In situ studies on free-standing synthesis of nanocatalysts via acoustic levitation coupled with pulsed laser irradiation

Acoustic levitation is a distinctive and versatile tool for levitating and processing free-standing single droplets and particles. Liquid droplets suspended in an acoustic standing wave provide container-free environments for understanding chemical reactions by avoiding boundary effects and solid surfaces. We attempted to use this strategy for the production of well-dispersed uniform catalytic nanomaterials in an ultraclean confined area without the addition of external reducing agents or surfactants. In this study, we report on the synthesis of gold and silver nanoparticles (NPs) via acoustic levitation coupled with pulsed laser irradiation (PLI). In situ UV–Visible and Raman spectroscopic techniques were performed to monitor the formation and growth of gold and silver NPs. The PLI was used for the photoreduction of targeted metal ions present in the levitated droplets to generate metal NPs. Additionally, the cavitation effect and bubble movement accelerate the nucleation and decrease the size of NPs. The synthesized Au NPs with ∼ 5 nm size showed excellent catalytic behavior towards the conversion of 4-nitrophenol to 4-aminophenol. This study may open a new door for synthesizing various functional nanocatalysts and for achieving new chemical reactions in suspended droplets.     

Utilization of surface plasmon resonance of Au/Pt nanoparticles for highly photosensitive ZnO nanorods network based plasmon field effect transistor

Hydrothermally processed highly photosensitive ZnO nanorods based plasmon field effect transistors (PFETs) have been demonstrated utilizing the surface plasmon resonance coupling of Au and Pt nanoparticles at Au/Pt and ZnO interface. A significantly enhanced photocurrent was observed due to the plasmonic effect of the metal nanoparticles (NPs). The Pt coated PFETs showed I_on/I_off ratio more than 3 × 10⁴ under the dark condition, with field-effect mobility of 26 cm² V⁻¹ s⁻¹ and threshold voltage of −2.7 V. Moreover, under the illumination of UV light (λ = 350 nm) the PFET revealed photocurrent gain of 10⁵ under off-state (−5 V) of operation. Additionally, the electrical performance of PFETs was investigated in detail on the basis of charge transfer at metal/ZnO interface. The ZnO nanorods growth temperature was preserved at 110 °C which allowed a low temperature, economical and simple method to develop highly photosensitive ZnO nanorods network based PFETs for large scale production.     

Effects of ultrasound irradiation on Au nanoparticles deposition on carbon-coated LiNi0.5Mn1.5O4 and its performance as a cathode material for Li ion batteries

LiNi_0.5Mn_1.5O₄ (LMNO) has attracted considerable attention as a Li-ion battery cathode material, owing to its high discharge voltage of 4.7 V (vs. Li/Li⁺) and high energy density. However, the electronic conductivity of LMNO is low, resulting in a low discharge capacity at high current density. To overcome this limitation, we deposited Au nanoparticles (NPs), which have a high conductivity and chemical stability at high battery voltages, on carbon-coated LMNO (LMNO/C) using ultrasound irradiation. Consequently, Au NPs that are ∼16 nm in size were deposited on LMNO/C, and ultrasound irradiation was reported to disperse the NPs on LMNO/C more effectively than stirring. Furthermore, the deposition of Au NPs on LMNO/C using ultrasound irradiation improved its electronic conductivity, which is related to an increase in the discharge capacity due to the reduction of Ni⁴⁺ to Ni²⁺ in LMNO/C at a high current density.     

Structural characterization and X-ray analysis by Williamson–Hall method for Erbium doped Aluminum Nitride nanoparticles,synthesized using inert gas condensation technique

We have synthesized AlN nanoparticles (NPs) doped in-situ with Er (AlN:Er) using inert gas condensation technique. Using x-ray diffraction (XRD) peak broadening analysis with the Williamson–Hall (W–H) Uniform Deformation Model (UDM) the crystallite size of the NPs and the strain in NPs were found to be 80±38 nm and 3.07×10⁻³±0.9×10⁻³ respectively. In comparison, using the Debye–Scherrer's (DS) formula, we have inferred that the crystallite size of the NPs was 23±6 nm and the average strain was 4.3×10⁻³±0.4×10⁻³. The scanning electron microscopy images show that the NPs are spherical and have an average diameter of ∼300 nm. The crystallite size is smaller than the size of the NPs revealing their polycrystalline behavior. In addition, the NPs strain, stress and energy density were also calculated using W–H analysis combined with the Uniform Deformation Stress Model (UDSM) and the Uniform Deformation Energy Density Model (UDEDM). Suggested by the spherical geometry and polycrystalline nature of the AlN NPs, the strain computed from UDM, UDSM and UDEDM were in agreement confirming an isotropic mechanical nature of the particle. Luminescence measurements revealed the temperature dependence of the optical emission of the Er³⁺ ions, confirming the use of AlN:Er NPs for nano-scale temperature sensing.     

Diamine-linked array of metal (Au,Ag) nanoparticles on glass substrates for reliable surface-enhanced Raman scattering (SERS) measurements

Metal (Au, Ag) nanoparticles (M NPs) (ca. 30–40 nm) prepared by citrate reduction method were arrayed on amine-terminated glass substrates using diamine linkers with different chain lengths. 1,4-diaminobutane (C-4 diamine) produced the uniform and densely-packed array of M NPs on glass substrates at appropriate concentration ranges, whereas diamine linkers with longer chain lengths (C-8 and C-12 diamines) produced more heterogeneous and aggregated array of M NPs. When compared to Ag NPs, Au NPs demonstrated more controllable and higher packing density due to their mono-dispersed size and higher affinity to diamine linkers. Uniformly arrayed M NPs (Au, Ag) on glass substrates exhibited high enhancement factors in SERS measurements of o-chlorothiophenol probes. Au NPs arrayed substrates exhibited an approximate power-law linearity of Raman intensity with probe concentrations (from 10⁻⁷ M to 10⁻⁴ M), demonstrating more reliable SERS substrates than Ag arrayed substrates with higher SERS activity.     

Importance of poly(ethylene glycol) conformation for the synthesis of silver nanoparticles in aqueous solution

Silver nanoparticles (NPs) were prepared using silver nitrate (AgNO₃) as a precursor in an aqueous solution of poly(ethylene glycol) (PEG), which acted as both a reducing and stabilizing agent. The UV/Vis spectra showed that PEG 100 (100 kg/mol) has a remarkable capability to produce silver NPs at 80 °C, but the production of silver NPs by both PEG 2 (2 kg/mol) and PEG 35 (35 kg/mol) was negligible. This difference was explained by the conformation of PEG in the reaction solution: the entangled conformation for PEG 100 and the single-coiled conformation for PEG 2 and PEG 35, which were confirmed by pulse-field-gradient ¹H NMR and viscosity measurements. In an aqueous solution, the entangled conformation of PEG 100 facilitated the reduction reaction by caging silver ions and effectively prevented the agglomeration of formed NPs. The reaction in an aqueous PEG 100 solution was observed to be stable under the conditions of a prolonged reaction time or an increased temperature, while no reduction reaction occurred in the PEG 2 solution. The synthesis of silver NPs by PEG 100 was well controlled to produce fine silver NPs with 3.68 ± 1.03 nm in diameter, the size of which remained relatively constant throughout the reaction.     

In situ electron beam irradiated rapid growth of bismuth nanoparticles in bismuth-based glass dielectrics at room temperature

In this study, in situ control growth of bismuth nanoparticles (Bi⁰ NPs) was demonstrated in bismuth-based glass dielectrics under an electron beam (EB) irradiation at room temperature. The effects of EB irradiation were investigated in situ using transmission electron microscopy (TEM), selected-area electron diffraction and high-resolution transmission electron microscopy. The EB irradiation for 2–8 min enhanced the construction of bismuth nanoparticles with a rhombohedral structure and diameter of 4–9 nm. The average particle size was found to increase with the irradiation time. Bismuth metal has a melting point of 271 °C and this low melting temperature makes easy the progress of energy induced structural changes during in situ TEM observations. This is a very useful technique in nano-patterning for integrated optics and other applications.     

Characterization of nanoporous carbon fibrous materials obtained by chemical activation of plane tree seed under ultrasonic irradiation

An ultrasonic irradiation was applied for the impregnation by chemical agents in the chemical activation process of new type of active carbon precursor. Plane tree seed, due to the unique fibrous structure and low cost is a promising eco-friendly raw material for the preparation of activated carbon materials. Ultrasonic irradiation was used for the impregnation step allowing the chemical activation by different agents: potassium or sodium hydroxide, hydrogen peroxide and pyrogallol. The porous structures were examined by nitrogen adsorption/desorption isotherms at 77 K and electrochemically by cyclic voltammetry. The textures of these materials were observed by scanning electron microscopy. The application of ultrasonic irradiation in the impregnation step increased surface area of the final material more than two times in comparison to the material which impregnation in the activation process was by conventional stirring. Ultrasonic irradiation enhances the chemical activation process and the activated carbon fibrous materials with nanoporous structure were obtained by impregnation of seeds with alkaline hydroxides. Total surface areas of these samples were 976 m² g⁻¹ and 1130 m² g⁻¹. These fibers have total specific capacitance as high as 125 F g⁻¹ and 53 F g⁻¹ which major fraction in both cases originate from internal micropores structure.     

Characterization and applications of as-grown β-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles prepared by hydrothermal method

The production of low-dimensional nanoparticles (NPs) with appropriate surface modification has attracted increasing attention in biological, biochemical, and environmental applications including chemical sensing, photocatalytic degradation, separation, and purification of toxic molecules from the matrices. In this study, iron oxide NPs have been prepared by hydrothermal method using ferric chloride and urea in aqueous medium under alkaline condition (pH 9 ~ 10). As-grown low-dimensional NPs have been characterized by UV–vis spectroscopy, FT-IR, X-ray diffraction, Field emission scanning electron microscopy, Raman spectroscopy, High-resolution Transmission electron microscopy, and Electron Diffraction System. The uniformity of the NPs size was measured by the scanning electron microscopy, while the single phase of the nanocrystalline β-Fe₂O₃ was characterized using powder X-ray diffraction technique. As-grown NPs were extensively applied for the photocatalytic degradation of acridine orange (AO) and electrochemical sensing of ammonia in liquid phase. Almost 50% photo-catalytic degradation with AO was observed in the presence of UV sources (250 W) with NPs. β-Fe₂O₃ NP-coated gold electrodes (GE, surface area 0.0216 cm²) have enhanced ammonia-sensing performances in their electrical response (I–V characterization) for detecting ammonia in liquid phase. The performances of chemical sensor were investigated, and the results exhibited that the sensitivity, stability, and reproducibility of the sensor improved significantly using β-Fe₂O₃ NPs on GE surface. The sensitivity was approximately 0.5305 ± 0.02 μAcm⁻²mM⁻¹, with a detection limit of 21.8 ± 0.1 μM, based on a signal/noise ratio of 3 with short response time.     

Sonochemical synthesis and fabrication of perovskite type calcium titanate interfacial nanostructure supported on graphene oxide sheets as a highly efficient electrocatalyst for electrochemical detection of chemotherapeutic drug

In green approaches for electrocatalyst synthesis, sonochemical methods play a powerful role in delivering the abundant surface areas and nano-crystalline properties that are advantageous to electrocatalytic detection. In this article, we proposed the sphere-like and perovskite type of bimetal oxides which are synthesized through an uncomplicated sonochemical procedure. As a yield, the novel calcium titanate (orthorhombic nature) nanoparticles (CaTiO₃ NPs) decorated graphene oxide sheets (GOS) were obtained through simple ultrasonic irradiation by a high-intensity ultrasonic probe (Titanium horn; 50 kHz and 60 W). The GOS/CaTiO₃ NC were characterized morphologically and chemically through the analytical methods (SEM, XRD, and EDS). Besides, as-prepared nanocomposites were modified on a GCE (glassy carbon electrode) and applied towards electrocatalytic and electrochemical sensing of chemotherapeutic drug flutamide (FD). Notably, FD is a crucial anticancer drug and also a non-steroidal anti-androgen chemical. Mainly, the designed and modified sensor has shown a wide linear range (0.015–1184 µM). A limit of detection was calculated as nanomolar level (5.7 nM) and sensitivity of the electrode is 1.073 μA μM⁻¹ cm⁻². The GOS/CaTiO₃ modified electrodes have been tested in human blood and urine samples towards anticancer drug detection.     

Synthesis and investigation of the luminescent properties of carbon doped lanthanum aluminate (LaAlO3) for application in radiation dosimetry

LaAlO₃ single crystals grown under hydrothermal conditions and co-doped with Ce and Dy atoms have been recently reported to show high thermoluminescent (TL) outputs for ultraviolet (UV) radiation fields (Oliveira et al., 2011). Due to this property, they have been considered for further investigation for applications in UV dosimetry. Encouraged by these results, we start an investigation about the TL properties of polycrystalline LaAlO₃ grown by an alternative method. In this method, equimolar amounts of Al₂O₃ and La₂O₃ are sintered, producing polycrystalline LaAlO₃ powder. Polycrystals doped with amounts of carbon ranging from 0.0 to 5.0 at.% were synthesized by sintering under hydrogen reducing atmosphere. After irradiation with a UV commercial lamp, the best TL outputs were observed for the undoped sample. The recorded TL glow curves show a main TL peak centered at 175 °C. The TL emission spectrum show a broad emission peak centered at 634 nm and another three narrow peaks centered at 724 nm, 738 nm and 754 nm, respectively. The undoped material show a huge TL output response for UV spectral irradiances ranging from 0.04 to 1.68 mJ cm⁻² that can be fitted by a 2nd order polynomial regression. The investigation demonstrates that undoped polycrystalline LaAlO₃ crystals sintered under reducing atmosphere are very attractive to be investigated as high sensitivity ultraviolet TL dosimeters.     

Acoustically induced light gyration in nickel nanoparticles

Circularly polarized acoustically induced light gyration (AILG) in nickel nanoparticles (NiNPs) attached to indium tin oxide (ITO) substrates was observed to be enhanced by nanosecond UV laser excitation at a wavelength in the surface plasmon resonance region. The AILG was observed during exposure to two acoustical waves with frequencies of 2 and 4 MHz and power densities of up to 5 W/cm². The maximum value of the AILG observed for NiNPs of average size ca. 8.7 nm, attached to an ITO substrate was about 2.8°/mm without UV-light illumination. Additional irradiation by 5 ns pulse UV laser light (λ: 337 nm) at the surface plasmon resonance region was found to favour the additional enhancement of the AILG up to 11°/mm. The effect was optimized at a temperature of 120 K. This increase was not observed when the size of NiNPs was 16.8 nm.     

Green synthesis of finely-dispersed highly bactericidal silver nanoparticles via modified Tollens technique

In this article, we represent a versatile and effective technique which using non-toxic chemicals to prepare stable aqueous dispersions of silver nanoparticles (NPs) via modified Tollens process. It was shown that as-prepared silver colloids consisted of finely-dispersed NPs with average diameter about 10 nm and a relatively narrow size distribution. Moreover, they could be stored very stable after several months without observation of aggregates or sedimentation. In comparison with previous works where Tollens process was being used, we for the first time applied UV-irradiation simultaneously with glucose reduction of silver salt through NPs preparation. The colloidal solutions of silver NPs were found to exhibit a high antibacterial activity against gram-negative Escherichia coli. The concentration of silver leading to a complete inhibition of bacteria growth was revealed as low as at 1.0 μg ml⁻¹ and found much lower compared to earlier reports. These advantages of aqueous dispersions of silver NPs make them ideal for green industrial, medicinal, microbiological and other applications.     

Electrical and dosimetric characterization of a CVD diamond detector with high sensitivity

A prototype detector has been built using commercial high quality single crystal epitaxial diamond and novel electrical contacts resulting in two asymmetric Schottky junctions able to operate the detector at zero bias like a photodiode. Aiming at evaluating the detector suitability for radiotherapy applications we report on results related to signal dynamics, linearity with the dose and dose rate, signal stability and measurement repeatability determined in a Co-60 reference beam. In addition, we measured the detector sensitivity and its dependence on the applied bias voltage. The detector has a wide active volume leading to high current signal values. The signal dynamics is wide, with a dark current of 3.2 × 10⁻¹⁴ A at zero bias and a current of 6.8 × 10⁻¹⁰ A under irradiation with a dose rate of 0.95 Gy min⁻¹. The sensitivity to ionizing radiation increases with the bias voltage and values up to 10⁴ nC Gy⁻¹ mm⁻³ have been evaluated at −300 V. When operated at −5 V, the detector shows a linear response on a wide range of Co-60 dose rates from 1.3 × 10⁻³ Gy min⁻¹ to 1.2 Gy min⁻¹ following the Fowler's power law with a coefficient Δ = 0.99 ± 0.01. The device also shows rise and fall times of less than 1.0 s with a stability of the signal under irradiation better than 0.3%. The characteristics of the detector, as determined in the Co-60 beam, appear suitable for radiotherapy dosimetry, when fast response on the transient, wide signal dynamics, linearity and high sensitivity are required.     

A High-Efficiency MRI Contrast Agent as well as a Tumor Therapeutic Agent

Inorganic/polymercore/shell nanoparticles (NPs) for theranostics have always attracted research interest due to their flexible composition and facile synthesis. Here, core/shell NPs are prepared with gadolinium hydroxide nanorods cores and Mn ion-doped polydopamine shells. After PEG modification, the relaxation rate of Gd(OH)₃@MnPDA-PEG NRs achieved 35 s⁻¹mm ⁻¹. The characterization results indicate that the predoping Mn ions obviously promote the effect of MRI compared with the nanorods without or with postdoping Mn ions, and the predoping method can effectively control the actual doping account of metal ions. Considering the toxicity, dopamine and manganese in molar ratio of 8:1 is finally chosen. Gd(OH)₃@MnPDA-PEG nanorods are conducted in vivo and in vitro imaging and therapeutic experiments. The results show that the nanorods has low biological toxicity, excellent magnetic resonance imaging effects, clear photoacoustic imaging, and photothermal therapy effects.     

UV-illuminated chemical bath deposition of CdS buffer layer for CIGSSe solar cells

In this paper, we compare the performance of Cu(In,Ga)(S,Se)₂ (CIGSSe) thin film solar cells with a CdS buffer layer grown by chemical bath deposition (CBD) with UV irradiation of 365 nm or 254 nm at an output power of 8 W. The effects of UV light irradiation on the CBD-CdS thin film deposition mechanism were investigated through chemical and electro-optical studies. UV light irradiation during the solution process promotes the hydrolysis of thiourea, thereby inhibiting the formation of the intermediate products being developed on the reaction pathways and decreasing the solution pH. Therefore, the efficiency of the CdS/CIGSSe solar cells was improved because of the increased elemental ratio of S/(S + O) in the CdS thin film. This very simple and effective approach can be used to control the S/O ratio of the CdS thin film fabricated by the CBD process without artificially controlling the process temperature, solution pH or concentration.     

Size-controlled synthesis of superparamagnetic iron oxide nanoparticles and their surface coating by gold for biomedical applications

The size mono-dispersity, saturation magnetization, and surface chemistry of magnetic nanoparticles (NPs) are recognized as critical factors for efficient biomedical applications. Here, we performed modified water-in-oil inverse nano-emulsion procedure for preparation of stable colloidal superparamagnetic iron oxide NPs (SPIONs) with high saturation magnetization. To achieve mono-dispersed SPIONs, optimization process was probed on several important factors including molar ratio of iron salts [Fe³⁺ and Fe²⁺], the concentration of ammonium hydroxide as reducing agent, and molar ratio of water to surfactant. The biocompatibility of the obtained NPs, at various concentrations, was evaluated via MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay and the results showed that the NPs were non-toxic at concentrations <0.1 mg/mL. Surface functionalization was performed by conformal coating of the NPs with a thin shell of gold (∼4 nm) through chemical reduction of attached gold salts at the surface of the SPIONs. The Fe₃O₄ core/Au shell particles demonstrate strong plasmon resonance absorption and can be separated from solution using an external magnetic field. Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, phase components, core–shell surface composition, and magnetic properties have confirmed the formation of the mono-dispersed core–shell nanostructure.     

High surface area monodispersed Fe3O4 nanoparticles alone and on physical exfoliated graphite for improved supercapacitors

Highly conductive, unsophisticated and easy to be obtained physical exfoliated graphite (PHG) supporting well dispersed magnetite, Fe₃O₄/PHG nanocomposite, has been prepared by a one-step chemical strategy and physico-chemical characterized. The nanocomposite, favoured by the a-polar nanoparticles (NPs) capping, results in a self-assembled monolayer of monodispersed Fe₃O₄, covering perfectly the hydrophobic surfaces of PHG. The nanocomposite as an electrode material was fabricated into a supercapacitor and characterized by cyclic voltammetry (CV) and galvanostatic charge–discharge measurements. It shows, after a suitable annealing, significant electrochemical properties (capacitance value of 787 F/g at 0.5 A g⁻¹ and a Fe₃O₄/PHG weight ratio of 0.31) and good cycling stability (retention 91% after 30,000 cycles). Highly monodispersed very fine Fe₃O₄ NPs, covered by organic chains, have been also synthesized. The high surface area Fe₃O₄ NPs, after washing to leave a low content of organic chains able to avoid aggregation without excessively affecting the electrical properties of the material, exhibit remarkable pseudocapacitive activities, including the highest specific capacitance over reported for Fe₃O₄ (300 F/g at 0.5 A g⁻¹).     

Synthesis of PMA stabilized silver nanoparticles by chemical reduction process under a two-step UV irradiation

Poly(methacrylic acid) (PMA) stabilized silver nanoparticles (Ag NPs), also used in the surface modification of clothing fibers, were fabricated via chemical reduction processes under UV irradiation. To obtain an uniform size distribution it has been designed a new “two-step” process which employs two different UV radiation densities in order to control the kinetics of NPs nucleation. The as produced nanoparticles were characterized by UV-vis absorption spectroscopy and TEM microscopy. The results show the reduction of the Ag ions and the nanoparticles nucleation in the first step. In the second step, the final Ag NPs size distribution is controlled through a quick cross-linking of the PMA that freezes out any further modification. A narrow size distribution with more than 80% NPs smaller than 10 nm and none larger than 25 nm was obtained and the long-term stability (one month) of the colloidal solution was verified.     

Sonocatalytic degradation of EDTA in the presence of Ti and Ti@TiO2 nanoparticles

The sonocatalytic degradation of EDTA (C₀ = 5 10⁻³ M) in aqueous solutions was studied under 345 kHz (P_ac = 0.25 W mL⁻¹) ultrasound at 22–51 °C, Ar/20%O₂, Ar or air, and in the presence of metallic titanium (Ti⁰) or core-shell Ti@TiO₂ nanoparticles (NPs). Ti@TiO₂ NPs have been obtained using simultaneous action of hydrothermal conditions (100–214 °C, autogenic pressure P = 1.0–19.0 bar) and 20 kHz ultrasound, called sonohydrothermal (SHT) treatment, on Ti⁰ NPs in pure water. Ti⁰ is composed of quasi-spherical particles (30–150 nm) of metallic titanium coated with a metastable titanium suboxide Ti₃O. SHT treatment at 150–214 °C leads to the oxidation of Ti₃O and partial oxidation of Ti⁰ and formation of nanocrystalline shell (10–20 nm) composed of TiO₂ anatase. It was found that Ti⁰ NPs do not exhibit catalytic activity in the absence of ultrasound. Moreover, Ti⁰ NPs remain inactive under ultrasound in the absence of oxygen. However, significant acceleration of EDTA degradation was achieved during sonication in the presence of Ti⁰ NPs and Ar/20%O₂ gas mixture. Coating of Ti⁰ with TiO₂ nanocrystalline shell reduces sonocatalytic activity. Pristine TiO₂ anatase nanoparticles do not show a sonocatalytic activity in studied system. Suggested mechanism of EDTA sonocatalytic degradation involves two reaction pathways: (i) sonochemical oxidation of EDTA by OH/HO₂ radicals in solution and (ii) EDTA oxidation at the surface of Ti⁰ NPs in the presence of oxygen activated by cavitation event. Ultrasonic activation most probably occurs due to the local heating of Ti⁰/O₂ species at cavitation bubble/solution interface.