Characterization and gas sensing properties of bead-like ZnO using multi-walled carbon nanotube templates

We report bead-like ZnO nanostructures for gas sensing applications, synthesized using multi-walled carbon nanotube (MWCNT) templates. The ZnO nanostructures are grown following a two-step process: in the first, ZnO nanoparticles are synthesized on MWCNTs by thermal evaporation of a Zn powder; and in the second, the hybrid nanostructures are heat-treated at 800 °C. Scanning and transmission electron microscopy images indicate that the bead-like ZnO nanostructures have surface protuberances with nanoparticle sizes ranging from 20 to 60 nm, and a well-crystallized hexagonal structure. Gas sensors based on multiple-networked bead-like ZnO showed considerably enhanced electrical responses and better stability to both oxidizing (NO₂) and reducing (CO) gases compared with previously reported nanostructured gas sensors, even if the response to CO gas was slow to increase. Both the NO₂ and CO gas sensing properties increased dramatically when the working temperature was increased up to 300 °C. The response sensitivities measured were 2953%, 5079%, 9641%, 3568%, and 3777% to 20 ppm NO₂ at 200, 250, 300, 350 and 400 °C, respectively. For CO gas on the other hand, the response sensitivities were 107%, 110%, 114%, 118%, and 122% at 5, 10, 20, 50, and 100 ppm concentrations, respectively. For concentrations between 5 and 20 ppm, the recovery time of the oxidizing gas was much shorter than the response time. The origin of the NO₂/CO gas sensing mechanism of the bead-like ZnO nanostructures is discussed.     

Temperature-dependent growth of ZnO structures by thermal oxidation of Zn coatings electrodeposited on steel substrates and their photocatalytic activities

In this work, zinc oxide (ZnO) nanostructures were successfully synthesized by thermal oxidation of zinc (Zn) coated steel substrates. Zn coatings were electrodeposited on the mild carbon steel sheet in the sulfate bath by DC current. The zinc coated samples were oxidized in air at distinct annealing temperatures between 400 °C and 800 °C. The phase structure and surface morphology of the ZnO films were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic activity of these ZnO layers was examined by means of decomposition of methylene blue (MB) aqueous solutions under UV lamp irradiation for various duration. The findings illustrated that annealing temperatures had a big effect on the morphology and structure of the ZnO layers. The annealed layers showed significantly enhanced photoactivity activity than the pure Zn layer under UV-irradiation. The sample with ZnO nanostructures oxidized at 800 °C exhibited a better photocatalytic degradation of MB than the other samples. This paper can provide an important contribution to the development of efficient photocatalysts for the solution of the environmental pollution problems.     

Facile synthesis of ZnO nanostructures and enhancement of their sinterability via short-time cryo-milling

Zinc oxide (ZnO), a wide band-gap semiconductor, has received a great interest due to its potential applications in various fields both as nanostructures and as sintered compacts. In this study, we report on the synthesis of the ZnO nanostructures and facilitation of their sintering for the production of fine-grained dense compacts. The facile synthesis of gram scale ZnO nanostructures was achieved by thermal decomposition of zinc acetate dihydrate (Zn(Ac)₂·2H₂O) or Zn(Ac)₂·2H₂O/graphite mixtures at 300 °C for 12 h. Thermal decomposition of Zn(Ac)₂ resulted in the formation of mostly ZnO nanoparticles with wurtzite structure along with ZnO nanorods, while the addition of graphite significantly promoted the growth of ZnO nanowires. Microstructural and phase properties of the obtained ZnO nanostructures were determined by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution TEM (HRTEM) techniques, all of which revealed the successful synthesis of high quality ZnO nanostructures. In addition to synthesis and characterization of the ZnO nanostructures, we report on the enhancement of their sinterability by a subsequent cryogenic milling for a short duration of 5 min. As a result of the applied cryo-milling, fabrication of highly dense (96.2%) sintered compacts with fine grain sizes (572 nm) could be achieved after pressureless sintering at 1000 °C for 2 h.     

SURFACE MODIFICATION OF HYDROTHERMALLY GROWN ZnO NANOSTRUCTURES WITH PROCESS PARAMETERS

ZnO nanorods (NRs) were hydrothermally synthesized by using equimolar zinc nitrate hydrate (Zn(NO₃)₂ [sdot] 6H₂O) and hexamethylenetetramine (C₆H₁₂N₄) solutions. The shape of the nanostructures, obtained by aqueous method, was greatly influenced by the growth temperature and the molar concentrations. NRs grown at higher temperature (90°C) have rounded tips, whereas nanostructures of hexagonal flat-end shape were obtained at 75°C. Hardly any nanostructures were observed by further reducing the temperature to 60°C. In addition, solutions with higher molarity favored the appearance of nanoflowers. Scattered ZnO NRs were observed on silicon substrate, whereas aligned ZnO nanowires (NWs) 50–70 nm in diameter were obtained at 75°C by introducing sputtered ZnO film as a seed layer. High-resolution transmission electron microscopy (HRTEM) confirmed the growth of ZnO nanowires along [001] direction. A band-edge luminescence along with a broad visible spectrum was observed for the ZnO nanowires.     

Growth and formation mechanism of sea urchin-like ZnO nanostructures on Si

Sea urchin-like nanostructures of ZnO consisting of ZnO nanowires with blunt faceted ends were grown on Si (100) substrates by oxidation of metallic Zn at 600 °C. ZnO nanowires having a diameter of 30–60 nm and length of 2–4 Μm were in similar shape with uniform diameter along its entire length with well faceted blunt ends. X-ray diffraction and transmission electron microscope analysis showed that the as-grown nanostructures were highly crystalline with wurtzite hexagonal structure having lattice constants of a=b=3.25 å and c=5.21 å. Room temperature photoluminescence (PL) measurements showed a weak near band-edge emission at 380 nm, but a strong green emission at 500–530 nm. A model for vapor-solid (VS) growth mechanism of ZnO nanowires was presented, in which nucleation of ZnO is crucial for the growth of the nanostructures.     

Hydrothermally Grown ZnO Micro/Nanotube Arrays and Their Properties

We reported the optical and wettability properties of aligned zinc oxide micro/nanotube arrays, which were synthesized on zinc foil via a simple hydrothermal method. As-synthesized ZnO micro/nanotubes have uniform growth directions along the [0001] orientations with diameters in the range of 100–700 nm. These micro/nanotubes showed a strong emission peak at 387 nm and two weak emission peaks at 422 and 485 nm, respectively, and have the hydrophobic properties with a contact angle of 121°. Single ZnO micro/nanotube-based field-effect transistor was also fabricated, which shows typical n-type semiconducting behavior.     

MgAl2O4 nanopowder synthesis by microwave assisted high energy ball-milling

This paper reports the development of a new process for the synthesis of spinel nano powder via microwave assisted high energy ball milling of a powder mixture containing Al(OH)₃ and Mg(OH)₂. X-ray diffraction (XRD), Simultaneous thermal analysis (STA), FTIR spectrometer, BET and scanning electron microscopy (SEM) techniques were utilized to characterize the as-milled and annealed samples. X-ray diffraction results provide evidence for the formation of a completely amorphous phase after milling for 8 h. It is found that highly ordered MgAl₂O₄ spinel can be obtained by calcination the as-milled powder over 800 °C. Also, SEM observations of synthesized powders showed that the particle size of powders lies in the nano meter range compared with the BET results (about 28–149 nm). The DTA–TG analyses were carried out to investigate the effect of microwave heating on the synthesis temperature compared to the conventional heat treatment by conventional furnace. Synthesis of powders with different heating methods showed that microwave heating reduces the synthesis temperature by about 200 °C.     

Preparation of zinc oxide ceramics with a sustainable antibacterial activity under dark conditions

Fabrication of ZnO ceramics with a sustainable antibacterial activity even in the dark has been conducted. Fine ZnO powders were hydrothermally treated in 0.5–3 mol ml^?1 Zn(NO₃)₂ aqueous solutions at 110–180 °C for 3–20 h. After an uniaxial pressing of the ZnO powders thus prepared, they were sintered at 400–600 °C for 1 h in air. Sustainability in antibacterial activity was evaluated using a colony count method with Escherichia coli bacteria on nutrient agar medium (36 °C/24 h) in a Na–P-buffer solution. The best data was attained for the ZnO ceramics prepared from the following conditions: a 3 mol ml^?1 zinc nitrate solution for the hydrothermal treatment at 120 °C for 7 h and sintering in air with a step-by-step pattern (470 °C/1 h–485 °C/1 h–500 °C/1 h). ESR and chemical photoluminescence analyses have cleared that radical oxygen of super-oxide (O₂^?) originated from the surface of ZnO might exhibit an antibacterial activity even under the dark condition.     

Preparation of nanostructure CuO/ZnO mixed oxide by sol–gel thermal decomposition of a CuCO3 and ZnCO3: TG,DTG, XRD,FESEM and DRS investigations

Nanostructure CuO/ZnO mixed oxide was systematically prepared via the sol–gel route using zinc and copper carbonates as precursors (molar ratio of 2:1) under thermal decomposition. The zinc and copper carbonates precursors have been synthesized by a simple chemical reaction in high yield and characterized by its melting point, FT-IR and thermal analysis (TG/DTG). The TG/DTG analysis proved that the thermal decomposition of zinc and copper carbonates precursors at 255 °C and 289 °C respectively. Thermo-gravimetric analysis (TG-DTG), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and diffuse reflectance spectroscopy (DRS) studies were undertaken to investigate the thermal properties and electronic structure of the CuO/ZnO mixed oxide catalysts. XRD data of the samples proved the formation of the nano-crystalline CuO/ZnO mixed oxide. Scanning electron microscopy (SEM) showed that the spherical-like particles have a diameter in the range 35–45 nm. Optical spectra of the nanostructure show a band peaked at 1.35 eV which is associated to near band gap transitions of CuO and a band centered at about 3.00 eV related to band gap transitions of ZnO nanostructures.     

Structural,textural, surface chemistry and sensing properties of mesoporous Pr,Zn modified SnO2–TiO2 powder composites

Mesoporous Zn and Pr modified SnO₂-TiO₂ mixed powders (Sn:Ti:Zn:Pr contents 60:20:15:5) have been prepared by a modified sol–gel method involving Tripropylamine (TPA) as chelating agent, TritonX100 as template and Polyvinylpyrrolidone as dispersant and stabilizer, respectively. The obtained gels have been dried at different temperatures and calcined in air at 600 and 800 °C, respectively. Phase identification of the synthesized samples and their evolution with the calcination temperature has been performed by X-ray diffraction. N₂ adsorption/desorption isotherms were found to be characteristic for mesoporous materials, showing relatively low values for the specific surface area (15–32 m² g⁻¹) and nanometric sized pores. In case of the sample calcined at 800 °C, a bimodal pore size distribution can be observed, with maxima at 20 and 60 nm. SEM results demonstrate a porous nanocrystalline morphology stable up to 800 °C. The surface chemistry investigated by XPS reveals the presence of the elements on the surface as well as the oxidation states for the detected elements. At 800 °C a diffusion process of Sn from surface to the subsurface/bulk region accompanied by a segregation of Ti and Zn to the surface is noticed, while Pr content is unchanged. The sensing properties of the prepared powders for CO detection have been tested in the range of 250–2000 ppm and working temperatures of 227–477 °C.     

Growth of hexagonal prism ZnO nanorods on Zn substrates by hydrothermal method and their photoluminescence

Hexagonal prism ZnO nanorods were successfully grown on Zn substrates by the 120 °C and 24 h hydrothermal reaction of the solutions with pH of 9–12. Results from XRD, SEM, TEM, SAED and HRTEM showed that the as-synthesized products were wurtzite ZnO with the shape of hexagonal prism nanorods grown along the [0 0 1] direction with smooth prismatic side planes. The PL spectra showed strong emission band at 543 nm in the green-yellow region due to the recombination of electrons trapped in singly ionized oxygen vacancies and photoexcited holes. This facile, reproducible and effective low-cost approach is promising for the future large-scale synthesis of wurtzite ZnO nanostructures for different applications in nanotechnology.     

Natural citric acid (lemon juice) assisted synthesis of ZnO nanostructures: Evaluation of phase composition,morphology, optical and thermal properties

In recent years, because of their excellent electrocatalytic action and applications in different fields, metal oxide nanostructures have received massive consideration from scientists. Zinc oxide nanostructures are useful materials for a range of sensing applications and possess admirable electrocatalytic properties and stability. The current research presents the natural citric acid assisted synthesis of ZnO nanostructures and their structural, optical, morphological and thermal properties. X-ray diffraction was studied for the phase assessment of as prepared (Z1) and annealed ZnO (Z2) nanostructures and the crystallite sizes of the Z1 and Z2 samples were also located in the range between 35 nm and 38 nm. FESEM and TEM experiments were carried out to explore the surface features of Z1 and Z2 samples. The polycrystalline existence of the samples is demonstrated by the hexagonal, cubic and spherical shaped ZnO nanostructures. The energy band gap of Z1 and Z2 samples was determined (3.16 eV for Z1 and 3.12 eV for Z2) from the UV spectrum. The impact of annealing treatment on the thermal stability of ZnO nanostructures was studied and the main peak was observed for the Z1 sample at ~249 °C and for the Z2 sample at ~289 °C.     

Growth mechanism of needle-shaped ZnO nanostructures over NiO-coated Si substrates

ZnO nanostructures were synthesized over NiO-coated Si substrate by a thermal evaporation of Zn powders in a vertical chemical vapor deposition reactor. The ZnO nanostructures had a needle-like morphology and the diameter of the structures decreased linearly from the bottom to the top. The bottom diameters of the ZnO nano-needles normally ranged from 20–100 nm and the lengths were in the range of 2–3 Μm. The clear lattice fringes in HRTEM image indicated the growth of good quality hexagonal single-crystal ZnO. Field emission characteristics of the ZnO nano-needles showed that the turn-on field was about 8.87 V/Μm with a field enhancement factor of about 1099. The growth mechanism of the ZnO nano-needles was proposed on the basis of experimental data.     

Synthesis,characterization, and microwave dielectric properties of ZnTiTa2O8 ceramics with ixiolite structure obtained through the aqueous sol–gel process

Nano-sized ZnTiTa₂O₈ powders with ixiolite structure, with particle sizes ranging from 10 nm to 30 nm, were synthesized by thermal decomposition at 950 °C. The precursors were obtained by aqueous sol–gel and the compacted and sintered ceramics with nearly full density were obtained through subsequent heat treatment. The microstructure and electrical performance were characterized by field emission scanning electron microscopy, x-ray diffraction, and microwave dielectric measurements. All the samples prepared in the range 950–1150 °C exhibit single ixiolite phase and relative density between ~87% and ~94%. The variation of permittivity and Q·ƒ value agreed with that of the relative density. Pure ZnTiTa₂O₈ ceramic sintered at 1050 °C for 4 h exhibited good microwave dielectric properties with a permittivity of 35.7, Q·ƒ value of 57,550 GHz, and the temperature coefficient of resonant frequency of about −24.7 ppm/°C. The relatively low sintering temperature and excellent dielectric properties in the microwave range would make these ceramics promising for applications in electronics.     

Ultra violet sensors based on nanostructured ZnO spheres in network of nanowires: a novel approach

The ZnO nanostructures consisting of micro spheres in a network of nano wires were synthesized by direct vapor phase method. X-ray Photoelectron Spectroscopy measurements were carried out to understand the chemical nature of the sample. ZnO nanostructures exhibited band edge luminescence at 383 nm. The nanostructure based ZnO thin films were used to fabricate UV sensors. The photoresponse measurements were carried out and the responsivity was measured to be 50 mA W⁻¹. The rise and decay time measurements were also measured.     

Synthesis of photoluminescent polycrystalline SiC nanostructures via a modified molten salt shielded method

Polycrystalline SiC (3C-, 6H-, 24R- and 27H-) nanostructures are synthesized via a modified molten salt shielded synthesis method (m-MS³) in open air using Si and carbon black as the starting materials. The influences of salt species and their amount, and the sintering temperature, are discussed and optimized. Well crystalline SiC nanopowders composed of bountiful microstructures (nanoparticles, nanowires, nanosheets and nanoblocks) are successfully synthesized by m-MS³ at 1250 °C, with KCl and NaCl as the shielding salt. The polycrystalline SiC powders showed excellent photoluminescence property at an excitation wavelength of 330 nm and relatively small band gaps of 2.57–2.74 eV, which are quite attractive among reports for SiC-based materials. The investigation in this paper may provide a prototype strategy for protection-free synthesis of nanostructured SiC powders applicable for ultraviolet luminescence devices.     

Synthesis and Sintering Behavior of Ultrafine (<10 nm) Magnesium Aluminate Spinel Nanoparticles

This article reports a comparative characterization of ultrafine MgAl₂O₄ spinel nanoparticles synthesized by polymeric precursor (Pechini) and coprecipitation methods. The nanoparticles were evaluated in terms of purity and surface cleanliness, size distribution, state of agglomeration, and sintering behavior. Powders synthesized by the Pechini technique were highly agglomerated and revealed a bimodal particle size distribution centered around 12 and 27 nm. Thermal analysis and infrared spectroscopy measurements indicated that carbon species remained on the surface of the powders only to be released when temperatures exceeded 1000°C. Isothermal sintering of such nanopowders at 1300°C showed a maximum relative density of only 54%. MgAl₂O₄ synthesized via coprecipitation created small nanoparticles, around 5–6 nm after calcination at 800°C, with significantly less agglomeration. Compared with the precursor‐derived powders, excellent sinterability of the coprecipitated powders was obtained under the same sintering conditions. Relative densities above 90% were obtained after only 10 min, which further increased to greater than 95% after 20 min with no sintering aids or dopants. The results highlight the importance of purity and processing control to exploit the beneficial high sinterability of nanoparticles.     

ZnO quantum dot based thin films as promising electron transport layer: Influence of surface-to-volume ratio on the photoelectric properties

ZnO quantum dots (QDs) with average particle size of 4.4 nm were prepared using a low temperature processing solvothermal route. ZnO QD based thin films were then prepared from the ZnO QD based solution using spin coating technique and annealed at 250, 350 and 450 °C. The average grain size and energy band gap of ZnO were respectively increased and decreased from 5.5 to 22.9 nm and 3.37 to 3.27 eV upon increasing the annealing temperature up to 450 °C. The photoluminescence analysis showed that the as-coated ZnO film and ZnO film annealed at 250 °C have high density of oxygen vacancies; these defects were reduced upon increasing the temperature to 350 and 450 °C. The photoelectric properties of the films were strongly affected by the grain size and the defects present in the films. The photo-to-dark current ratio (PDCR) was decreased from 3723 to 371%, whereas the responsivity was increased from 1.25 to 218 mA/W with the increase of temperature to 450 °C. As-coated and 250 °C-annealed films exhibited better photoresponse than others in terms of PDCR, rise time and fall time due to their larger surface-to-volume ratio, making them promising candidate as electron transport layer in perovskite solar cells.     

Synthesis and cathodoluminescence of ZnO tetrapods prepared by a simple oxidation of Zn powder in air atmosphere

Tetrapod-shaped ZnO crystals were synthesized by an oxidation process of Zn powder at temperatures over 930 °C in air. The ZnO crystals were formed in an alumina crucible in which metallic Zn powder was put. X-ray diffraction patterns revealed that the tetrapods were ZnO with wurtzite structure. Any impurities including Zn were not detected, indicating that the ZnO crystals were of high quality. As the oxidation temperature increased, the size of tetrapods was getting larger and longer. However at 1100 °C, tetrapod morphology was disappeared and changed to irregular shape. Strong UV emission at 380 nm was observed in the CL spectra taken for the ZnO tetrapods. The increase in the intensity of green emission at 510 nm was also observed with increased oxidation temperature.     

Hydrothermal synthesis of titanate nanostructures with high UV absorption characteristics

The titanate nanostructures with high UV absorption characteristics could be fabricated by hydrothermal method within a temperature range of 90–150 °C. TEM, XRD, BET analyses, and UV–vis spectroscopy were employed to elucidate the synthesized titanate nanostructure characteristics which were microstructure, phase transformation, specific surface area, and band gap energy, respectively. With an increase in the hydrothermal treating temperature from 90 to 120 °C, the specific surface area of titanate nanostructures was increased from 83 to 258 m²/g, while the band gap energy of titanate nanostructures was increased from 3.44 to 3.84 eV and then slightly decreased to 3.81 eV at 150 °C. The fabricated titanate nanostructures could exhibit higher UV adsorption capability but lower photocatalytic activity when compared with that of commercial TiO₂ powders.