A series of hybrid inorganic–organic niobates HCa2Nb3O10×ROH, containing n-alkoxy groups of primary alcohols (R = Me, Et, Pr, Bu, Hx, and Dc) grafted in the interlayer space, has been studied for the first time in relation to photocatalytic hydrogen generation from a model 1 mol % aqueous solution of methanol under ultraviolet irradiation. Photocatalytic activity was measured both for bare samples and for their composites with Pt nanoparticles as a cocatalyst. The advanced measurement scheme allowed monitoring the volume concentration of a sample in a suspension during the experiment, its pH, and possible exfoliation of layered compounds into nanolayers. In the series of n-alkoxy derivatives, the maximum rate of hydrogen evolution was achieved over a Pt-loaded ethoxy derivative HCa2Nb3O10×EtOH/Pt. Its apparent quantum efficiency of 20.6% in the 220–350 nm range was found not to be caused by changes in the light absorption region or specific surface area upon ethanol grafting. Moreover, the amounts of hydrogen released during the measurements significantly exceeded those of interlayer organic components, indicating that hydrogen is generated from the reaction solution rather than from the hybrid material.
Mixed-matrix membranes based on amorphous and semi-crystalline polyimides with zirconium dioxide (ZrO2) nanostars were synthesized. Amorphous poly(4,4′-oxydiphenylenepyromellitimide) and semi-crystalline polyimide prepared from 1,4-bis(4-aminophenoxy)benzene and 4,4’-oxydiphthalic anhydride were used. The effect of ZrO2 nanostars on the structure and morphology of nanocomposite membranes was studied by wide-angle X-ray scattering, scanning electron microscopy, atomic force microscopy, and contact angle measurements. Thermal properties and stability were investigated by thermogravimetric analysis and differential scanning calorimetry. Transport properties of hybrid membranes containing 5 wt % ZrO2 were tested for pervaporation of a mixture of butanol–water with 10 wt % H2O content. It was found that a significant amount of the ZrO2 added to the semi-crystalline polyimide is encapsulated inside spherulites. Therefore, the beneficial influence of inorganic filler on the selectivity of mixed-matrix membrane with respect to water was hampered. Mixed-matrix membranes based on amorphous polymer demonstrated the best performance, because water molecules had higher access to inorganic particles.
We present the results of a temperature-dependent photoluminescence (PL) spectroscopy study on CuInS2 quantum dots (QDs). In order to elucidate the influence of QD size on PL temperature dependence, size-selective precipitation was used to obtain several nanoparticle fractions. Additionally, the nanoparticles’ morphology and chemical composition were studied using transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The obtained QDs showed luminescence in the visible–near infrared range. The PL energy, linewidth, and intensity were studied within an 11–300 K interval. For all fractions, a temperature decrease led to a shift in the emission maximum to higher energies and pronounced growth of the PL intensity down to 75–100 K. It was found that for large particle fractions, the PL intensity started to decrease, with temperature decreasing below 75 K, while the PL intensity of small nanoparticles remained stable.
On the basis of pyromellitic dianhydride, p-phenylenediamine, and poly(butylene adipate) diol (Mn = 1 × 103) and poly(ethylene adipate) diol (Mn = 1 × 104) taken at a molar ratio of 10 : 1, initial samples of multiblock poly(ester imide) and its composites with nanoparticles of two types—zirconia ZrO2 surface-treated with γ-aminopropyltriethoxysilane and zirconia doped with yttria (Y0.03Zr0.97O1.985)—are synthesized. Nanoparticles are introduced into the polymer matrix at the stage of synthesis of the poly(ester imide) prepolymer. The mechanical properties of films of poly(ester imide) and its nanocomposites are determined under static and dynamic testing conditions, and the permeabilities and separation selectivities of corresponding solid films for mixtures of aromatic and aliphatic hydrocarbons (toluene-n-octane and benzenecyclohexane) of various compositions are measured under pervaporation testing conditions. It is shown that the different mechanical and pervaporation properties of film samples are due to the presence of zirconiabased nanoparticles.
1 January 2016 in International Journal of Nanotechnology
This study investigates the thermal and structural properties of multilayer composites based on chitosan (CS) and polyanions with different functionalities, including sodium sulfoethyl cellulose (SEC), sodium alginate (ALG), and sodium hyaluronate (HA). Unlike polyelectrolyte complexes (PECs) obtained by polymer mixing, the formation of a PEC layer by a process of layer-by-layer deposition of oppositely charged polymers is accompanied by the transformation of the CS polymorphic state, and this affects the relaxation and thermal properties of the resulting multilayer composite. X-ray diffraction analysis showed that the formation of the PEC layer in the CS/SEC multilayer film is accompanied by crystallization of the CS chains and the formation of a predominantly anhydrous CS modification. Thermogravimetric analysis of the CS/SEC film registers a high-temperature peak associated with the thermal decomposition of crystalline CS in the PEC composition. According to the dynamic mechanical analysis, the CS/SEC composite was characterized by a single glass transition temperature, indicating a strong interaction between the layers when using SEC (a strong acid salt) as the counterion to CS. For multilayer composites with weak polyacid salts (ALG and HA), the crystallization of CS in the PEC layer is weaker, as reflected in the thermal degradation of these films. A high-temperature peak is recorded in the thermal decomposition of CS/HA and is absent in the case of CS/ALG. Dynamic mechanical analysis of the CS/ALG composite showed two glass transition temperatures close to those of the original polymers, indicating weak PEC formation. The CS/HA composite showed an intermediate response. Thus, the effect of the PEC layer on the properties of the poly-layer composites decreases in the order CS/SEC > CS/HA > CS/ALG.