Microwave-assisted method for preparation of Zn1−xMgxO nanostructures and their activities for photodegradation of methylene blue

Nanostructures of Zn_1−xMg_xO (0 ⩽ x ⩽ 0.2) were prepared in water by one-pot method under microwave irradiation for 5 min. In this method, zinc acetate, magnesium nitrate and sodium hydroxide were used as starting materials without using any additive and post preparation treatment. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), electrochemical impedance spectroscopy (EIS), Fourier transform-infrared (FT-IR), and the Brunauer–Emmett–Teller (BET) techniques. The nanostructures have wurtzite hexagonal crystalline phase and doping of Mg²⁺ ions does not change the phase of ZnO. The SEM and TEM images show that morphology of the samples is changing by doping of Mg²⁺ ions. The EIS data show that by doping the ion, interfacial charge transfer resistance of the nanostructures decreases. Photocatalytic activity of the nanostructures was evaluated by degradation of methylene blue (MB) under UV irradiation. The degradation rate constant on the nanostructures with 0.15 mol fraction of Mg²⁺ ions is about 2-fold greater than for ZnO. Moreover, influence of various operational parameters such as microwave irradiation time, calcination temperature, weight of catalyst, concentration of MB, pH of solution and scavengers of reactive species on the degradation rate constant was investigated and the results were discussed.     

Potato starch-assisted green synthesis of nanoferrite and ferrite–semiconductor nanocomposites for effective visible light photocatalytic degradation of methylene blue

Journal of Materials Science - Biodegradable potato starch-assisted nanoferrite and ferrite–semiconductor nanocomposites have been synthesized by the co-precipitation method for the...     

Effect of annealing on the magnetic properties of solution synthesized Zn1−xMnxO nanorods

Mn-doped ZnO nanorods with ～30 nm in diameter and ～200 nm in length were synthesized by a seed-mediated solution method. The structures, magnetic properties, as well as the annealing effect were characterized by transmission electron microscopy, electron energy loss spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectrum and physical properties measurement system. Magnetic properties measurement revealed that the Zn_0.97Mn_0.03O nanorods exhibited ferromagnetism with a saturation magnetization of 0.005 emu g^?1 and a coercivity of 110 Oe at 305 K. After annealing the samples at 900 °C for 2 h in air, the nanorods were transformed into nanoparticle aggregates. The coercivity and saturation magnetization increased obviously. Detailed analyses proved that a phase-separation process was happened at the high temperature. In this process, most of the particles preserved the wurtzite ZnO structure, while a few small ones evolved into spinel-structured particles. The increasing of the ferromagnetism of the annealed sample is attributed to the formation of secondary phase Zn_xMn_3?xO_4.     

Fabrication of n-Zn1−xGaxO/p-(ZnO)1−x(GaP)x thin films and homojunction

Ga doped ZnO (GZO) and GaP codoped ZnO (GPZO) thin films of different concentrations (1–4 mol%) have been grown on sapphire substrates by RF sputtering for the fabrication of ZnO homojunction. The grown films have been characterized by X-ray diffraction (XRD), photoluminescence (PL), Hall measurement, energy dispersive spectroscopy (EDS), time-of-flight secondary ion mass spectrometer (ToF-SIMS), UV–Vis–NIR spectroscopy and atomic force microscopy (AFM). Unlike in conventional codoping, here we directly doped (codoped) GaP into ZnO to realize p-ZnO. The Hall measurements indicate that 2 and 4% GPZO films exhibit p-conductivity due to the sufficient amount of phosphorous incorporation while all the monodoped GZO films showed n-conductivity as expected. Among the p-ZnO films, 2% GPZO film shows low resistivity (2.17 Ωcm) and high hole concentration (1.8 × 10¹⁸ cm^?3) by optimum incorporation of phosphorous due to best codoping. Similarly, among the n-type films, 2% GZO shows low resistivity (1.32 Ωcm) and high electron concentration (2.02 × 10¹⁹ cm^?3) by optimum amount of Ga incorporation. The blue shift and red shift in NBE emission observed from PL acknowledged the formation of n- and p-conduction in monodoped and codoped films, respectively. The neutral acceptor bound exciton recombination (A⁰X) observed by low temperature PL for 2% GPZO confirms the p-conductivity. Further, the high concentration of P atoms than Ga observed from ToF-SIMS (2% GPZO) also supports the p-conductivity of the films. The fabricated p–n junction with best codoped p-(ZnO)_0.98(GaP)_0.02 and best monodoped n-Zn_0.98Ga_0.02O films showed typical rectification behavior of a diode. The diode parameters have also been estimated for the fabricated homojunction.     

Adsorption and photocatalysis of nanocrystalline TiO2 particles prepared by sol–gel method for methylene blue degradation

Titanium dioxide (TiO₂) powders were synthesized by using TiO₂ colloidal sol prepared from titanium-tetraisopropoxide (TTIP) and used as a starting material by applying the sol–gel method. The effect of aging times and temperatures on physical and chemical properties of TiO₂ sol particles was systematically investigated. The results showed that the crystallinity and average particle size of TiO₂ can be successfully controlled by adjusting the aging time and temperature. The samples after calcination of TiO₂ powders were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and nitrogen adsorption measurements. In addition, the photocatalytic activity of synthesized TiO₂ powders was evaluated by studying the degradation of 10 ppm aqueous methylene blue dye under 32 W high pressure mercury vapor lamp with 100 mg of TiO₂ powders. The highest photocatalytic activity was observed in TiO₂ powder synthesized at 90 °C for 0 h attributed to the presence of anatase and rutile phases in an 80:20 ratio.     

Morphology, optical, and photoelectrochemical properties of electrodeposited nanocrystalline ZnO films sensitized with Cd x Zn1−x S nanoparticles

Nanocrystalline ITO/ZnO films formed by porous zinc oxide microplatelets 1–3 μm in size and 100–200 nm in thickness, which consist of 30–50 nm ZnO crystallites, were sensitized to visible light by Cd _x Zn_1?x S nanocrystals deposited using the method of successive ionic layer adsorption and reaction (SILAR). The composition of Cd _x Zn_1?x S nanocrystals as well as the dependence between molar Cd(II) fraction in the films and the ratio of cadmium and zinc nitrate concentrations in solutions used for the SILAR procedure were determined by a combination of electron, Raman, and energy-dispersive X-ray spectroscopies. The photovoltage observed at illumination of the ITO/ZnO/Cd _x Zn_1?x S heterostructures by white light (λ >400 nm) in aqueous Na₂S solution increases with a decrease of Cd(II) content proportionally to an increment in the conduction band potential of the Cd _x Zn_1?x S nanocrystals. The photocurrent density normalized to the light absorbance of the ITO/ZnO/Cd _x Zn_1?x S films increases by a factor of around four when the conduction band potential of Cd _x Zn_1?x S nanocrystals grows by 220 mV as a result of Cd(II) fraction changing from 1.0 to 0.62–0.67. The results show that Cd _x Zn_1?x S solid solutions are more advantageous sensitizers for the short-wavelength part of the sensitivity window of the liquid-junction solar cells (400–450 nm) than conventionally used cadmium sulfide.     

Growth and characteristics of ternary Zn1−x Mg x O films using magnetron co-sputtering

ZnMgO thin films with different Mg compositions were grown on Si (001) substrates by radio frequency magnetron co-sputtering, and their structural and optical properties have been investigated. As the Mg content was increased up to 10 at.%, the surface became smoother and the growth rate decreased. The strong peaks at 34.5–34.7^° corresponding to the (0002) diffraction peak of ZnMgO indicated the preferred growth along the c-axis. From the photoluminescence measurements, a shift of the emission peak and an increase of the activation energy were also observed with increasing Mg content.     

Structural and optical properties of Cd1−xZnxS (0 ≤ x ≤ 0.3) nanoparticles

Cd_1?xZn_xS nanoparticles for Zn = 0–30 % were successfully synthesized by a conventional chemical co-precipitation method at room temperature. X-ray diffraction spectra confirmed the pure zinc blend cubic structure of undoped CdS; but Zn-doping on Cd–S matrix induced the mixed phases of cubic and hexagonal structure. The reduced crystal size, d-value, cell parameters and higher micro-strain at lower Zn concentration were due to the distortion produced by Zn²⁺ in Cd–S lattice. The enhancing diffraction intensity at lower Zn concentrations was due to the substitution of Zn²⁺ ions instead of Cd²⁺ ions whereas the reduced intensity after 20 % was due to the presence of Zn²⁺ ions both as substitutionally and interstitially in Cd–S lattice. The nominal stoichiometry and chemical purity was confirmed by energy dispersive X-ray analysis. The initial blue shift of energy gap from undoped CdS (3.75 eV) to Zn = 10 % (3.82 eV) was due to the size effect and also the incorporation of Zn²⁺ in the Cd–S lattice. The observed red shift of energy gap at higher Zn concentrations could be attributed to the improved crystallinity. The band gap tailoring was useful to design a suitable window material in fabrication for solar cells and other opto-electronic devices. The characteristic IR peaks around 617–619 cm^?1 and the reduced intensity by Zn-doping confirmed the presence of Zn in Cd–S lattice.     

Structural and optical properties of Cd x Zn(1 − x)Te thin films

Seven Cd _x Zn_{(1 ? x} Te solid solutions with x = 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 were synthesized by fusing stoichiometric amounts of CdTe and ZnTe constituents in silica tubes. Each composition was used in the preparation of a group of thin films of different thicknesses. Structural investigation of the obtained films indicates they have a polycrystalline structure with predominant diffraction lines corresponding to (111) (220) and (311) reflecting planes, which can be attributed to the characteristics of growth with the (111) plane. The optical constants (the refractive index n, the absorption index k, and the absorption coefficient α) of Cd _x Zn_{(1 \s -x)} Te thin films were determined in the spectral range 500–2000 nm. At certain wavelengths it was found that the refractive index, n, increases with increasing molar fraction, x. It was also found that plots of α² (hv) and α^1/2 (hv) yield straight lines, corresponding to direct and indirect allowed transitions respectively obeying the following two equations: $$\begin{gathered} E_g^d = 1.583 + 0.277x + 0.197x^2 \hfill \\ E_g^{ind} = 1.281 + 0.111x + 0.302x^2 \hfill \\ \end{gathered}$$      

Solvent-dependent tuning of blue–green emission of chemically synthesized ZnO nanomaterials with high colour purity and electroluminescence efficiency

A series of nanomaterials of ZnO have been synthesized via chemical co-precipitation method with fixed proportions of precursors and varied solvents. X-ray diffraction confirms wurtzite crystalline structure with nanometric crystallites (< 23 nm). Texture coefficient of crystallographic orientations show remarkable change for switching the solvents from water to alcohol. Morphological study reveals nanomaterials resembling prolate, sphere and oblate shaped structures for the solvents water, methanol and ethanol, respectively, with increasing particle size. All the nanomaterials show a similar absorption band in the UV region; though, more absorption covering a wider region in visible range is observed for nanomaterials prepared in alcoholic solutions. Red shifting in band gap of nanomaterials is correlated with band-tail effect. Variation in Urbach energy indicates that the nature of solvent plays a vital role in creating defects in ZnO, justifying enhanced absorptions in visible region. Photoluminescence (PL) spectra show various emission bands consisting of blue, green and yellow emissions corresponding to different intrinsic defects in nanomaterials. PL displays a tuning trend for blue–green emission by changing solvent from water to alcohol. However, overall enhanced PL intensity and particularly intense blue emission have been achieved by replacing water with alcohol. Tunability in emission colours and high colour purity is observed in the CIE chromaticity analysis. Theoretically, estimated electroluminescence of ZnO prepared in alcohol shows superiority compared to ZnO prepared in water. The mechanism of solvent-mediated defect creation and emission in ZnO will be beneficial for future QD LED applications.

     

(Sr1−xCax)WO4 and (Sr1−xCax)WO4:Eu3+ nanoparticles: synthesis and luminescence

(Sr_1?xCa_x)WO₄ and (Sr_1?xCa_x)WO₄:0.05Eu³⁺ nanoparticles were synthesized by precipitation without using any complexing agent. The XRD patterns show that the obtained samples present a scheelite-type tetragonal structure without deleterious phase, and the increase of Ca concentration decreases the cell volume of materials. The TGA/DTA curve shows that the materials began to crystallize at temperature of 650 °C. The excitation and emission spectra of (Sr_1?xCa_x)WO₄ samples show bands originating from the charge transfers within WO₄ ^2? groups. All (Sr_1?xCa_x)WO₄ samples show broad blue emission at room temperature. The excitation and emission spectra of (Sr_1?xCa_x)WO₄:0.05Eu³⁺ samples show bands originating from the charge transfers of Eu³⁺ ions. All (Sr_1?xCa_x)WO₄:0.05Eu³⁺ samples show prominent red emission at room temperature. The substitutions of Ca²⁺ ions to Sr²⁺ ions have obvious influence on luminescence properties. The intensity and quantum efficiency increase with the substituted Ca concentrations.     

Photoelectric properties of undoped and lithium-doped Zn1−xMgxTe alloys

The room temperature photoelectric response of undoped and lithium-doped Zn_1–xMg_xTe (0 x 0.50) alloys has been measured in the wavelength range 0.50 3.0 m. The response curve for undoped samples is characterized by a single peak in the band edge region. The peak shifts with composition in accordance with the expected shift in the energy band gap. Lithium-doped samples show an additional peak centred at 1.04 eV for all compositions. This peak is attributed to photo-generated holes in the split-off band created as the result of electronic transitions to shallow acceptor impurities.     

In situ incorporation of well-dispersed Cu–Fe oxides in the mesochannels of AMS and their utilization as catalysts towards the Fenton-like degradation of methylene blue

Multi-components active metal oxide-supported catalysts are highly promising in heterogeneous catalysis due to some special promoting effects. In this study, by the controllable amount of Cu, Cu–Fe decorated anionic surfactant-templated mesoporous silica (Cu _x Fe/AMS) was directly prepared. The obtained catalysts were characterized by X-ray diffraction, N₂ adsorption–desorption, inductively coupling plasma emission spectroscopy, scanning electron microscopy, transmission electron microscopy, UV–visible, hydrogen temperature-programmed reduction, and X-ray photoelectron spectroscopy techniques. The results revealed that bimetallic Cu–Fe oxides were directly formed and highly dispersed in the mesochannels during the calcinations and the introduction of Cu²⁺ and Fe²⁺ on the micelles has influence on the structure properties. As compared to the monometallic Fe-modified AMS, the presence of Cu promotes the effects between Fe species and silica wall, leading to the better dispersion of Fe in the mesochannels of AMS. Finally, a series of Cu–Fe-modified AMS were used as Fenton-like catalysts and exhibited good catalytic activity in the degradation of methylene blue (MB), which resulted from high dispersion of Fe species and synergetic effect between Cu and Fe active sites. 1.0 was the optimum molar ratio of Cu²⁺ to Fe²⁺ ions to achieve the best catalytic activity and stability.     

Study of La1−xMnO3−δ non-stoichiometry and defect structure using ESR and iodometry

The oxidation states of manganese in the La_1–xMnO_3– (x = 0.09–0.11) were investigated by electron spin resonance (ESR) and iodometry. The ESR analysis carried out at room temperature for the samples prepared in air revealed the presence of broad peaks at g = 2.0, considered to be relevant to Mn²⁺. It was also found that the intensity of the peak increased as lanthanum vacancy content increased. The average valence state of manganese, determined by iodometry, was approximately 3.2, and decreased by 1 as the lanthanum vacancy increased by 1. Similar trends were observed with the samples prepared at P _{o 2} = 1×10^–7. The results indicated that Mn²⁺ is stably present in the La_1–xMnO_3– having an average valence number exceeding 3.0. A series of experimental results with respect to the non-stoichiometry of La_1–xMnO_3– can be explained by assuming that Mn²⁺ is stabilized after forming a complex with a lanthanum vacancy and two oxygen vacancies.     

Efficient removal of U(VI) from solution using a MoS42− ion-exchange functionalized polypyrrole composite material

Journal of Materials Science - MoS4–Ppy was synthesized by a simple oxidative polymerization method and functionalized with the MoS42? ions. Because of the good stability and excellent...     

Low temperature synthesis of Co3O4 and (Co1−xMnx)3O4 spinels nanoparticles

The (Co_1?xMn_x)₃O₄ solid solution have been synthesized in water at 60 °C by soda addition to a cationic solution. XRD patterns show that spinel oxide has been obtained except for pure cobalt composition which exhibits also the presence of hydroxide and oxy-hydroxide. Therefore, to reach this composition, a different synthesis route has been developed: the cationic solution is added to the soda and for the first time Co₃O₄ nanoparticles have been synthesized by a direct precipitation in aqueous solution at low temperature. For each composition, the particles are well crystallized and exhibit a size close to 50 nm. Each particle is composed by several crystallographic domains of about 10 nm. The cubic to tetragonal transition reported in the literature for x = 0.46 is observed in between x = 0.33 and x = 0.50. Raman spectra show that substitution of Co by Mn, in the cubic phase, introduces a random high disorder. In the tetragonal phase, occupation of the octahedral site remains a random occupation, while the tetrahedral site seems to be preferentially occupied by Co ions. All these results show that the precipitation is a simple, fast and safe process to synthesize pure phase of (Co_1?xMn_x)₃O₄ spinel solid solution in aqueous media at low temperature.     

Effect of reducing atmosphere on the magnetism of Zn(1-x)Co(x)O (0≤x≤0.10) nanoparticles

We report the crystal structure and magnetic properties of Zn(1-x)Co(x)O?(0≤x≤0.10) nanoparticles synthesized by heating metal acetates in organic solvent. The nanoparticles were crystallized in the wurtzite ZnO structure after annealing in air and in a forming gas (Ar95%?+?H5%). The x-ray diffraction and x-ray photoemission spectroscopy (XPS) data for different Co content show clear evidence for the Co(2+) ions in tetrahedral symmetry, indicating the substitution of Co(2+) in the ZnO lattice. However, samples with x = 0.08 and higher cobalt content also indicate the presence of Co metal clusters. Only those samples annealed in the reducing atmosphere of the forming gas, that showed the presence of oxygen vacancies, exhibited ferromagnetism at room temperature. The air annealed samples remained non-magnetic down to 77?K. The essential ingredient in achieving room temperature ferromagnetism in these Zn(1-x)Co(x)O nanoparticles was found to be the presence of additional carriers generated by the presence of the oxygen vacancies.     

A green route approach to the synthesis of Ni(II) and Zn(II) templated metal–organic frameworks

A new synthetic route involving mixing of solid reactants followed by heating has been developed for the preparation of two templated metal–organic frameworks (MOFs). [Ni(NO₃)₂(bipy)₂](pyrene)₂ (1) was obtained by mixing together Ni(NO₃)₂·6H₂O, 4,4-bipyridine and pyrene followed by heating at 85 °C for 4 h, while [Zn₂(fumarate)₂(bipy)] (2) was synthesized by mixing together Zn(O₂CCH₃)₂·2H₂O, fumaric acid and 4,4-bipyridine followed by heating at 160 °C for 16 h. The materials were characterized by elemental analysis, FT-IR spectroscopy and X-ray powder diffraction analysis (XRPD). Comparison of XRPD patterns of the materials with patterns simulated from the single crystal X-ray diffraction data, obtained from Cambridge Structural database, allowed identification of the products. Conversion of solid reactants to MOFs occurs spontaneously even when reactants are not mechanically stressed. Overall, the study suggests that MOFs can be synthesized in solid state simply by mixing together appropriate reactants without co-mill (ball-mill). Compared with traditional synthetic techniques such as solvothermal, ball-milling and solution-based, this method is environmentally friendly and highly efficient in the manufacture of these MOFs on a large scale.