is used to evidence both the nature of the interphase reaction between ZnO and MnO₂ particles and its kinetic evolution. Zn cations migrate from the ZnO grains during oxygen vacancies formation process and diffuse into the MnO₂ particles leading to an interphase region with an intermediate valence Mn⁺³-O-Mn⁺⁴. Large amounts of desorbed Zn cations promote the formation of ZnMn₂O₄ structure, in addition to the intermediate valence state. The system evolves towards complete formation of the spinel phase at higher thermal treatment times. The reactivity of the ZnO plays an important role in the formation of this interphase. Low-reactivity ZnO powder, in which the oxygen vacancies are previously produced, shows a stabilization of the intermediate valence state with very limited formation of the spinel phase. A clear correlation between the amount of the intermediate state interphase and the magnetic properties has been established.     

MAA-modified and luminescence properties of ZnO quantum dots

The precursor of ZnO has been prepared by refluxing in ethanol at 70°C for 4 h using ZnAc₂·H₂O as the initial agent. Then ZnO has been prepared from the reaction of LiOH·H₂O and the precursor. The ZnO is modified by mercaptoacetic acid (MAA) and detected by SEM and XRD. These ZnO particles have single phase, like-sphere and size of 4.6 nm. The modified effectivity of MAA for the quantum dots (QDs) has been investigated with UV-visible and fluorescence analysis, and the mechanism and property of ZnO light emitting have been discussed under given conditions. The reasons why the fluorescent emission peak of surface defects disappear and the exciton emission peak increase are that MAA effectively covers the surface defects of ZnO and stably coats ZnO particles. At the same time, the effect of the added amount of the MAA, temperature and electrolyte on light-emitting properties of modified product has also been studied. The result shows that the modified ZnO QDs have good fluorescence property, stability and suitable capability of resisting electrolyte. These results are important for biological analysis.     

碱式硫酸锌转化法制备ZnO多孔片及其光致发光性能

采用化学浴沉积法制备了碱式硫酸锌(ZSH)纳米片, 并经1000 ℃煅烧处理得到了ZnO多孔片. 详细研究了ZSH在Zn²⁺-六亚甲基四胺前驱体溶液体系中的形成机理、ZSH 的热解过程、ZnO的结晶性、微结构以及光致发光性能. 结果表明, 所得ZnO多孔片呈规则六角形状, 其尺寸为10-50 μm, 厚度为200-500 nm, 由于高温固相反应中传质等因素的限制, 构成薄片的ZnO晶粒呈多边形或不规则形貌, 晶粒间的孔为亚微米孔, 尺寸在100-500 nm范围. ZnO多孔薄片结晶性良好, 在388 nm处表现出较强紫外发光, 无可见光区的缺陷发光. 机理分析表明, SO₄^2- 与Zn²⁺的高亲和力是Zn²⁺-六亚甲基四胺体系中ZSH生成的根本原因, 而ZSH的热分解过程对ZnO多孔片的形貌和微结构影响显著. 本研究提出了一种制备高结晶质量ZnO多孔材料的新方法, 所得ZnO多孔片可望在催化、染料敏化太阳能电池、紫外光电器件等领域得到应用.     

Bi基化合物膜包覆ZnO的制备和电化学性能

为提高锌镍电池ZnO的循环充放电性能,采用Bi(NO3)3水解沉积法对ZnO包覆Bi基化合物膜,系统研究了包覆ZnO的微结构和电化学性能。TEM,XRD和EDS表明由Bi6(NO3)4(OH)2O6·2H2O,BiO和Bi2O3组成的Bi基化合物膜包覆在ZnO表面。表面包覆能提高ZnO的循环性能和放电容量,含5.1wt%Bi的包覆ZnO循环性能稳定,平均放电容量为509mAh·g-1,利用率为78%,性能有较大改善。充放电曲线和循环伏安结果均表明包覆Bi基化合物膜能降低锌镍电池的充电平台,加宽放电平台,提高ZnO的电化学活性。包覆Bi基化合物膜能有效减小活性材料与碱性电解液的接触,抑制ZnO的溶解,提高循环稳定性;而包覆膜的微孔结构又可使活性材料接触到电化学反应必须的H2O和OH-,保证了高的放电容量。     

Mechanism of the conductivity and sensor response of nanostructured In2O3+ZnO films

The conductivity and sensor properties of mixed nanostructured In₂O₃+ZnO metal oxide systems with different component ratios are investigated. It is found that maximum sensor sensitivity in detecting hydrogen and CO in composite films containing 15 and 80 wt % In₂O₃ considerably exceeds the sensitivity of individual oxides. A mechanism of the sensor action, which is largely determined by the dependency of the paths of conductivity in a composite metal-oxide film on its composition, is proposed. It is established that the main factors determining the conductivity and sensor sensitivity of In₂O₃ + ZnO composite are modifications in the electron structure of crystals (mainly by In₂O₃) during the formation of composites, electron transfer from In₂O₃ to ZnO, and the catalytic activity of ZnO. It is shown in particular that ZnO effectively catalyzes the reaction of hydrogen dissociation and, in contact with In₂O₃, favors the chemical sensibilization of the sensor response of such mixed metal oxide systems in detecting H₂ and CO.     

Photocatalytic decomposition of dyes using ZnO doped SnO2 nanoparticles prepared by solvothermal method

ZnO doped SnO₂ has been successfully synthesized by the solvothermal method using methanol as organic solvent. The effect of ZnO/SnO₂ molar ratios on the crystal structure, microstructure, optical and photocatalytic properties has been investigated. The synthesized samples are characterized by X-ray diffraction, transmission electron microscopy, N₂ physical adsorption, FT-IR spectroscopy and UV–Vis spectroscopy. XRD results revealed that all diffraction peaks positions agree well with the reflection of a tetragonal rutile structure of SnO₂ phase without extra peaks at 0.1ZnO:0.9SnO₂ and 0.2ZnO:0.8SnO₂ molar ratios. However, the secondary phase of ZnO at 0.3ZnO:0.7SnO₂ molar ratio was investigated. TEM images revealed that the shape of SnO₂ particles was spherical and the particle sizes of SnO₂ and 0.3ZnO:0.7SnO₂ molar ratio were 6.2 and 16.4 nm, respectively. The newly prepared samples have been tested by the determination of photocatalytic degradation of methylene blue (MB). The results indicated that Zn²⁺ doping at 0.3ZnO:0.7 SnO₂ molar ratio showed the highest photocatalytic activity for the MB photodegradation. The heightened photocatalytic activity of ZnO/SnO₂ could be ascribed to the enhanced charge separation derived from the coupling of ZnO with SnO₂ due to the potential energy differences between SnO₂ and ZnO. The recycling tests demonstrated that 0.3ZnO:0.7 SnO₂ photocatalysts were quite stable during that liquid–solid heterogeneous photocatalysis since no decrease in activity in the first four cycles was observed.