Solvent-tuned ultrasonic synthesis of 2D coordination polymer nanostructures and flakes

Herein, a new 2-dimensional coordination polymer based on copper (II), {Cu₂(L)(DMF)₂}_n, where L stands for 1,2,4,5-benzenetetracarboxylate (complex 1) is synthesized. Interestingly, we demonstrate that both solvent and sonication are relevant in the top-down fabrication of nanostructures. Water molecules are intercalated in suspended crystals of complex 1 modifying not only the coordination sphere of Cu(II) ions but also the final chemical formula and crystalline structure obtaining {[Cu(L)(H₂O)₃]·H₂O}_n (complex 2). On the other hand, ultrasound is required to induce the nanostructuration. Remarkably, different morphologies are obtained using different solvents and interconversion from one morphology to another seems to occur upon solvent exchange. Both complexes 1 and 2, as well as the corresponding nanostructures, have been fully characterized by different means such as infrared spectroscopy, x-ray diffraction and microscopy.     

Ultrasound-assisted exfoliation of a layered 2D coordination polymer with HER electrocatalytic activity

Large blue rectangular crystals of the 2D layered coordination polymer 1 have been obtained. The interest for this complex is two-fold. First, complex 1 is made of 2D layers packing along the (0–11) direction favored by the presence of lattice and coordinated water molecules. And second, nanostructures that could be derived by delamination are potentially suitable for catalytic purposes. Therefore it represents an excellent example to study the role of interlayer solvent molecules on the ultrasound-assisted delamination of functionally-active 2D metal-organic frameworks in water, a field of growing interest. With this aim, ultrasound-assisted delamination of the crystals was optimized with time, leading to stable nanosheet colloidal water suspensions with very homogeneous dimensions. Alternative bottom-up synthesis of related nanocrystals under ultrasound sonication yielded similar shaped crystals with much higher size dispersions. Finally, experimental results evidence that the nanostructures have higher catalytic activities in comparison to their bulk counterparts, due to larger metallic center exposition. These outcomes confirm that the combination of liquid phase exfoliation and a suitable synthetic design of 2D coordination polymers represents a very fruitful approach for the synthesis of functional nanosheets with an enhancement of catalytic active sites, and in general, with boosted functional properties.     

Ultrasound irradiation effect on morphology and size of two new potassium coordination supramolecule compounds

Two new potassium coordination supramolecular compounds (2D and 1D), [K(H₃L)(H₂L)(H₂O)]_n·H₂O (1) and [K(H₂L′)(HL′)(H₂O)₂]·H₂O (2), (L = 1,3,5-tricarboxylic acid, L′ = 2,6-pyridinedicarboxylic acid), have been synthesized under different experimental conditions. Micrometric crystals (bulk) or nano-sized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by field emission scanning electron microscopy (FE-SEM), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), FT-IR spectroscopy and elemental analyses. Single crystal X-ray analyses on compounds 1 and 2 show that K⁺ ions are 3- and 7-coordinated, respectively. Additionally, H-bonds incorporate the layers and chains in 1 and 2 into 3D and 2D (along (0,0,1) direction) frameworks. Topological analysis shows that the compound 1 and 2 are 3,6-coordinated kgd and 2,4-coordinated 2,4C4 net. The thermal stability of compounds 1 and 2 in bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal analyses (DTA) and compared each other. The role of different parameters like temperature, reaction time and ultrasound irradiation power on the growth and morphology of the nano-structures are studied. Results suggest that an increase of temperature, sonication power and reduction of reaction time led to a particle size decrease.     

Influence of solvents on the morphological properties of AgBr nano-structures prepared using ultrasound irradiation

Nano-structures of AgBr have been prepared by reaction between AgNO₃ and KBr under ultrasound irradiation. Particle sizes and morphology of nanoparticle are depending on temperature, power of sonicating, reaction time and concentration. The effects of these parameters in growth and morphology of the nano-structures have been studied. Results suggest that an increasing of temperature, sonication power and concentration led to a decreasing of particle size. The samples were characterized with powder X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

Ultrasound irradiation based in-situ synthesis of star-like Tragacanth gum/zinc oxide nanoparticles on cotton fabric

Application of natural biopolymers for green and safe synthesis of zinc oxide nanoparticles on the textiles is a novel and interesting approach. The present study offers the use of natural biopolymer, Tragacanth gum, as the reducing, stabilizing and binding agent for in-situ synthesis of zinc oxide nanoparticles on the cotton fabric. Ultrasonic irradiation leads to clean and easy synthesis of zinc oxide nanoparticles in short-time at low-temperature. FESEM/EDX, XRD, FT-IR spectroscopy, DSC, photocatalytic activities and antimicrobial assay are used to characterize Tragacanth gum/zinc oxide nanoparticles coated cotton fabric. The analysis confirmed synthesis of star-like zinc oxide nanoparticles with hexagonal wurtzite structure on the cotton fabric with the average particle size of 62 nm. The finished cotton fabric showed a good photocatalytic activity on degradation of methylene blue and 100% antimicrobial properties with inhibition zone of 3.3 ± 0.1, 3.1 ± 0.1 and 3.0 ± 0.1 mm against Staphylococcus aureus, Escherichia coli and Candida albicans.     

Radiation effect on optical,morphological and magnetic properties of aluminum-substituted M phase barium hexaferrite

The effect of gamma irradiation on the features of aluminum-substituted barium hexagonal ferrite particles BaAl_xFe_12?xO₁₉ with 0?≤?x?≤?3.5 has been studied. Optical absorption measurements have been performed and the results reflected a great dependence of the fundamental absorption edge on the radiation dose. It is found that the calculated optical band gap (E_g) increases due to an increase in the homogeneity with an increase in the Al content. Increasing the radiation dose up to 1?MGy induces a direct transition and consequently decreases the energy gap. This behavior is associated with the generation of excess electronic localized states. Moreover, the characteristic features of the irradiated samples have been studied using a scanning electron microscope. Also, all samples were characterized using the X-ray diffraction technique, and the values of crystal size, microstrain and dislocation density were calculated. On the other hand, the magnetic behavior of the samples was studied using a vibrating sample magnetometer technique after each radiation dose. The saturation magnetization (M_s) and the magneton number (n_B) decrease with an increase in the Al³⁺ substitution and at the same time decrease with the radiation dose 250?kGy to 1?MGy.     

Organic functionalization of thermally reduced graphene oxide nanoplatelets by adsorption: structural and morphological characterization

Adsorption of chlorinated poly(ethylene-co-vinyl acetate)-g-maleic anhydride copolymer and in situ-generated polyaniline (PANI) on thermally reduced graphene oxide (TRGO) platelets was studied in the current study. The adsorption was characterized structurally and morphologically through thermogravimetric analysis, differential scanning calorimetry (DSC), elemental analysis, infra-red and Raman spectroscopy, X-ray diffraction and microscopy. The amount of copolymer adsorption reached a plateau of 0.22 g per g of TRGO, when the initial copolymer to TRGO weight ratio of 1 was used. In the case of PANI modification, much higher extent of adsorption of 0.92 g/g of TRGO (without reaching plateau) was observed due to in situ polymer synthesis and the absence of any steric hindrance to the chains. Shift in the DSC melting transition temperatures of copolymer also indicated that some change in the polymer chain morphology took place after immobilization of polymer on TRGO. PANI modification led to significant reduction in peak melting point from 175C to 140 °C owing to the hindrance in polymer crystallization. The basal plane spacing in the TRGO platelets increased the copolymer adsorption as the 0?0?1 basal plane diffraction shifted from 27° 2Θ for pristine TRGO to 22.5° 2Θ for modified TRGO. For the PANI modified TRGO, no diffraction signal corresponding to TRGO was observed due to extensive adsorption of polymer on the surface. A much thicker polymer phase wrapping the TRGO platelets was observed for PANI modified TRGO. This was also observed through EFTEM and EDX, where the presence of Cl and N (along with other atoms) indicated layer of copolymer and PANI, respectively on the surface of the platelets. EELS analysis also confirmed the semi-crystalline nature of the modified TRGO resulting from the adsorption of semi-crystalline polymers on TRGO. The adsorption approaches used in the study demonstrate successful generation of the functional nanomaterials with tunable extent of surface coverage and potential of employing diverse surface modifications.     

Ultrasound assisted chitosan coated iron oxide nanoparticles: Influence of ultrasonic irradiation on the crystallinity,stability, toxicity and magnetization of the functionalized nanoparticles

Due to unique reaction conditions of the acoustic cavitation process, ultrasound-assisted synthesis of nanoparticles has attracted increased research attention. In this study, we demonstrate the effect of ultrasonic irradiation on the crystallinity, stability, biocompatibility, and magnetic properties of chitosan-coated superparamagnetic iron oxide nanoparticles (CS-SPIONs). CS solution and colloidal suspension of SPIONs were mixed and sonicated using an ultrasonic probe of 1.3 cm tip size horn, frequency (20 kHz), and power (750 W). Different samples were sonicated for 1.5, 5, and 10 min with corresponding acoustic powers of 67, 40 and 36 W, and the samples were denoted S_1.5, S_5, and S₁₀, respectively. The samples were characterized using X-ray diffractometer (XRD), Energy dispersive X-ray (EDX), Transmission electronic microscope (TEM), Fourier transform infrared spectroscopy (FTIR), Zeta sizer, and vibrating sample magnetometer (VSM). Cell cytotoxicity and cell uptake were investigated with human embryonic kidney 293 (HEK-293) cells through MTT assay and Prussian blue staining, respectively. The sharp peaks of the XRD pattern were disappearing with an increase in the sonication period but a decrease in acoustic power. EDX analysis also demonstrates that atomic and weight percentages of the various elements in the samples were decreasing with an increase in the sonication period. However, the Zeta potential (ζ) values increase with an increase in the sonication period.The saturation magnetization (M_s) of the S_1.5 before and after the coating is 62.95 and 86.93 emu/g, respectively. Cell cytotoxicity and uptake of the S_1.5 show that above 70% of cells were viable at the highest concentration and the longest incubation duration. Importantly, the CS-SPIONs synthesized by the sonochemical method are non-toxic and biocompatible.     

Nanocomposite materials based on poly(vinyl chloride) and bovine serum albumin modified ZnO through ultrasonic irradiation as a green technique: Optical,thermal, mechanical and morphological properties

In this project, physicochemical properties of poly(vinyl chloride) (PVC) reinforced by ZnO nanoparticles (NPs) were studied. Firstly, ZnO NPs were modified with bovine serum albumin (BSA) as an organo-modifier and biocompatible substance through ultrasound irradiation as environmental friendly, low cost and rapid means. Nanocomposite (NC) films were prepared by loadings of various ratios of ZnO/BSA NPs (3, 6 and 9 wt%) inside the PVC. Structural morphology and physical properties of the ZnO-BSA NPs and NC films were investigated via Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis (TGA), transmission electron microscopy and field emission scanning electron microscopy. According to the obtained information from the TGA, an increase in the thermal stability can be clearly observed. Also the results of contact angle analysis indicated with increasing percent of ZnO/BSA NPs into PVC the hydrophilic behaviors of NCs were increased.     

The effect of non-contact heating (microwave irradiation) and contact heating (annealing process) on properties and performance of polyethersulfone nanofiltration membranes

In this work the effect of microwave irradiation on morphology and performance of polyethersulfone (PES) membranes was investigated. The membranes were prepared with 20 wt.% of PES by phase inversion method. N,N-dimethylformamide (DMF) and mixture of water and ethyl alcohol (90/10 vol.%) were employed as solvent and coagulant respectively. Polyvinylpirrolidone (PVP) with the concentration of 2 wt.% was selected as pore former. The effects of irradiation time (10, 30, 60, 90, 120 s) and microwave power (180, 360, 720 and 900 W) on structure and performance of membranes were studied. Increasing the irradiation time and power caused variation in permeate flux and ion rejection. Moreover, the effects of annealing processes (60, 70, 80 °C) were studied. Transmembrane pressure was selected around 1.5 MPa for all experiments. Scanning electron microscope (SEM) and atomic force microscope (AFM) were employed to describe the surface morphology of the prepared membranes. The effect of microwave irradiation time in different power revealed alterations in membrane surface morphology and AFM images represented that surface parameters (such as surface roughness) have been changed. The membrane exhibited moderate rejection (47%) and low permeate flux (4.5 kg/m² h) at 80 °C for NaCl solution. The SEM images indicate that the dense skin layer is formed at 80 °C annealing.     

Sonochemically preparation and characterization of bimetallic Ni-Co/Al2O3-ZrO2 nanocatalyst: Effects of ultrasound irradiation time and power on catalytic properties and activity in dry reforming of CH4

The catalytic performance of nanostructured Ni-Co/Al₂O₃-ZrO₂ catalysts, prepared by ultrasound-assisted impregnation method was examined in the dry reforming of methane. The effect of irradiation power and irradiation time have been studied by changing time (0, 20, 80 min) and power of the sonication (30, 60, 90 W) during the synthesis which resulted in different physiochemical properties of the nanocatalyst. The nanocatalysts were characterized by XRD, FESEM, PSD, EDX, TEM, TPR-H₂, BET, FTIR and TG analyses. Based on the characterization results, ultrasound treatment endowed the sample with more uniform and smaller nanoparticles; higher surface area, stronger metal-support interaction and more homogenous dispersion. Moreover, the analyses exhibited smaller particles with higher surface area and less population of particle aggregates at longer and highly irradiated nanocatalysts. The nanocatalyst irradiated at 90 W for 80 min (the longest irradiation time and the most intense power) showed a uniform morphology and a very narrow particles size distribution. More than 65% of particles of this nanocatalyst were in the range of 10–30 nm. Activity tests demonstrated that employing ultrasound irradiation during impregnation improves feed conversion and products yield, reaching values close to equilibrium. Among sonicated nanocatalysts, with increasing power and time of irradiation, the nanocatalyst represents higher activity. The superior performance amongst the various bimetallic catalysts tested was observed over the catalyst with 90 W and 80 min ultrasonic irradiation which is stable in 24 h time on stream test. The excellent anti-coking performance of this bimetallic catalyst, confirmed by TG and FESEM analyses of spent catalyst, is closely related to the promoting effect of sonication on the metal-support interaction, Ni dispersion and particle size; and probably, the synergy between metallic species.     

The effect of aminoalcohols (MEA, DEA and TEA) on morphological control of nanocrystalline ZnO powders and its optical properties

The potential of using encapsulation by MEA, DEA and TEA to control the morphology of ZnO powders was investigated. The crystallite and particle size decreased as a function of aminoalcohol concentration. We found that aminoalcohols can inhibit the crystal growth of ZnO along the c-axis. A steric effect by TEA more strongly influenced the formation of different ZnO shapes than did MEA and DEA. The value of the band gap was dependent on the crystallite size, particle size and particle shape.     

Effects of ultrasonic irradiation on crystallization kinetics,morphological and structural properties of zeolite FAU

In this work, NaX zeolite was synthesized and the effect of ultrasound irradiation on reaction kinetics, morphological and structural properties was investigated. Ultrasound was applied, by using a plate transducer (91.8 kHz), for the first time during the crystallization of zeolite NaX, at high temperature, varying the irradiation moment and its duration. Furthermore, ultrasound was applied after the crystallization by a horn-type transducer (20–24 kHz) at low temperature. The effects of irradiated volume (100–300 mL), sonication time (2–10 min) and ultrasound power (10–200 W) were studied with a power intensity up to 100 W/cm². It was found that the application of ultrasound during the first hour of crystallization resulted in 20% reduction of reaction time compared to a standard crystallization. Ultrasound can also reduce the agglomeration degree of the final powder by combining high power and long sonication time. After 5 min sonication time at 0.3 W/mL, the tapped density of the powder was increased by 10%, from 0.37 to 0.41 g/mL. Finally, by scanning electron microscopy (SEM) it was demonstrated that ultrasound can disrupt the agglomerates without affecting the morphology of individual crystals.     

Effects of annealing rate and morphology of sol–gel derived ZnO on the performance of inverted polymer solar cells

The effects of annealing rate and morphology of sol–gel derived zinc oxide(ZnO)thin films on the performance of inverted polymer solar cells(IPSCs)are investigated.ZnO films with different morphologies are prepared at different annealing rates and used as the electron transport layers in IPSCs.The undulating morphologies of ZnO films fabricated at annealing rates of 10 C/min and 3 C/min each possess a rougher surface than that of the ZnO film fabricated at a fast annealing rate of 50 C/min.The ZnO films are characterized by atomic force microscopy(AFM),optical transmittance measurements,and simulation.The results indicate that the ZnO film formed at 3 C/min possesses a good-quality contact area with the active layer.Combined with a moderate light-scattering,the resulting device shows a 16%improvement in power conversion efficiency compared with that of the rapidly annealed ZnO film device.     

Influence of 120 MeV S9+ ion irradiation on structural,optical and morphological properties of zirconium oxide thin films deposited by RF sputtering

The calibrated and controlled swift heavy ions (SHI) beam irradiation generate defects which can cause modifications in various properties of the materials such as structural, optical, magnetic, morphological, and chemical etc. The passage of ion through the target material causes the nuclear energy losses ($S_n$) and electronic energy losses ($S_e$). The $S_e$ dominates over $S_n$ in SHI irradiation. In the present study, ZrO₂ thin films were grown on silicon and glass substrate by using RF sputtering deposition technique. For the purpose of modifications induced by swift heavy ions, these films were irradiated by a 120 MeV S⁹⁺ ion beam of 1 pnA current, with varying ion fluences from 5E12 to 1E13 ions/cm², using the tandem accelerator at the Inter University Accelerator Center (IUAC), New Delhi, India. The X-ray diffraction (XRD) patterns confirmed the formation of monoclinic and tetragonal phases and it was observed that XRD peaks intensity increased up to the fluence of 5E12 ions/cm² followed by opposite behavior at higher fluences. Atomic force microscope (AFM) study revealed the increased surface roughness after SHI irradiation. In addition to it, the formation of electronic transition states in optical band gap region and enhancement of absorption edge was observed from UV-visible spectroscopy (UV-Vis) results due to which direct band gap energy value decreased from those of un-irradiated samples. Photoluminescence (PL) broad emission spectra were determined using the excitation wavelength at 290 nm with the prominent peak at 415 nm which can be ascribed to Zr vacancies due to band edge emission as a result of free-exciton recombination. Rutherford backscattering spectrometry (RBS) technique was used for depth profiling and elemental composition in zirconia thin films. The expected role of electronic energy loss during ion irradiation is to modify the properties of the material has been discussed.     

Effect of UV irradiation on the structural,optical and electrical properties of platinum

Investigations are performed on thermal, optical and electrical response of UV laser-irradiated platinum (Pt). 4N pure, annealed and fine polished samples are exposed to the KrF Excimer laser (248 nm, 20 ns, 50 mJ) under vacuum ～10^?6 torr at different laser fluences (0.5–2.5 J/cm²). Space-resolved plasma plume dynamics is studied by analyzing the captured plume images with the help of a computer controlled image-grabbing system. The irradiated targets are characterized for surface morphology, structural, optical and electrical investigations using the diagnostics; scanning electron microscopy, X-ray diffraction, rotating compensator auto-aligned ellipsometer and four-point probe, respectively. The value of maximum intensity emitted by Pt plasma plume is 250 grey scales. Surfaces of the target metals are modified by craters, moltens and redeposited material. Laser-induced periodic surface structures are produced at low laser fluence. Irradiation of Pt causes changes in diffracted X-rays intensity and grain sizes, dislocation in line densities and strain in the target materials. Considerable changes occur in optical parameters as well. A decrease in electrical conductivity of the irradiated targets also takes place in an exponential way with the change in laser fluence.     

Surface morphological changes and magnetic properties of Sc-substituted Y3Fe5O12 epitaxial films deposited on the GGG substrate

Sc-doped YIG films were grown on (1 1 1) oriented GGG crystalline substrate with disorientation angle within the range 0-25′. Sc³⁺ ion substitution was varied within the range 0.25-0.3 per formula unit. The films demonstrate different types of surface morphology versus film growth rate and substrate disorientation. Conditions for existence of these types of the surface morphology were defined. The field dependence of magnetic susceptibility at magnetization reversal in film plane and Faraday rotation at wavelength 633 nm for a magnetic field applied in perpendicular direction were measured to characterize the films grown. Films with “mirror-like” surface demonstrate a planar magnetization at room temperature.     

Filler effect on formation and properties of reinforced interpenetrating polymer networks

The formation processes of unfilled and filled interpenetrating polymer networks (IPNs) and some of their physico-mechanical properties have been investigated. The formation kinetics and constituent network curing rates determine the rate and degree of microphase separation. This in turn determines the boundary layer composition and structure. Introduction of filler into the IPN during formation affects greatly the crosslinking reaction and the microphase segregation of homopolymers. It has been shown that the degree of phase segregation in filled IPNs differs from that in unfilled ones. All the fillers were found to shorten the time of internal stress appearance and to increase its value for IPNs with predominantly high-modulus component content. Some filled IPNs were shown to have greater thermodynamic stability than unfilled ones.     

Ultrasound assisted reduction of graphene oxide to graphene in l-ascorbic acid aqueous solutions: Kinetics and effects of various factors on the rate of graphene formation

The reduction of graphene oxide (GO) to graphene (rGO) was achieved by using 20 kHz ultrasound in l-ascorbic acid (l-AA, reducing agent) aqueous solutions under various experimental conditions. The effects of ultrasound power, ultrasound pulse mode, reaction temperature, pH value and l-AA amount on the rates of rGO formation from GO reduction were investigated. The rates of rGO formation were found to be enhanced under the following conditions: high ultrasound power, long pulse mode, high temperature, high pH value and large amount of l-AA. It was also found that the rGO formation under ultrasound treatment was accelerated in comparison with a conventional mechanical mixing treatment. The pseudo rate and pseudo activation energy (E_a) of rGO formation were determined to discuss the reaction kinetics under both treatment. The E_a value of rGO formation under ultrasound treatment was clearly lower than that obtained under mechanical mixing treatment at the same condition. We proposed that physical effects such as shear forces, microjets and shock waves during acoustic cavitation enhanced the mass transfer and reaction of l-AA with GO to form rGO as well as the change in the surface morphology of GO. In addition, the rates of rGO formation were suggested to be affected by local high temperatures of cavitation bubbles.