Inorganic Nanophase Research Articles

High Thermoelectric Performance of n-type BiTeSe-Based Composites Incorporated with Both Inorganic and Organic Nanoinclusions.

N-type Bi2Te2.7Se0.3 (BTS) alloy has relatively low thermoelectric performance as compared to its p-type counterpart, which restricts its widespread applications. Herein, we designed and prepared a novel composite system, which consists of an n-type BTS matrix incorporated with both inorganic and organic nanoinclusions. The results indicate that the thermopower of the composite samples can be enhanced by more than 19% upon incorporating inorganic nanophase AgBi3S5 (ABS) due to the energy-dependent carrier scattering, which ensures a high power factor. On the other hand, further incorporation of organic nanophase polypyrrole (PPy) can drastically reduce its lattice thermal conductivity owing to the strong scattering of mid- and low-frequency phonons at these nanoinclusions. As a result, high figures of merit ZTmax = 1.3 at 348 K and ZTave = 1.17 (300-500 K) are achieved with improved mechanical properties in BTS-based composites incorporated with 1.5 wt % ABS and 0.5 wt % PPy, demonstrating that the incorporation of both inorganic and organic nanoinclusions is an effective way to improve its thermoelectric performance.

Synthesis and DC Electrical Conductivity of Nanocomposites Based on Poly(1-vinyl-1,2,4-triazole) and Thermoelectric Tellurium Nanoparticles.

In this work, the structural characteristics and DC electrical conductivity of firstly synthesized organic-inorganic nanocomposites of thermoelectric Te0 nanoparticles (1.4, 2.8, 4.3 wt%) and poly(1-vinyl-1,2,4-triazole) (PVT) were analyzed. The composites were characterized by high-resolution transmission electron microscopy, X-ray diffractometry, UV-Vis spectroscopy, and dynamic light scattering analysis. The study results showed that the nanocomposite nanoparticles distributed in the polymer matrix had a shape close to spherical and an average size of 4-18 nm. The average size of the nanoparticles was determined using the Brus model relation. The optical band gap applied in the model was determined on the basis of UV-Vis data by the Tauc method and the 10% absorption method. The values obtained varied between 2.9 and 5.1 nm. These values are in good agreement with the values of the nanoparticle size, which are typical for their fractions presented in the nanocomposite. The characteristic sizes of the nanoparticles in the fractions obtained from the Pesika size distribution data were 4.6, 4.9, and 5.0 nm for the nanocomposites with percentages of 1.4, 2.8, and 4.3%, respectively. The DC electrical conductivity of the nanocomposites was measured by a two-probe method in the temperature range of 25-80 °C. It was found that the formation of an inorganic nanophase in the PVT polymer as well as an increase in the average size of nanoparticles led to an increase in the DC conductivity over the entire temperature range. The results revealed that the DC electrical conductivity of nanocomposites with a Tellurium content of 2.8, 4.3 wt% at 80 °C becomes higher than the conventional boundary of 10-10 S/cm separating dielectrics and semiconductors.

Chlorella vulgaris meets TiO2 NPs: Effective sorbent/photocatalytic hybrid materials for water treatment application

A new class of bio-nano hybrid catalyst useable in downstream wastewater treatment was developed. We combined the sorption potentialities of Chlorella vulgaris microalgae with the photocatalytic properties of TiO2 NPs in order to investigate unexplored synergistic effects that could push the algal remediation technology toward a more promising cost-effective balance. We exploited non-living C. vulgaris, which keeps the biosorption properties of the living microalgae, but greatly enhancing the overall processability.C. vulgaris biomass was coupled with TiO2 NPs and the nanosols were then dried by means of a spray freeze drying (SFD) process able to produce highly reactive granules. A widespread physicochemical characterization supported the preparation and the performance evaluation, so highlighting the key-role of C. vulgaris/TiO2 interaction at the colloidal state.Heavy metal adsorption, tested for copper ions, and photocatalytic activity, assessed for Rhodamine B (RhB) photodegradation, were evaluated as key performances. The results pointed out a positive synergistic effect for hybrid samples consistent with the enhancement of metal biosorption which ranges from 103 mg g−1, for pristine C. vulgaris, to about 4000 mg g−1, when the biomass was coupled with the inorganic nanophase. The photocatalytic activity was well preserved with a complete RhB conversion after 1 h and even advanced in presence of SiO2NPs into the inorganic counterpart, so increasing the kinetic constant from 8.70 to 10.7 10−2 min−1. The results pave the way for the integration of these sorbent/photocatalytic hybrid materials into water remediation systems in an innovative sustainable design perspective.

PH-dependent nanodiamonds enhance the mechanical properties of 3D-printed hyaluronic acid nanocomposite hydrogels

Nanocomposite hydrogels capable of undergoing manufacturing process have recently attracted attention in biomedical applications due to their desired mechanical properties and high functionality. 3D printing nanocomposite hydrogels of hyaluronic acid (HA)/nanodiamond (ND) revealed that the addition of ND with the low weight ratio of 0.02 wt% resulted in higher compressive force and gel breaking point, compared with HA only nanocomposites. These HA nanocomposite hydrogels loaded with surface functionalized ND allowed for the enforced compressive stress to be tuned in a pH-dependent manner. HA nanocomposite hydrogels with ND-OH at pH 8 showed an increase of 1.40-fold (0.02%: 236.18 kPa) and 1.37-fold (0.04%: 616.72 kPa) the compressive stress at the composition of 0.02 wt% and 0.04 wt, respectively, compared to those of ND-COOH (0.02%: 168.31 kPa, 0.04%: 449.59 kPa) at the same pH. Moreover, the compressive stress of HA/ND-OH (0.04 wt%) at pH 8 was mechanically enhanced 1.29-fold, compared to that of HA/ND-OH (0.04 wt%) at pH 7. These results indicate that the tunable buffering environment and interaction with the long chains of HA at the molecular level have a critical role in the dependency of the mechanical properties on pH. Due to the pH stability of the ND-OH nanophase, filament-based processing and layer-based deposition at microscale attained enforced mechanical properties of hydrogel. Fine surface tuning of the inorganic ND nanophase and controlled 3D printing leads to improved control over the pH-dependent mechanical properties of the nanocomposite hydrogels reported herein.

New Insights in the Ion Beam Sputtering Deposition of ZnO-Fluoropolymer Nanocomposites

Surface modification treatments able to confer antistain/antibacterial properties to natural or synthetic materials are receiving increasing attention among scientists. Ion beam co-sputtering (IBS) of zinc oxide (ZnO) and poly-tetrafluoroethylene (PTFE) targets allows for the preparation of novel multifunctional coatings composed of antimicrobial ZnO nanoparticles (NPs) finely dispersed in an antistain PTFE polymeric matrix. Remarkably, IBS has been proved to be successful in the controlled deposition of thin nanocoatings as an alternative to wet methods. Moreover, tuning IBS deposition parameters allows for the control of ZnONP loadings, thus modulating the antibacterial/antistain coating’s final properties. All the deposited coatings were fully characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and transmission electron microscopy (TEM) in order to obtain information on the materials’ surface composition, with deep insight into the nanocoatings’ morphology as a function of the ZnONP loadings. An analysis of high-resolution XP spectra evidenced a high degree of polymer defluorination along with the formation of inorganic fluorides at increasing ZnO volume ratios. Hence, post-deposition treatments for fluorides removal, performed directly in the deposition chamber, were successfully developed and optimized. In this way, a complete stoichiometry for inorganic nanophases was obtained, allowing for the conversion of fluorides into ZnO.

New bioactive bone-like microspheres with intrinsic magnetic properties obtained by bio-inspired mineralisation process

A bio-inspired mineralisation process was investigated and applied to develop novel hybrid magnetic materials by heterogeneous nucleation of Fe2+/Fe3+-doped hydroxyapatite nanocrystals onto a biopolymeric matrix made of a Type I collagen-based recombinant peptide (RCP). The effect of the synthesis temperature on the phase composition, crystallinity and magnetic properties of the nucleated inorganic phase was studied. The as-obtained magnetic materials were then engineered, by using a water-in-oil emulsification process, into hybrid magnetic microspheres, which were stabilized by de-hydrothermal treatment yielding cross-linking of the macromolecular matrix.Thorough investigation of the physicochemical, morphological and biological properties of the new hybrid microspheres, as induced by the presence of the inorganic nanophase and controlled iron substitution into hydroxyapatite lattice, revealed bone-like composition, good cytocompatibility, designed shape and size, and tailored magnetization. Such features are interesting and promising for application as new biomaterials with ability of remote activation and control by using external magnetic fields, for smart and personalized applications in medicine, particularly in bone tissue regeneration.

Scaffolds based on hyaluronan and carbon nanotubes gels.

Physico-chemical and mechanical properties of hyaluronic acid/carbon nanotubes nanohybrids have been correlated with the proportion of inorganic nanophase and the preparation procedure. The mass fraction of -COOH functionalized carbon nanotubes was varied from 0 to 0.05. Hyaluronic acid was crosslinked with divinyl sulfone to improve its stability in aqueous media and allow its handling as a hydrogel. A series of samples was dried by lyophilization to obtain porous scaffolds whereas another was room-dried allowing the collapse of the hybrid structures. The porosity of the former, together with the tighter packing of hyaluronic acid chains, results in a lower water absorption and lower mechanical properties in the swollen state, because of the easier water diffusion. The presence of even a small amount of carbon nanotubes (mass fraction of 0.05) limits even more the swelling of the matrix, owing probably to hybrid interactions. These nanohybrids do not seem to degrade significantly during 14 days in water or enzymatic medium.

Biomimetic nanosystems and novel composite nanobiomaterials

Biophysicochemical approaches to the solution of nanotechnology problems associated with the design of functional biomimetic nanosystems, hybrid and composite nanobiomaterials and study of their structure-function relationships. The results of studies concerned with physicochemical mechanisms of the formation of organized biomimetic nanostructures and bioinorganic nanomaterials in systems involving a bulky liquid phase and the interface (gas-liquid, solid-liquid, liquid-liquid) during the synthesis and structure formation with the participation of the components of colloid systems, inorganic nanoparticles of various composition and clusters of metals, surfactants, polyelectrolytes and their complexes are discussed. In the development of the methods for the formation of composite bioinorganic nanosystems containing inorganic nanocomponents, two major approaches were used: adsorption and incorporation into the biomolecular matrix or colloid system of presynthesized inorganic nanoparticles, as well as the synthesis of the inorganic nanophase immediately in the biomolecular system. The methods of obtaining biomaterials and nanosystems are based on the principles of biomimetics, biomineralization, self-assembly and self-organization, combination and integration of a number of synthetic and physicochemical methods (physical and chemical adsorption, Langmuir technique, the formation of polycomplexes, chemical linking, competitive interactions, and substitution of ligands in supramolecular and coordination complexes) and nanocomponents of different nature. In particular, a novel approach to the preparation of highly organized nanofilm materials was developed, which is based on the effect of self-assembly and self-organization of colloid nanoparticles during the formation of their complexes with polyfunctional biogenic ligands in the volume of the liquid phase in the absence of any surfaces and interfaces. The physical and chemical factors responsible for the formation of structurally ordered biomolecular and composite nanosystems including nano-sized components of different nature and the possibilities to control the composition, structure, and properties of resulting nanomaterials and nanosystems are discussed. The experimental methods and approaches developed may be useful in studies of structure-property relationships and basic mechanisms of structural organization and transformation at the nanoscales level in biological, artificial, and hybrid nanosystems. The problems of practical application of the synthetic methods and the corresponding nanomaterials are discussed.

Use of atomic force microscopy for imaging the initial stage of the nucleation of calcium phosphate in Langmuir–blodgett films of stearic acid

The nucleation of calcium phosphate on the substrate of steatic acid Langmuir–blodgett film at the initial stage was investigated by atomic force microscopy. Nano-dots, nano-wires and nano-islands were observed in sequence for the first time, reflecting the nucleation of calcium phosphate and the molecular arrangement of carboxylic layer. The nucleation rates perpendicular and parallel to the carboxylic terminal group were estimated from the height and diameter of the calcium phosphate crystals, respectively. And this stage was distinct from the late explosive grown stage, in which the change of the morphology was not obvious. The approaches based on this discovery would lead to the development of new strategies in the controlled synthesis of inorganic nano-phases and the assembly of organized composite and ceramic materials.

High-Temperature-Tolerant, Proton-Conducting Polytetramethylene Oxide/Zirconia Hybrid Membranes

Nanohybrid membrane of zirconia/polytetramethylene oxide synthesized by sol-gel processes was shown to possess flexible and temperature-tolerant properties. The polymeric membrane showed enhanced thermal stability up to 300°C due to the presence of cross-linkable inorganic nanophase in the hybrid macromolecular matrix. The membrane becomes proton-conducting polymer electrolyte when added with 12-phosphotungstic acid (PWA) or soaked by phosphoric acid. The proton-conducting properties of the hybrid membranes with various PWA or phosphoric acid concentrations were investigated in the temperature range from room temperature to 150°C under saturated humidity conditions. The flexible and large-sized hybrid polymer membrane has been found to have high proton conductivities from to under saturated humidity condition between 100 and 150°C. © 2004 The Electrochemical Society. All rights reserved.

Proton conducting polydimethylsiloxane/metal oxide hybrid membranes added with phosphotungstic acid(II)

Flexible polymer electrolyte membranes consisting of zirconia (titania) and polydimethylsiloxane (PDMS) with the different molecular mass of 4500 and 600 have been synthesized by sol–gel processes. The polymeric membranes showed thermal stability and flexibility up to 300 °C due to the presence of cross-linkable inorganic nano-phase in the hybrid macromolecular matrix. The membrane becomes proton conducting polymer electrolyte by addition of 12-phosphotungstic acid (PWA). The conductivity increased up to 7.7×10 −2 S/cm through ultrasonic treatment on the membrane, which is in the application level to polymer electrolyte fuel cells. The hybrid materials can be recognized as new, low cost and environment friendly electrolyte membranes.

Template-Assisted Growth of Nanowires Using Novel Nanoporous Films Fabricated by Inorganic Nano Phase Separation

AbstractUltrahigh pore density nanoporous films with a pore diameter of less than 10nm and a pore density exceeding 1016 pores/m2 were developed. Nano phase separation of a eutectic Al-Si system was used for the fabrication of these nanoporous films. Co-sputtered AlSi films form Al nano-cylinders, perpendicular to the substrate and parallel to each other, embedded in an amorphous Si matrix during film growth due to phase separation. Removal of the Al nano-cylinders from the co-sputtered AlSi films by chemical etching gives us ultrahigh pore density nanoporous films. The nanoporous films consist of mainly oxidized silicon. Depending on the film compositions and the film preparation conditions, such as RF power and the deposition temperature, the average pore diameter can be varied systematically from less than 5nm to 13nm with the pore density from 1015 to exceeding 1016 pores/m2. Furthermore we have demonstrated a template-assisted growth of ultrahigh-density Ni nanowire arrays with an aspect ratio of ∼100 in the nanoporous films by electrodeposition. The fabrication method for nanowire arrays using the nanoporous films is quite simple and promising for the fabrication of nanostructured devices.

Synthesis of binary polyelectrolyte/inorganic composite capsules of micron size

Different approaches for the synthesis of binary polyelectrolyte/inorganic layered composite capsules of micron size are described. As the polyelectrolyte part of the composite, a poly(styrene sulfonate)/poly(allylamine hydrochloride) complex was taken; the inorganic component was composed of magnetic nanoparticles (Fe3O4, CoFe2O4, MnFe2O4, ZnFe2O4), insulator nanoparticles (rare-earth fluorides) or metal nanoparticles (Ag). An inner inorganic layer was formed inside the hollow polyelectrolyte capsule via chemical or photochemical reaction in a spatially restricted capsule volume. The inorganic nanophase synthesized was characterized by transmission electron microscopy, scanning electron microscopy, and wide angle X-ray scattering techniques and weakly crystallized particles 6–9 nm in diameter were detected, presumably attached to the inner side of the capsule shell. Polyelectrolyte capsules filled with ferrite (magnetite) particles possess substantial magnetic activity and are easily manipulated in water solution by an external magnetic field.

Functionalized Europium Oxide Nanoparticles Used as a Fluorescent Label in an Immunoassay for Atrazine

A method for simply and cheaply preparing inorganic phosphor nanoparticles of Eu2O3 as labels in biology has been demonstrated with a simple microwave-assisted surface chemistry. The capping process adds a silane layer to the surface of the particles and provides amine groups that can be used for biological conjugation. The surface layer also protects the particles during conjugation chemistry. The particles retain their desirable optical properties that are typical of europium, that is, a spectrally narrow, red emission and a long fluorescence lifetime. The application of the nanoparticle labels in an immunoassay yields very good sensitivity in an immunoassay for atrazine (sub-parts-per-billion detection limit) without optimization of the detection system. The microwave functionalization technique will permit a broad range of inorganic nanophase phosphors to be used in high-throughput assays for environmental monitoring.

Proton Conducting Nano Hybrid Membranes Synthesized from Temperature Tolerant Polydimethylsiloxane (PDMS) Polymers

ABSTRACTFlexible and temperature tolerant nano-hybrid membranes consisting of zirconium (titanium) oxides and polydimethysiloxane (PDMS) with the different molecular mass of 4500 and 600 have been synthesized by sol-gel processes. The membrane of zirconium/PDMS=2 (in molar) showed enhanced thermal stability and flexibility up to 300 °C due to the presence of cross-linkable inorganic nano-phase in the hybrid macromolecular matrix. The membrane becomes proton conducting polymer electrolyte when doped with 12-phosphotungstic acid (PWA). The proton conducting properties of the hybrid membranes with various PWA concentration were measured in the temperature range from room temperature to 150°C under saturated humidity conditions. A maximum conductivity of 2×10-2 S/cm was obtained at 150°C when the PDMS/zirconium oxides hybrid matrix was changed to gel state due to the higher water activity at elevated temperatures.

Impact of natural nanophases on heavy-metal retention in zeolite-supported reactive filtration facilities for urban run-off treatment.

The retention of lead in zeolite-supported sand-filter columns has been tested with focus on the effect of potentially mobile natural nanophases (natural colloids, humic substances). It could be shown that interaction of lead with natural nanophases enhanced the mobility of the contaminant. In the presence of iron oxide particles (goethite) a normal breakthrough of lead was observed. Humic substance can act as a carrier for lead itself and can enhance the mobility of lead bound to inorganic nanophases, because of the increased mobility of the nanophases in the presence of humic substances.

Crystallization at Inorganic-organic Interfaces: Biominerals and Biomimetic Synthesis

Crystallization is an important process in a wide range of scientific disciplines including chemistry, physics, biology, geology, and materials science. Recent investigations of biomineralization indicate that specific molecular interactions at inorganic-organic interfaces can result in the controlled nucleation and growth of inorganic crystals. Synthetic systems have highlighted the importance of electrostatic binding or association, geometric matching (epitaxis), and stereochemical correspondence in these recognition processes. Similarly, organic molecules in solution can influence the morphology of inorganic crystals if there is molecular complementarity at the crystal-additive interface. A biomimetic approach based on these principles could lead to the development of new strategies in the controlled synthesis of inorganic nanophases, the crystal engineering of bulk solids, and the assembly of organized composite and ceramic materials.