Dielectric response of water confined in metal–organic frameworks

Dielectric response of water confined in metal–organic frameworks was investigated in broad temperature range from 140 to 410 K and from 20 Hz to 1 MHz using a capacitance bridge. Several dispersion regions of characteristic shape were found, caused by freezing–melting of adsorbed water molecules, which disappear after a prolonged heating at 410 K. Temperature dependencies of relaxation time of confined water molecules were obtained and are compared to those of water confined in MCM-41 mesoporous molecular sieves.     

Sonochemical synthesis of nanoplates of two Cd(II) based metal–organic frameworks and their applications as precursors for preparation of nano-materials

Nano plates of two Cd(II)-based metal–organic frameworks, [Cd₂(oba)₂(4-bpdb)₂]_n·(DMF)_x(TMU-8) and [Cd(oba)(4,4′-bipy)]_n·(DMF)_y (TMU-9) were synthesized via sonochemical reaction by using various time and concentrations of initial reagents and power of irradiation and characterized by scanning electron microscopy, X-ray powder diffraction and IR spectroscopy. Moreover, the effect of triethylamine on speed of nucleation during the synthesis was investigated. Thermolysis of these MOFs at 550 °C under air atmosphere yields CdO nanoparticles.     

High yield synthesis of Ni-BTC metal–organic framework with ultrasonic irradiation: Role of polar aprotic DMF solvent

Nickel based porous solid was synthesized with 20 kHz ultrasonic irradiation. The reaction of Ni(II) nitrate hexahydrate with 1,3,5-benzene tricarboxylic acid in N,N-Dimethylformamide (DMF) as the sole solvent under ultrasonic radiation produced porous Ni-BTC MOF. Choice of correct solvent for the ultrasonic treatment was proven important. The effect of varying ultrasonic powers (40%, 60% and 80% of 750 W) along with different temperature conditions (50 °C, 60 °C, 70 °C and 80 °C) influenced the respective yield. A very high yield of 88% Ni-BTC MOF was obtained from 80% ultrasonic power at 60 °C. BET surface areas of the MOF crystals measured by N₂ gas adsorption isotherms were in the range of 960–1000 m²/g.     

Self-assembly of metal–organic frameworks and graphene oxide as precursors for lithium-ion battery applications

We fabricated composites of Fe₂O₃/reduced graphene oxide as lithium-ion batteries anode material with controlled structures by employing self-assembly of metal–organic frameworks (MOFs) and polymer-functionalized graphene oxide as precursors. By electrostatic interaction, the negatively charged MOFs, Prussian Blue (PB), are assembled on poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene oxide (positive charge). Then the PB cubes become FeOOH nanosheets when treated with sodium hydroxide. Upon further annealing, the FeOOH nanosheets transform to Fe₂O₃ nanoparticles while the graphene oxide become reduced graphene oxide simultaneously. It was found that the composites have good performance as anode of lithium-ion battery. This work shows a new way for self-assembling MOFs and 2D materials.     

Cyclodextrin metal–organic framework by ultrasound-assisted rapid synthesis for caffeic acid loading and antibacterial application

Cyclodextrin metal–organic framework by ultrasound-assisted rapid synthesis for caffeic acid (CA) loading and antibacterial application (U-CD-MOF) was successfully studied and this method shortened the preparation time to a few minutes. It was found that the ultrasonic power, reaction time and temperature would affect the morphology and size of the obtained crystal. Under the optimal conditions, U-CD-MOF had a cubic structure with uniform size of 8.60 ± 1.95 μm. U-CD-MOF was used to load the antibacterial natural product CA to form the composite (CA@U-CD-MOF) and the loading rate of CA@U-CD-MOF to CA could reach 19.63 ± 2.53%, which was more than twice that of γ-CD. Various techniques were applied to characterize the synthesized crystal, including Powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and N₂ adsorption. In addition, antibacterial tests were performed on the obtained crystal. The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of CA@U-CD-MOF for Escherichia coli O157: H7 (E. coli O157: H7) were both 25 mg·mL⁻¹, and the MIC for Staphylococcus aureus (S. aureus). was 25 mg·mL⁻¹. The sustained release behavior of CA@U-CD-MOF to CA in ethanol fitted well to Higuchi model and the loading of CA was supported by molecular docking results. In general, U-CD-MOF was successfully achieved by ultrasound-assisted rapid synthesis and the obtained crystal was further evaluated for potential antibacterial application.     

Substrate and pretreatment dependence of Cu nucleation by metal–organic chemical vapor deposition

The nucleation of copper (Cu) with (hfac)Cu(VTMS) organometallic precursor is investigated for Si, SiO₂, TiN, and W₂N substrates. As the deposition temperature is increased, the dominant growth mechanism is observed to change from the nucleation of Cu particles to the clustering of Cu nuclei around 180 °C independent of the employed substrates. It is also observed that the cleaning of substrate surfaces with the diluted HF solution improves the selectivity of Cu nucleation between TiN and SiO₂ substrates. Dimethyldichlorosilane treatment is found to passivate the surface of TiN substrate, contrary to the generally accepted belief, when the TiN substrate is cleaned by H₂O₂ solution before the treatment.     

Low temperature synthesis of titanium diboride nanosheets by molten salt–assisted borothermal reduction of TiO2

Journal of Nanoparticle Research - In this work, impact of synthesized silica nanotubes (SNTs) on morphology and performance of polyvinylidene fluoride (PVDF) nanocomposite membrane was studied....     

Mid-gap photoluminescence and magnetic properties of GaMnN films grown by metal–organic chemical vapor deposition

Metal-organic chemical vapor deposition （MOCVD） grown ferromagnetic GaMnN films are investigated by photo- luminescence （PL） measurement with a mid-gap excitation wavelength of 405 nm. A sharp PL peak at 1.8 eV is found and the PL intensity successively decreases with the addition of Mn, in which the Mn concentration of sample A is below 1% （[Mn]A =0.75%） but its PL intensity is stronger than other samples＇. The 1.8-eV PL peak is attributed to the recombination of electrons in the t2 state of the neutral Mn3＋ acceptor with holes in the valence band. With Mn concentration increasing, the intensity of the PL peak decreases and the magnetic increment reduces in our samples. The correlation between the PL peak intensity and ferromagnetism of the samples is discussed in combination with the experimental results.     

Synthesis of titanium dioxide by ultrasound assisted sol–gel technique: Effect of amplitude (power density) variation

Titanium dioxide was successfully synthesized by utilizing sol–gel technique modified by incorporation of ultrasound as a reaction aid. The effect of amplitude of irradiation (power input varied from 19.9 to 80.8 W) on % Rutile, % yield, % crystallinity, crystallite size and morphological (scanning electron microscopy) properties of the obtained nano-TiO₂ was studied. Calcination temperatures of all the samples were kept constant at 750 °C. With increasing ultrasonic irradiation amplitude it is observed that the values of % Rutile (after calcination) increased and reached a peak value after which further increase in amplitude resulted in a decrease in the % Rutile. A similar trend was observed in the case of % crystallinity and % yield of the reaction. On the basis of these results an optimum operating ultrasonic irradiation amplitude for the reaction has been suitably established.     

Preparation of metal–ceramic composites by sonochemical synthesis of metallic nano-particles and in-situ decoration on ceramic powders

Copper and nickel nanoparticles were synthesized using reducing agents in the presence of direct high energy ultra-sonication. The metallic nanoparticles were decorated on various ceramic substrates (e.g. α-Al₂O₃, and TiO₂) leading to metal reinforced ceramics with up to 45% metallic content. Different parameters, such as the amount of precursor material or the substrate, as well as the intensity of ultrasound were examined, in order to evaluate the percentage of final metallic decoration on the composite materials. All products were characterized by means of Inductively Coupled Plasma Spectroscopy in order to investigate the loading with metallic particles. X-ray Diffraction and Scanning Electron Microscopy were also used for further sample characterization. Selected samples were examined using Transmission Electron Microscopy, while finally, some of the powders synthesized, were densified by means of Spark Plasma Sintering, followed by a SEM/EDX examination and an estimation of their porosity.     

Study of tryptophan assisted synthesis of gold nanoparticles by combining UV–Vis, fluorescence, and SERS spectroscopy

We developed a rapid and non-toxic method for the preparation of colloidal gold nanoparticles (GNPs) by using tryptophan (Trp) as reducing/stabilizing agent. We show that the temperature has a major influence on the kinetics of gold ion reduction and the crystal growth, higher temperatures favoring the synthesis of anisotropic nanoparticles (triangles and hexagons). The as-synthesized nanostructures were characterized by UV–Vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), fluorescence, and surface-enhanced Raman scattering (SERS) spectroscopy. The UV–Vis measurements confirmed that temperature is a critical factor in the synthesis process, having a major effect on the shape of the synthesized GNPs. Moreover, fluorescence spectroscopy was able to monitor the quenching of the Trp fluorescence during the in situ synthesis of GNPs. Using Trp as molecular analyte to evaluate the SERS efficiency of as-prepared GNPs at different temperatures, we demonstrated that the Raman enhancement of the synthesized gold nanoplates is higher than that of the gold spherical nanoparticles.     

Detection of nano-interfacial space charge field at metal–organic film interface by SHG and surface potential

At the metal–organic film nano-interface, surface polarization phenomena are observed, due to the displacement of excess charges from metal to the films as well as alignment of polar dipoles. Surface potential method has been employed to examine these surface polarization phenomena, and the distribution of space charges and distribution of electronic density of states have been determined. However, for further understanding of the nanometric interface phenomena, it is very helpful to develop an experimental method that can detect electrical and optical phenomena induced by the space charge formation. In this paper, it is shown that optical second harmonic generation measurement is effective through our experiment on phthalocyanine films deposited on Al and Au electrodes.     

Electrical metal contacts to atomically thin 2H-phase MoTe2 grown by metal–organic chemical vapor deposition

We grow atomically thin molybdenum ditelluride (MoTe₂) films on a SiO₂/Si substrate by means of metal–organic chemical vapor deposition (MOCVD). Our Raman spectroscopy measurements reveal the formation of 2H-phase MoTe₂ films. Further, transmission electron microscopy and X-ray photoelectron spectroscopy studies indicate a three-atomic-layer structure and the surface element composition of MoTe₂ films. In this study, we mainly focus on the influence of metal contacts attached to the films on their electrical performance. We fabricate 2H-phase-MoTe₂-based field-effect transistors (FETs) with various metal contacts such as titanium/gold, nickel and palladium, which present p-type semiconductor properties. We also examine the influence of the work functions of the contact metals on the electrical properties of three-atomic-layer-MoTe₂-based FET devices. For a p-type MoTe₂ semiconductor, higher work functions of the contact metals afford narrower Schottky barrier heights (SBHs) and eventually highly efficient carrier injection through the contacts.     

Nanodots and microwires of ZrO_2 grown on LaAlO_3 by photo-assisted metal–organic chemical vapor deposition

ZrO_2 nanodots are successfully prepared on LaAlO_3(LAO)(100) substrates by photo-assisted metal-organic chemical vapor deposition(MOCVD). It is indicated that the sizes and densities of ZrO_2 nanodots are controllable by modulating the growth temperature, oxygen partial pressure, and growth time. Meanwhile, the microwires are observed on the surfaces of substrates. It is found that there is an obvious competitive relationship between the nanodots and the microwires. In a growth temperature range from 500℃ to 660℃, the microwires turn longest and widest at 600℃, but in contrast, the nanodots grow into the smallest diameter at 600℃. This phenomenon could be illustrated by the energy barrier, decomposition rate of Zr(tmhd)_4, and mobility of atoms. In addition, growth time or oxygen partial pressure also affects the competitive relationship between the nanodots and the microwires. With increasing oxygen partial pressure from 451 Pa to 75_2 Pa,the microwires gradually grow larger while the nanodots become smaller. To further achieve the controllable growth, the coarsening effect of ZrO_2 is modified by varying the growth time, and the experimental results show that the coarsening effect of microwires is higher than that of nanodots by increasing the growth time to quickly minimize ZrO_2 energy density.     

Ultrasound and microwave assisted synthesis of high loading Fe-supported Fischer–Tropsch catalysts

Supported iron-based Fischer–Tropsch (FT) catalysts with high loading of active metal have been prepared using both traditional and innovative methods. In these latter the impregnation of silica support has been performed by adding a step involving an ultrasound (US) or a microwave (MW) treatment to improve the metal deposition and to increase the catalyst activity. FT results have indicated the catalysts prepared by US as the most efficient, particularly when sonication is performed in argon atmosphere. MW prepared samples have given results very similar to those obtained with the traditional method. In order to explain the different catalytic activity, all the samples have been characterized by BET, TPR, SEM, TEM, XRD and micro-Raman analyses.     

Growth of polymer–metal nanocomposites by pulsed laser deposition

Complex polymer–metal nanocomposites have a wide range of applications, e.g. as flexible displays and packaging materials. Pulsed laser deposition was applied to form nanostructured materials consisting of metal clusters (Ag, Au, Pd and Cu) embedded in a polymer (polycarbonate, PC) matrix. The size and amount of the metal clusters are controlled by the number of laser pulses hitting the respective targets. For Cu and Pd, smaller clusters and higher cluster densities are obtained as in the cases of Ag and Au due to a stronger reactivity with the polymers and thus a lower diffusivity. Implantation effects, differences in metal diffusivity and reactivity on the polymer surfaces, and the coalescence properties are discussed with respect to the observed microstructures on PC and compared to the metal growth on poly (methyl methacrylate), PMMA.     

Laser-induced synthesis of metal–carbon materials for implementing surface-enhanced Raman scattering

Metal–carbon materials exhibiting surface-enhanced Raman scattering have been synthesized by laser irradiation of colloidal systems consisting of carbon and noble metal nanoparticles. The dependence of the Raman scattering intensity on the material composition and laser irradiation conditions has been investigated. The possibility of recording the Raman spectrum of organic dye rhodamine 6G, deposited in amount of 10^–6 M on the substrate obtained from a colloidal solution is demonstrated.     

Atmospheric-pressure metal–organic vapor-phase epitaxy of GaAsBi alloys on high-index GaAs substrates

We investigated the growth characteristics and properties of GaAsBi layers grown by atmospheric-pressure metal–organic vapor-phase epitaxy on different GaAs substrate orientations. The surface morphology of GaAsBi alloys was investigated by means of scanning electron microscopy. The structural and optical properties of the alloys were examined using high-resolution X-ray diffraction (HRXRD) and photoreflectance spectroscopy, respectively. HRXRD results show that the GaAsBi growth rate was significantly lower on (1 1 5)A than on (0 0 1), (1 1 1)A and (1 1 4)A GaAs. The highest Bi content was obtained for GaAsBi layers grown on (1 1 5)A GaAs substrates.