Garcinia xanthochymus mediated green synthesis of ZnO nanoparticles: Photoluminescence,photocatalytic and antioxidant activity studies

Green synthesis of multifunctional zinc oxide nanoparticles (ZnO Nps) was achieved employing water extract of Garcinia xanthochymus by solution combustion synthesis. The structure and morphology were determined by XRD, UV–visible and scanning electron microscopy studies. The ZnO Nps were evaluated for photoluminescence (PL), photocatalytic and antioxidant properties. The water extract was found to comprise significantly high amounts of polyphenols and flavonoids. Powder XRD studies indicate the formation of pure wurtzite structure with absorption maximum of 370 nm corresponding to band gap energy of 3.33 eV. SEM studies reveal the formation of spongy cave like structures. The PL spectra exhibited 4 emission edges at 397, 436, 556 and 651 nm upon excitation at 325 nm because of oxygen deficiencies and zinc interstitials. Nps exhibit remarkable photodegradation of methylene blue (MB) in presence of UV and sun light. They exhibit antioxidant activity by inhibiting the 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radicals. Therefore, the study reveals an efficient, ecofriendly and simple method for the green synthesis of multifunctional ZnO Nps.     

Hydrothermal synthesis of dumbbell-shaped ZnO microstructures

Dumbbell-shaped ZnO microstructures have been successfully synthesized by a facile hydrothermal method using only Zn(NO₃)₂·6H₂O and NH₃·H₂O as raw materials at 150 °C for 10 h. The results from X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) show that the prepared ZnO samples exhibit dumbbell-shaped morphology and hexagonal wurtzite structure. The length of ZnO dumbbells is about 5–20 μm, the diameters of the two ends and the middle part are about 1–5 μm and 0.5–3 μm, respectively. The dumbbell-shaped ZnO microstructures may be formed by self-assembly of ZnO nanorods with 1–5 μm in length and 100–200 nm in diameter. The photoluminescence (PL) spectrum of dumbbell-shaped ZnO microstructures at room temperature shows three emission peaks at about 362, 384 and 485 nm.     

Structural and optical characterization of Zn0.95−xMg0.05AlxO nanoparticles

The structural and optical properties of ZnO nanoparticles doped simultaneously with Mg and Al were investigated. XRD results revealed the hexagonal wurtzite crystalline structure of ZnO. The FE-SEM study confirmed the formation of nano-sized homogeneous grains whose sizes decreased monotonously with increasing doping concentrations of Mg and Al. The absorption spectra showed that band gap increased from 3.20 to 3.31 eV with Mg doping. As the Al concentration changed from x=0.01 to x=0.06 mol% at constant Mg concentration the band gap observed to be decreased. Particle sizes estimated from effective mass approximation using absorption data and these values are in good agreement with the crystallite sizes calculated from XRD data. Raman spectra of ZnO showed a characteristic peak at 436 cm⁻¹ correspond to a non-polar optical phonon E₂ (high). With increase of the Al doping concentrations, E₂ (high) phonon frequency shifted to 439 cm⁻¹ from to 436 cm⁻¹. The origin of E₂ (high) peak shift in ZnO nanoparticles is attributed to optical phonon confinement effects or the presence of intrinsic defects on the nanoparticles. PL spectra indicated that with increase of Al co-doping along with Mg into ZnO, intensity of the peak positioned at 395 nm was initially increased at x=0 and then decreased with increase of the Al concentrations from x=0.01 to x=0.06 mol%.     

Effect of Mg doping on photoluminescence of ZnO/MCM-41 nanocomposite

In this paper, photoluminescence (PL) behavior of Mg_xZn_1?xO/MCM-41 nanocomposite (where x = 0.05, 0.15, 0.25 and 0.30) is reported. Samples were characterized with small angle X-ray diffraction (SAXRD), wide angle XRD, BET (Brunauer–Emmet–Teller) surface area and pore size analyzer, field emission scanning electron microscope (FE-SEM), high resolution transmission electron microscope (HR-TEM) and PL spectrometer. The structure of MCM-41 was confirmed from both SAXRD and BET results. A broad PL band positioned at around 393 nm has been exhibited by ZnO/MCM-41 nanocomposite. With Mg doping, intensity of this PL band decreased for x = 0.05 and 0.15 and above this there was gradual enhancement in intensity. It was found that the intensity of the PL band, strongly depends on the particle size of ZnO. The increase in particle size along with MgO phase separation for x = 0.30 was proved by HR-TEM analysis. Interestingly, the differences in particle sizes at different concentrations of Mg did not account for shift in the PL band. A twofold enhancement in the intensity of PL band when x = 0.30 compared to bare ZnO/MCM-41 nanocomposite was observed. It is attributed for the increase in particle size which preserves the energy saved by passivation of ZnO nanoparticles and the other one is formation of heterojunction structures between ZnO and MgO. It was also evident from these results that there is increase in oxygen vacancies of ZnO crystallites with increase in particle size.     

The O2-dependent growth of ZnO nanowires and their photoluminescence properties

ZnO nanowires were massively synthesized on a Ni(NO₃)₂-coated silicon substrate under oxygen-containing argon atmosphere by a simple chemical vapor deposition method. The average diameter of the ZnO nanowires was about 50 nm and the average length was about 20 μm. The morphologies of the ZnO nanowires strongly depended on oxygen content in the growth atmosphere. At low oxygen concentration (about 5–10 ppm), ZnO nanocones and nanoneedles were obtained, while at high oxygen concentration (about ∼250 ppm), ZnO nanoparticles deposited on the substrate. The room temperature photoluminescence (PL) spectrum of the ZnO nanowires revealed that a strong UV band at 384 nm dominated the whole spectrum. These results indicate that the ZnO nanowires grown under oxygen-containing atmosphere possess better crystalline quality and UV luminescence properties than those grown in reducing hydrogen atmosphere. Based on the analysis of oxygen effect on the ZnO nanostructures, a vapor–liquid–solid mechanism assisted by the redox growth mode was proposed to understand the growth of the ZnO nanowires.     

Structural,optical and photocatalytic properties of hafnium doped zinc oxide nanophotocatalyst

A series of novel hafnium (Hf) doped ZnO nanophotocatalyst were synthesized using a simple sol–gel method with a doping content of up to 6 mol%. The structure, morphology and optical characteristics of the photocatalysts were characterized by XRD, SEM, TEM, FTIR, XPS, DRS and PL spectroscopy. The successful synthesis and chemical composition of pure and doped ZnO photocatalysts were confirmed by XRD and XPS. DRS confirmed that the spectral responses of the photocatalysts were shifted towards the visible light region and showed a reduction in band gap energy from 3.26 to 3.17 eV. Fluorescence emission spectra indicated that doped ZnO samples possess better charge separation capability than pure ZnO. The photocatalytic activity of Hf-doped ZnO was evaluated by the methylene blue (MB) degradation in aqueous solution under sunlight irradiation. Parameters such as irradiation time and doping content were found effective on the photoactivity of pure ZnO and Hf-doped ZnO. The photocatalysis experiments demonstrated that 2 mol% Hf-ZnO exhibited higher photocatalytic activity as compared to ZnO, ZnO commercial and other hafnium doped ZnO photocatalysts and also revealed that MB was effectively degraded by more than 85% within 120 min. The enhanced photoactivity might be attributed to effective charge separation and enhanced visible light absorption. It was concluded that the presence of hafnium within ZnO lattice could enhance the photocatalytic oxidation over pure ZnO.     

Direct microwave synthesis of graphitic C3N4 with improved visible-light photocatalytic activity

The graphitic carbon nitride (g-C₃N₄) was rapidly synthesized via direct high-energy microwave heating approach. During the preparation process, only low-cost melamine and artificial graphite powders were used, without any metal catalysts or inert protective gas. The microstructure was investigated by using X-ray diffraction (XRD), Flourier transformed infrared (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM). The spectra of XRD and HRTEM indicated that the obtained g-C₃N₄ had a high crystallinity. The optical spectra covering Photoluminescence (PL) and Ultraviolet-visible (UV–vis) were also measured at room temperature. PL peak and UV–vis absorption edge of the g-C₃N₄ were shown at 455 nm and 469 nm, respectively, indicating visible-light photocatalytic property. Finally, the photocatalytic activity of g-C₃N₄ was investigated and evaluated as photocatalyst for the photo-degradation of Rhodamine B (RhB) and Methyl Orange (MO) in aqueous solution under visible-light (λ>420 nm) irradiation, respectively. Results indicated that the g-C₃N₄ sample displayed an excellent performance of removing of RhB and MO due to the improved crystallinity and large surface area of 126 m²/g. After the visible-light photocatalytic reaction for 40 min, the decolorization ratios of RhB and MO reached up to 100% and 94.2%, respectively.     

Transparent semiconductor zinc oxide thin films deposited on glass substrates by sol–gel process

Transparent semiconductor ZnO thin films were spin-coated onto alkali-free glass substrates by a sol–gel process. The influence of ZnO sols synthesized via different solvents (2-ME, EtOH or IPA) on the surface morphologies, microstructures, optical properties and resistivities of the obtained films were investigated. The as-coated films were annealed in ambient air at 500 °C for 1 h. X-ray diffraction results showed all polycrystalline ZnO thin films to have preferred orientation along the (0 0 2) plane. The surface morphologies, optical transmittances and resistivity values of the sol–gel derived ZnO thin films depended on the solvent used. The ZnO thin films synthesized with IPA as the solvent exhibited the highest average transmittance 92.2%, an RMS roughness of 4.52 nm and a resistivity of 1.5 × 10⁵ Ω cm.     

Synthesis of the hexagonal pillar shaped ZnOs using a hydrothermal method

This study focused on the stable synthesis to obtaining nanometer sized hexagonal pillar-like ZnO, which can be utilized as LED (light emission device) materials. Various zinc oxides were successfully synthesized by hydrothermal treatment at 150, 200 and 250 °C for 8 h, with their morphologies controlled at pHs 9, 11 and 13, by the addition of ammonium hydroxide. The SEM (scanning electron microscopy) results reveal that the as-prepared particles at pH 13 and 200 °C for 8 h were a complete hexagonal pillar shaped. On the other hand, the morphology was flower shaped at lower pH and temperature. This result indicates that hexagonal pillar shaped ZnO can be easily formed higher pH and temperature reaction conditions. Two types of emitting band for all ZnO samples were observed at around 400 nm (violet) and above 550 nm (green) in the photoluminescence (PL) spectra.     

Synthesis of Ag3PO4–ZnO nanorod composites with high visible-light photocatalytic activity

Ag₃PO₄ nanoparticles with 50–100 nm in size distributed on the surface of ZnO nanorods with ca. 20 nm in diameter and 1–2 μm in length have been synthesized by a facile method. The Ag₃PO₄–ZnO nanorod composites had much higher photocatalytic activity toward degradation of Rhodamine B (RhB) under visible light irradiation than pure ZnO nanorods, and had better recyclability and stability than pure Ag₃PO₄ nanoparticles. The Ag₃PO₄–ZnO nanorod composite with the molar ratio of Ag₃PO₄:ZnO = 1:40 exhibited the highest photodegradation efficiency of RhB (93%), which was 1.5 times of pure ZnO nanorods.     

Time dependent growth of ZnO nanoflowers with enhanced field emission properties

Herein, we report the facile growth of ZnO nanoflowers composed of nanorods on silicon substrate by non-catalytic thermal evaporation process. The grown nanoflowers were examined in terms of their morphological, structural, optical and field emission properties. The detailed characterizations revealed that the nanoflowers are grown in high density, possessing well-crystallinity and exhibiting wurtzite hexagonal phase. The Raman-scattering spectrum shows a sharp optical-phonon E₂ mode at 437 cm⁻¹ which confirmed the wurtzite hexagonal phase for the grown nanoflowers. The room-temperature PL spectrum depict a strong ultraviolet emission at 381 nm, revealed good optical properties for the ZnO nanoflowers. The field emission studies revealed that a turn-on field for the ZnO nanoflowers based field emission device was 4.3 V/μm and the emission current density reached to 0.075 mA/cm² at an applied electric field of 7.2 V/μm and exhibit no saturation. The field enhancement factor ‘β’ for the fabricated device was estimated from the F-N plot and found to be ~2.75×10³. Finally, systematic time-dependent experiments were performed to determine the growth process for the formation of ZnO nanoflowers composed of nanorods.     

Enhanced photoluminescence and photocatalytic activity of ZnO-ZnWO4 nanocomposites synthesized by a precipitation method

Zinc oxide (ZnO)-zinc tungstate (ZnWO₄) nanocomposites ((ZnO)_1−x(ZnWO₄)_x, x=0, 0.1, 0.2, 0.3, 0.5, 0.7, 0.9, 1) were prepared using a convenient precipitation method. The structural, morphological and optical properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), Ultraviolet-visible (UV–vis) absorbance measurements and photoluminescence (PL) spectroscopy. The photocatalytic performance of the samples was evaluated utilizing methyl orange (MO) under UV light irradiation. The SEM and HR-TEM analyses revealed that an intimate contact was possibly formed at the ZnO-ZnWO₄ interface. The PL spectra of the composites of ZnO and ZnWO₄ exhibited a stronger blue-green emission band in the range of 400–540 nm under 272 nm radiations compared with that of single phase ZnWO₄. And their photocatalytic performances were also elevated significantly when the value of the x was 0.1, 0.2, 0.3 and 0.5, almost twice as much to that of ZnO. The superior fluorescent and photocatalytic performances might be ascribed to the suitable energy levels related to the intimate contact between two different semiconductors, which are beneficial to the interfacial charge transfer between the conduction and valence bands.     

Enhanced blue-light photocatalytic H2 production using CdS nanofiber

The photocatalytic activity of CdS nanosphere, nanorod or nanofiber was investigated for the hydrogen production from either methanol–water or sulfide/sulfite solution irradiated with blue light. The nanostructured CdS were obtained by the precipitation method at high ethylenediamine content solutions and at moderate temperature conditions. The synthesized CdS nanofiber using CS₂ as sulfur source presented the highest photocatalytic activity for the H₂ production (954 μmol h^− 1 g^− 1) in the reaction system with four blue LED lamps. This high photoactivity was attributed to the quantum confinement effect generated by the small particle size of the nanofibers (D = ~ 5 nm and L = 25 nm).     

Electro-optical and electrochemical properties of an ionic polyacetylene derivative with azobenzene anisole moieties

An ionic polyacetylene derivative with azoanisole moieties was prepared by the activated polymerization of 2-ethynylpyridine by using 4-[4-(9-bromononyloxy)phenylazo]anisole without any additional initiator or catalyst in high yield. The chemical structure of poly[2-ethynyl-N-(p-methoxyphenylazophenyl)oxynonylpyridinium bromide] (PEMPB) was characterized by instrumental methods such as NMR (¹H and ¹³C), IR, UV–vis spectroscopies to have a conjugated polymer backbone system with the designed azobenzene moieties as substituents. This polymer was completely soluble in organic solvents and well processible. The electrochemical and electro-optical properties of PEMPB were studied. The cyclovoltammograms of this polymer exhibited the irreversible electrochemical behaviors between the oxidation and reduction peaks. The oxidation current density of PEMPB versus the scan rate is approximately linear relationship in the range of 30 mV/s–120 mV/s. The exponent of scan rate, x value of PEMPB, is found to be 0.6. The absorption spectrum starts around 700 nm and shows a characteristic absorption band at visible region of 464 nm due to the π → π* interband transition of the polymer backbone, which is a peak of the conjugated polyene backbone. The photoluminescence spectrum showed that the PL peak is located at 539 nm corresponding to the photon energy of 2.30 eV.     

Optical properties of Yb-doped ZnO/MgO nanocomposites

Yb³⁺ doped ZnO/MgO nanocomposite were prepared by combustion synthesis method. The samples were further heated to 1000 °C to improve their crystallinity and photoluminescent efficiency. The concentrations of Yb³⁺ and Mg²⁺ were varied between 1–2% and 5–70% respectively in prepared samples. The nano-powders were characterized by Scanning Electron Microscopy and X-ray Diffraction for morphology and structural determination. XRD studies have revealed the wurtzite structure for Mg_xZn_1−xO for Mg concentrations below 30%. Higher concentrations of Mg results in Yb³⁺ doped ZnO/MgO nanocomposite containing three phases; the wurzite hexagonal phase typical of ZnO, the cubic phase of MgO and a small amount of cubic Yb₂O₃ phase. As expected, the amount of cubic phase in nano-powders increased with the increase of Mg concentration in ZnO. The crystallite size of ZnO/MgO composites decreased from 55 nm to 30 nm with increase of Mg content. SEM images of Yb³⁺ doped ZnO/MgO nanocomposite with higher Mg content (>50%) showed clearly distinct hexagonal and cubical shaped nano-particles. Photoluminescent emission showed a broad band in the range (435 nm to 700 nm). Pure ZnO nano-phosphor showed an emission peak around 545 nm, which is blue shifted with Mg content. The photoluminescence intensity increased with increase of Mg content in ZnO and it became maximum with 30% Mg concentration. Time resolved decay curves of photoluminescence indicated decay time in microsecond time scale.     

Dy3+ doped LiCl–CaO–Bi2O3–B2O3 glasses for WLED applications

Dy³⁺ doped calcium bismuth borate glasses were synthesized in the composition range of xLiCl-(30 − x)CaO-20Bi₂O₃-50B₂O₃ + 1 mol% Dy₂O₃ (x = 0, 2, 5, 7, 10 and 15 mol%, LC0, LC2, LC5, LC7, LC10 and LC15 respectively) using conventional melt-quench technique. Broad XRD profiles confirmed non-crystalline nature of synthesized compositions. The compositional dependencies of structural changes (using FTIR spectra), thermal behavior (using DSC thermographs) and optical band gap (using UV–Vis–NIR spectra) were discussed. Photoluminescence (PL) excitation spectra recorded at 577 nm yielded six different excitation peaks belonging to Dy³⁺ ions. The PL emission spectra recorded at 451 nm were analyzed to extract different light emission parameters viz. Y/B ratio, color coordinates, correlated color temperature (CCT) following CIE 1931 chromaticity diagram. The emission colors were found to lie in white light region and lies very close to standard white light emission. The CCT of sample LC10 (5335 K) is closest to CCT of standard white light (5615 K) which depicted the optimized concentration of LiCl for application of these glasses in WLED application.     

One-step synthesis of ZnO and Ag/ZnO heterostructures and their photocatalytic activity

By following a one-step, novel methodology, ZnO and Ag/ZnO heterostructures were successfully synthesized at room-temperature. This route is simple, effective, high yield (91%), environmentally friendly (green synthesis) and consists of a mechanically assisted metathesis reaction. The metathesis reaction used in this investigation showed two results: the in-situ generation of alkaline nitrates, LiNO₃/NaNO₃, and the direct crystallization of the desired Zn-based compounds in milling media; revealing a true mechanochemical synthesis of ZnO and Ag/ZnO (1.25, 2.50 and 4.50 mol% of Ag) heterostructures. Particles showed spherical-like morphologies and sizes smaller than 20 nm. The Ag/ZnO heterostructures exhibited higher photocatalytic activity than ZnO for degrading methylene blue (MB) dye. It was also shown that the presence of Ag (up to 1.25 mol%) nanoparticles (NPs) in ZnO accelerates the photodegradation reaction and then slows down with further increases in Ag contents. The 1.25-Ag/ZnO sample (10 mg) showed the highest photocatalytic activity (96%) for degrading MB (100 ml, 10 mg L^?1) within 100 min under UV–Vis light irradiation (λ = 310 nm).     

Monochromatic photoluminescence obtained from embedded ZnO nanodots in an ultrahard diamond-like carbon matrix

At room temperature, we observe the self assembly of nanoclusters in an amorphous matrix using a vacuum deposition technique. Self-assembled ZnO nanoclusters embedded in hard diamond-like amorphous carbon thin films, deposited by high vacuum Filtered Cathodic Vacuum Arc (FCVA) technique at room temperature without post-processing, have been observed. A selective self assembly of metal and oxygen ions in a 3-element plasma was observed. XPS distinctly showed presence of ZnO and DLC-mixture in 5, 7 and 10 at.% Zn (in target) films while maintaining high sp³ content. This in turn improved the Young's modulus value of the ZnO nanoclusters embedded in DLC film (~ 220 GPa) compared to bulk ZnO (~ 110 GPa). Films with ZnO detected were observed to exhibit absorption edge at 377 nm monochromatic UV light emissions. This corresponded to a band gap value of about 3.30 eV. The emission with greatest intensity (after normalization) was detected from 10 at.% Zn (in target) film where presence of ZnO nanoclusters (~ 40 nm) in DLC matrix were confirmed by TEM. This showed that well-defined crystalline ZnO nanoclusters contributed to strong PL signal. Strong monochromatic emissions detected hinted that no defect states were present.     

Bright green emission and temperature dependent localized bound exciton transitions from undoped ZnO films

Bright green luminescence is achieved from undoped ZnO films prepared by the reaction of oxygen and zinc powder. The green emission band is considered to be mainly due to the singly ionized oxygen vacancies. Temperature dependence of exciton transitions in the undoped ZnO films has been investigated in the range from 10 to 270 K. The PL spectrum at 10 K is dominated by neutral donor-bound exciton (D°X) emissions. The dominant emission centered at about 3.303 eV at above 45 K can be attributed to the localized bound exciton (LBX) transitions related to basal plane stacking faults. LBX transitions can survive up to near room temperature due to the LBX binding energy of 68 meV.     

Graphene quantum dots directly generated from graphite via magnetron sputtering and the application in thin-film transistors

This work presents a novel method to prepare graphene quantum dots (GQDs) directly from graphite. A composite film of GQDs and ZnO was first prepared using the composite target of graphite and ZnO via magnetron sputtering, followed with hydrochloric acid treatment and dialysis. Morphology and optical properties of the GQDs were investigated using a number of techniques. The as-prepared GQDs are 4–12 nm in size and 1–2 nm in thickness. They also exhibited typical excitation-dependent properties as expected in carbon-based quantum dots. To demonstrate the potential applications of GQDs in electronic devices, pure ZnO and GQD–ZnO thin-film transistors (TFTs) using ZrO_x dielectric were fabricated and examined. The ZnO TFT incorporating the GQDs exhibited enhanced performance: an on/off current ratio of 1.7 × 10⁷, a field-effect mobility of 17.7 cm²/Vs, a subthreshold swing voltage of 90 mV/decade. This paper provides an efficient, reproducible and eco-friendly approach for the preparation of monodisperse GQDs directly from graphite. Our results suggest that GQDs fabricated using magnetron sputtering method may envision promising applications in electronic devices.