Polycrystalline CuInSe2 (CISe) nanorods are promising for the fabrication of highly efficient active layers in solar cells. In this work we report on a nanocasting approach, which uses track-etched polycarbonate films as hard templates for obtaining three-dimensionally (3D) arranged CISe nanorod arrays. Copper and indium ketoacidoximato complexes and selenourea were employed as molecular precursors. Arrays of parallel isolated cylindrical pores of 100 nm nominal diameter and 5 μm length were used for the infiltration of the precursor solution under inert atmosphere, followed by drying, thermal conversion into a preceramic ‘green body’, a subsequent dissolution of the template, and a final thermal treatment at 450 °C. The nanorods that where synthesised in this way have dimensions equal to the pore sizes of the template. Investigation of the CuInSe2 nanorod samples by spectroscopic and diffraction methods confirmed a high purity and crystallinity, and a stoichiometric composition of the CISe ternary semiconductor compound.
CIS; light absorption; nanocasting; nanorod arrays; precursor synthesis
Colemanite (Ca2B6O11·5H2O) is a natural and new precursor material for the synthesis of boron nitride nanotubes (BNNTs). BNNTs have been synthesized from unprocessed colemanite for the first time. The reaction parameters such as time, catalyst type, catalyst amount and temperature were optimized. It was found that the BNNT formation follows the base growth mechanism, which was initiated with a complex of boron nitride (BN) and iron atoms. The obtained BNNTs were characterized by using SEM, TEM, and spectroscopic techniques such as UV–vis, Raman, FTIR and XRD. The BNNTs were randomly oriented and multi-walled with an outer diameter of 10–30 nm and a wall thickness of 5 nm. This novel BNNT synthesis method can be used to obtain high yield, low cost and pure BNNTs.
boron nitride nanotube; chemical vapor deposition; colemanite; synthesis
Flower-like ZnO nanostructures were synthesized by a facile wet chemical method. Structural, optical and photocatalytic properties of these nanostructures have been studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) and UV–vis absorption spectroscopy. SEM and TEM studies revealed flower-like structures consisting of nanosheets, formed due to oriented attachment of ZnO nanoparticles. Flower-like ZnO structures showed enhanced photocatalytic activity towards sun-light driven photodegradation of methylene blue dye (MB) as compared to ZnO nanoparticles. XRD, UV–vis absorption, PL, FTIR and TEM studies revealed the formation of Zn(OH)2 surface layer on ZnO nanostructures upon ageing. We demonstrate that the formation of a passivating Zn(OH)2 surface layer on the ZnO nanostructures upon ageing deteriorates their efficiency to photocatalytically degrade of MB.
ageing; nanoparticles; nanosheets; photocatalysis; ZnO
In recent years, nanotechnology has gained significant interest for applications in the medical field. In this regard, a utilization of the ZnO nanoparticles for the efficient degradation of bilirubin (BR) through photocatalysis was explored. BR is a water insoluble byproduct of the heme catabolism that can cause jaundice when its excretion is impaired. The photocatalytic degradation of BR activated by ZnO nanoparticles through a non-radiative energy transfer pathway can be influenced by the surface defect-states (mainly the oxygen vacancies) of the catalyst nanoparticles. These were modulated by applying a simple annealing in an oxygen-rich atmosphere. The mechanism of the energy transfer process between the ZnO nanoparticles and the BR molecules adsorbed at the surface was studied by using steady-state and picosecond-resolved fluorescence spectroscopy. A correlation of photocatalytic degradation and time-correlated single photon counting studies revealed that the defect-engineered ZnO nanoparticles that were obtained through post-annealing treatments led to an efficient decomposition of BR molecules that was enabled by Förster resonance energy transfer.
bilirubin; Förster resonance energy transfer (FRET); neonatal jaundice; oxygen vacancy; photocatalysis; phototherapy; zinc oxide nanoparticles
This paper reports the structural and optical properties and comparative photocatalytic activity of TiO2 and Ag-doped TiO2 nanoparticles against different bacterial strains under visible-light irradiation. The TiO2 and Ag-doped TiO2 photocatalysts were synthesized by acid catalyzed sol–gel technique and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–vis spectroscopy and photoluminescence (PL). The XRD pattern revealed that the annealed sample of TiO2 has both anatase and rutile phases while only an anatase phase was found in Ag-doped TiO2 nanoparticles. The decreased band-gap energy of Ag-doped TiO2 nanoparticles in comparison to TiO2 nanoparticles was investigated by UV–vis spectroscopy. The rate of recombination and transfer behaviour of the photoexcited electron–hole pairs in the semiconductors was recorded by photoluminescence. The antimicrobial activity of TiO2 and Ag-doped TiO2 nanoparticles (3% and 7%) was investigated against both gram positive (Staphylococcus aureus) and gram negative (Pseudomonas aeruginosa, Escherichia coli) bacteria. As a result, the viability of all three microorganisms was reduced to zero at 60 mg/30 mL culture in the case of both (3% and 7% doping) concentrations of Ag-doped TiO2 nanoparticles. Annealed TiO2 showed zero viability at 80 mg/30 mL whereas doped Ag-TiO2 7% showed zero viability at 40 mg/30 mL culture in the case of P. aeruginosa only.
Ag-doped TiO2; antimicrobial activity; sol–gel
Herein, we present an approach for the rapid, straightforward and economical preparation of a tailored reactor device using three-dimensional (3D) printing, which can be directly linked to a high-resolution electrospray ionisation mass spectrometer (ESI-MS) for real-time, in-line observations. To highlight the potential of the setup, supramolecular coordination chemistry was carried out in the device, with the product of the reactions being recorded continuously and in parallel by ESI-MS. Utilising in-house-programmed computer control, the reactant flow rates and order were carefully controlled and varied, with the changes in the pump inlets being mirrored by the recorded ESI-MS spectra.
continuous parallel analysis; ESI-MS; 3D printing; reactionware; supramolecular chemistry
Four novel organotin(IV) complexes containing phosphoric triamide ligands were synthesized and characterized by multinuclear (1H, 31P, 13C) NMR, infrared, ultraviolet and fluorescence spectroscopy as well as elemental analysis. The 1H NMR spectra of complexes 1–4 proved that the Sn atoms adopt octahedral configurations. The nanoparticles of the complexes were also prepared by ultrasonication, and their SEM micrographs indicated identical spherical morphologies with particles sizes about 20–25 nm. The fluorescence spectra exhibited blue shifts for the maximum wavelength of emission upon complexation.
luminescence; nanoparticles; organotin(IV) complexes; phosphoric triamide; ultrasonic
Nanostructure-decorated n-type semiconductor interfaces are studied in order to develop chemical sensing with nanostructured materials. We couple the tenets of acid/base chemistry with the majority charge carriers of an extrinsic semiconductor. Nanostructured islands are deposited in a process that does not require self-assembly in order to direct a dominant electron-transduction process that forms the basis for reversible chemical sensing in the absence of chemical-bond formation. Gaseous analyte interactions on a metal-oxide-decorated n-type porous silicon interface show a dynamic electron transduction to and from the interface depending upon the relative strength of the gas and metal oxides. The dynamic interaction of NO with TiO2, SnO2, NiO, CuxO, and AuxO (x >> 1), in order of decreasing acidity, demonstrates this effect. Interactions with the metal-oxide-decorated interface can be modified by the in situ nitridation of the oxide nanoparticles, enhancing the basicity of the decorated interface. This process changes the interaction of the interface with the analyte. The observed change to the more basic oxinitrides does not represent a simple increase in surface basicity but appears to involve a change in molecular electronic structure, which is well explained by using the recently developed IHSAB model. The optical pumping of a TiO2 and TiO2−
xNx decorated interface demonstrates a significant enhancement in the ability to sense NH3 and NO2. Comparisons to traditional metal-oxide sensors are also discussed.
chemical sensors; gas interface interactions; IHSAB theory; nitrated oxides; porous silicon
Monitoring emissions in high-temperature-combustion applications is very important for regulating the discharge of gases such as NO2 and CO as well as unburnt fuel into the environment. This work reports the detection of H2 and CO gases by employing a metal–metal oxide nanocomposite (gold–yttria stabilized zirconia (Au–YSZ)) film fabricated through layer-by-layer physical vapor deposition (PVD). The change in the peak position of the localized surface plasmon resonance (LSPR) was monitored as a function of time and gas concentration. The responses of the films were preferential towards H2, as observed from the results of exposing the films to the gases at temperatures of 500 °C in a background of dry air. Characterization of the samples by XRD and SEM enabled the correlation of material properties with the differences in the CO- and H2-induced LSPR peak shifts, including the relative desensitization towards NO2. Sensing characteristics of films with varying support thicknesses and metal-particle diameters have been studied, and the results are presented. A comparison has been made to films fabricated through co-sputtered PVD, and the calibration curves of the sensing response show a preferential response towards H2. The distinction between H2 and CO responses is also seen through the use of principal-component analysis (PCA). Such material arrangements, which can be tuned for their selectivity by changing certain parameters such as particle size, support thickness, etc., have direct applications within optical chemical sensors for turbine engines, solid-oxide fuel cells, and other high-temperature applications.
hydrogen detection; nanocomposites gold nanoparticles; optical sensor; plasmonics; physical vapor deposition; surface plasmon resonance
Paper with antimicrobial properties was developed through in situ growth of ZnO nanorods. The targeted application for this type of paper is in health centers as wallpaper, writing paper, facemasks, tissue paper, etc. The paper was tested on three model microbes, Gram-positive bacteria Staphylococcus aureus, Gram-negative bacteria Escherichia coli and common airborne fungus Aspergillus niger. No viable bacterial colonies or fungal spores could be detected in the areas surrounding test samples of the antimicrobial paper. Gram-negative bacteria Escherichia coli were found to be inhibited in an area that is 239% and 163% the area of the paper sample under different room lighting conditions, i.e., halogen and fluorescent lamp illumination, respectively. For Gram-positive bacteria Staphylococcus aureus the zones of inhibition surrounding the paper samples are 102% and 70%, and for Aspergillus niger, 224% and 183% of the sample area, under similar lighting conditions.
antimicrobial; nanorod; paper; photocatalysis; zinc oxide
In a proof-of-concept study we demonstrate in situ reaction monitoring of DeNOx-SCR on proton-conducting zeolites serving as catalyst and gas sensor at the same time. By means of temperature-dependent impedance spectroscopy we found that the thermally induced NH3 desorption in H-form and in Fe-loaded zeolite H-ZSM-5 follow the same process, while a remarkable difference under DeNOx-SCR reaction conditions was found. The Fe-loaded catalyst shows a significantly lower onset temperature, and time-dependent measurements suggest different SCR reaction mechanisms for the two catalysts tested. These results may help in the development of catalysts for the reduction of NOx emissions and ammonia consumption, and provide insight into the elementary catalytic process promoting a full description of the NH3-SCR reaction system.
DeNOx-SCR; gas sensing; in situ; impedance spectroscopy; zeolite
In this work the applicability of neopentasilane (Si(SiH3)4) as a precursor for the formation of silicon nanowires by using gold nanoparticles as a catalyst has been explored. The growth proceeds via the formation of liquid gold/silicon alloy droplets, which excrete the silicon nanowires upon continued decomposition of the precursor. This mechanism determines the diameter of the Si nanowires. Different sources for the gold nanoparticles have been tested: the spontaneous dewetting of gold films, thermally annealed gold films, deposition of preformed gold nanoparticles, and the use of “liquid bright gold”, a material historically used for the gilding of porcelain and glass. The latter does not only form gold nanoparticles when deposited as a thin film and thermally annealed, but can also be patterned by using UV irradiation, providing access to laterally structured layers of silicon nanowires.
chemical vapor deposition; gold; nanoparticle; patterning; radiation-induced nanostructures; vapor-liquid-solid mechanism
Nanocrystalline lead selenide (PbSe) thin films were prepared on glass substrates by a chemical bath deposition method, using sodium selenosulfate (Na2SeSO3) as a source of Se2− ions, and lead acetate as a source of Pb2+ ions. Trisodium citrate (TSC) was used as a complexing agent. PbSe films were prepared at various deposition temperatures while the pH value was kept fixed at 11, and the effect on the resulting film properties was studied by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM) and optical absorption studies. The structural parameters, such as the lattice constant (a), crystallite size (D), dislocation density (ρ) and microstrain (ε) were evaluated from the XRD spectra. It was found that average crystallite size, as calculated from Scherrer’s formula, increased from 23 to 33 nm as the deposition temperature was varied from 303 to 343 K. The dislocation density and microstrain were found to vary inversely with the crystallite size, whereas the lattice constant was found to increase with an increase in crystallite size. The optical absorption spectra of the nanocrystalline PbSe films showed a blue shift, and the optical band gap (E
) was found to increase from 1.96 to 2.10 eV with the decrease in crystallite size.
chemical bath deposition; lattice parameter; lead selenide; Nelson–Riley plot; optical absorption
Periodic mesoporous materials of the type (R′O)3Si-R-Si(OR′)3 with benzene as an organic bridge and a crystal-like periodicity within the pore walls were functionalized with SO3H or SO3
− groups and investigated by small-angle neutron scattering (SANS) with in situ nitrogen adsorption at 77 K. If N2 is adsorbed in the pores the SANS measurements show a complete matching of all of the diffraction signals that are caused by the long-range ordering of the mesopores in the benzene-PMO, due to the fact that the benzene-PMO walls possess a neutron scattering length density (SLD) similar to that of nitrogen in the condensed state. However, signals at higher q-values (>1 1/Å) are not affected with respect to their SANS intensity, even after complete pore filling, confirming the assumption of a crystal-like periodicity within the PMO material walls due to π–π interactions between the organic bridges. The SLD of pristine benzene-PMO was altered by functionalizing the surface with different amounts of SO3H-groups, using the grafting method. For a low degree of functionalization (0.81 mmol SO3H·g−1) and/or an inhomogeneous distribution of the SO3H-groups, the SLD changes only negligibly, and thus, complete contrast matching is still found. However, for higher amounts of SO3H-groups (1.65 mmol SO3H·g−1) being present in the mesopores, complete matching of the neutron diffraction signals is no longer observed proving that homogeneously distributed SO3H-groups on the inner pore walls of the benzene-PMO alter the SLD in a way that it no longer fits to the SLD of the condensed N2.
contrast matching; crystal-like periodicity; distribution of functional groups; PMO; SANS; surface functionalization
Silver nanoparticles were synthesized by an enzyme-induced growth process on solid substrates. In order to customize the enzymatically grown nanoparticles (EGNP) for analytical applications in biomolecular research, a detailed study was carried out concerning the time evolution of the formation of the silver nanoparticles, their morphology, and their chemical composition. Therefore, silver-nanoparticle films of different densities were investigated by using scanning as well as transmission electron microscopy to examine their structure. Cross sections of silver nanoparticles, prepared for analysis by transmission electron microscopy were additionally studied by energy-dispersive X-ray spectroscopy in order to probe their chemical composition. The surface coverage of substrates with silver nanoparticles and the maximum particle height were determined by Rutherford backscattering spectroscopy. Variations in the silver-nanoparticle films depending on the conditions during synthesis were observed. After an initial growth state the silver nanoparticles exhibit the so-called desert-rose or nanoflower-like structure. This complex nanoparticle structure is in clear contrast to the auto-catalytically grown spherical particles, which maintain their overall geometrical appearance while increasing their diameter. It is shown, that the desert-rose-like silver nanoparticles consist of single-crystalline plates of pure silver. The surface-enhanced Raman spectroscopic (SERS) activity of the EGNP structures is promising due to the exceptionally rough surface structure of the silver nanoparticles. SERS measurements of the vitamin riboflavin incubated on the silver nanoparticles are shown as an exemplary application for quantitative analysis.
EGNP; enzymatically grown silver nanoparticles; enzyme-induced deposition; nanoflower; SERS
This work describes a general method for the preparation of salt nanoparticles (NPs) made from an aqueous solution of ionic compounds (NaCl, CuSO4 and KI). These nanoparticles were created by the application of ultrasonic waves to the aqueous solutions of these salts. When the sonication was carried out in the presence of a glass microscope slide, a parylene-coated glass slide, or a silicon wafer the ionic NPs were embedded in these substrates by a one-step, ultrasound-assisted procedure. Optimization of the coating process resulted in homogeneous distributions of nanocrystals, 30 nm in size, on the surfaces of the substrates. The morphology and structure of each of the coatings were characterized by physical and chemical methods, such as X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). After 24 h of leaching into water the nanoparticles of the inorganic salts were still present on the slides, and complete leaching of nanoparticles occurred only after 96 h. A mechanism of the ultrasound-assisted coating is proposed.
deposition; ionic salt nanoparticles; parylene; sonochemistry
Ordered mesoporous, crystalline MgTa2O6 thin films with a mesoscopic nanoarchitecture were synthesized by evaporation-induced self-assembly (EISA) in combination with a sol–gel procedure. Utilization of novel templates, namely the block copolymers KLE (poly(ethylene-co-butylene)-b-poly(ethylene oxide)) and PIB6000 (CH3C(CH3)2(CH2C(CH3)2)107CH2C(CH3)2C6H4O(CH2CH2O)100H), was the key to achieving a stable ordered mesoporous structure even upon crystallization of MgTa2O6 within the mesopore walls. The effect of the calcination temperature on the ability of the mesoporous films to assist the photodegradation of rhodamine B in water was studied. As a result, two maxima in the photocatalytic activity were identified in the calcination temperature range of 550–850 °C, peaking at 700 °C and 790 °C, and the origin of this was investigated by using temperature-dependent X-ray scattering. Optimal activity was obtained when the mesoporous film was heated to 790 °C; at this temperature, crystallinity was significantly high, with MgTa2O6 nanocrystals of 1.6 nm in size (averaged over all reflections), and an ordered mesoporous structure was maintained. When considering the turnover frequency of such photocatalysts, the optimized activity of the present nanoarchitectured MgTa2O6 thin film was ca. four times that of analogous anatase TiO2 films with ordered mesopores. Our study demonstrated that high crystallinity and well-developed mesoporosity have to be achieved in order to optimize the physicochemical performance of mesoporous metal-oxide films.
magnesium tantalate; mesoporous materials; photocatalytic activity; self-assembly; thin films
In order to enhance the resistance of cobalt nanoparticles to oxidation in air, the impact of different stabilization strategies on the isothermal oxidation of particle dispersions and powders was kinetically investigated and compared to as-prepared particle preparations. A post-synthesis treatment with different alcohols was employed, and we also investigate the influence of two different polymer shells on the oxidation process. We found a parabolic decrease of the magnetization for all particle charges, indicating that the process is dominated by a diffusion of oxygen to the cobalt core and a radial growth of the oxide layer from the particle surface to the core. A significant deceleration of the oxidation process was observed for all alcohol-passivated particle preparations, and this resulted finally in a stagnation effect. The stabilizing effect increases in the sequence Co@OA/MeOH < Co@OA/EtOH < Co@OA/iPrOH. For polymer-coated particle preparations Co@PCL and Co@PS, the deceleration was even more pronounced. The results demonstrate that cobalt nanoparticles can effectively be protected against oxidation in order to improve their mid- to longterm stability.
cobalt nanoparticles; core–shell particles; isothermal oxidation; nanoscale passivation; parabolic rate constant
Polymethylmethacrylate (PMMA)/ceria composite fibres were synthesized by using a sequential combination of polymer electrospinning, spray-coating with a sol, and a final calcination step to yield microstructured ceria tubes, which are composed of nanocrystalline ceria particles. The PMMA template is removed from the organic/inorganic hybrid material by radio frequency (rf) plasma etching followed by calcination of the ceramic green-body fibres. Microsized ceria (CeO2) tubes, with a diameter of ca. 0.75 µm, composed of nanocrystalline agglomerated ceria particles were thus obtained. The 1-D ceramic ceria material was characterized by X-ray diffraction, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), UV–vis and photoluminescence spectroscopy (PL), as well as thermogravimetric analysis (TGA). Its catalytic performance was studied in the direct carboxylation of methanol with carbon dioxide leading to dimethyl carbonate [(CH3O)2CO, DMC], which is widely employed as a phosgene and dimethyl sulfate substitute, and as well as a fuel additive.
activation of CO2; ceria; electrospinning; exotemplating; nanotubes
In the last decade, research concerning nanoporous siliceous materials has been focused on mesoporous materials with intrinsic zeolitic features. These materials are thought to be superior, because they are able to combine (i) the enhanced diffusion and accessibility for larger molecules and viscous fluids typical of mesoporous materials with (ii) the remarkable stability, catalytic activity and selectivity of zeolites. This review gives an overview of the state of the art concerning combined zeolitic/mesoporous materials. Focus is put on the synthesis and the applications of the combined zeolitic/mesoporous materials. The different synthesis approaches and formation mechanisms leading to these materials are comprehensively discussed and compared. Moreover, Ti-containing nanoporous materials as redox catalysts are discussed to illustrate a potential implementation of combined zeolitic/mesoporous materials.
catalysis; characterization; combined zeolitic/mesoporous materials; synthesis
Mass-selected, ligand-free FeN clusters with N = 10–30 atoms (cluster diameter: 0.6–0.9 nm) were implanted into [Al@SiOx] surfaces at a low surface coverage corresponding to a few thousandths up to a few hundredths of a monolayer in order to avoid initial cluster agglomeration. These studies are aimed towards gaining an insight into the lower limit of the size regime of carbon nanotube (CNT) growth by employing size-selected sub-nm iron clusters as catalyst or precatalyst precursors for CNT growth. Agglomeration of sub-nm iron clusters to iron nanoparticles with a median size range between three and six nanometres and the CNT formation hence can be observed at CVD growth temperatures of 750 °C. Below 600 °C, no CNT growth is observed.
carbon nanotubes; CNT growth; metal clusters; size selected clusters
We describe the formation of SiC nanopowder using an atmospheric argon microwave plasma with tetramethylsilane (TMS) as precursor. The impact of several process conditions on the particle size of the product is experimentally investigated. Particles with sizes ranging from 7 nm to about 20 nm according to BET and XRD measurements are produced. The dependency of the particle size on the process parameters is evaluated statistically and explained with growth-rate equations derived from the theory of Ostwald ripening. The results show that the particle size is mainly influenced by the concentration of the precursor material in the plasma.
atmospheric microwave plasma; nanoparticle; SiC
For the first time we present the synthesis of CeO2/Si(O)C core–shell particles prepared by the miniemulsion technique. The Si(O)C core was obtained by means of a polycarbosilane precursor (SMP10), which was subsequently functionalized with ceria and pyrolyzed to the ceramic. The size of these particles could easily be adjusted by varying the surfactants and the surfactant concentration, or by the addition of comonomers. Hence particle sizes ranged from 100 to 1000 nm, tunable by the preparation conditions. All materials were characterized by photon cross correlation spectroscopy, scanning electron microscopy and elemental mapping investigations. Furthermore, first catalytic tests were carried out by temperature programmed oxidation (TPO) of methane, and the activity of this material in lowering the onset temperature of methane combustion by 262 K was documented.
ceria; cerium dioxide; core shell; miniemulsion; oxycarbide; silicon carbide; TPO catalytic
Hexagonal molybdenum oxide (h-MoO3) was synthesized by a solution based chemical precipitation technique. Analysis by X-ray diffraction (XRD) confirmed that the as-synthesized powder had a metastable hexagonal structure. The characteristic vibrational band of Mo–O was identified from Fourier transform infrared spectroscopy (FT-IR). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images clearly depicted the morphology and size of h-MoO3. The morphology study showed that the product comprises one-dimensional (1D) hexagonal rods. From the electron energy loss spectroscopy (EELS) measurement, the elemental composition was investigated and confirmed from the characteristic peaks of molybdenum and oxygen. Thermogravimetric (TG) analysis on metastable MoO3 revealed that the hexagonal phase was stable up to 430 °C and above this temperature complete transformation into a highly stable orthorhombic phase was achieved. The optical band gap energy was estimated from the Kubelka–Munk (K–M) function and was found to be 2.99 eV. Finally, the ethanol vapor-sensing behavior was investigated and the sensing response was found to vary linearly as a function of ethanol concentration in the parts per million (ppm) range.
fiber optic sensor; hexagonal phase; molybdenum oxide; one dimensional rod; phase transition