Anastasia V. Grigorieva

Iodobismuthates Containing One-Dimensional BiI4– Anions as Prospective Light-Harvesting Materials: Synthesis, Crystal and Electronic Structure, and Optical Properties

Four iodobismuthates, LiBiI4·5H2O (1), MgBi2I8·8H2O (2), MnBi2I8·8H2O (3), and KBiI4·H2O (4), were prepared by a facile solution route and revealed thermal stability in air up to 120 °C. Crystal structures of compounds 1-4 were solved by a single crystal X-ray diffraction method. 1: space group C2/c, a = 12.535(2), b = 16.0294(18), c = 7.6214(9) Å, β = 107.189(11)°, Z = 4, R = 0.029. 2: space group P21/c, a = 7.559(2), b = 13.1225(15), c = 13.927(4) Å, β = 97.14(3)°, Z = 2, R = 0.031. 3: space group P21/c, a = 7.606(3), b = 13.137(3), c = 14.026(5) Å, β = 97.14(3)°, Z = 2, R = 0.056. 4: space group P21/n, a = 7.9050(16), b = 7.7718(16), c = 18.233(4) Å, β = 97.45(3)°, Z = 4, R = 0.043. All solid state structures feature one-dimensional (BiI4)(-) anionic chains built of [BiI6] octahedra that share two opposite edges in such a fashion that two iodine atoms in cis-positions remain terminal. The calculated electronic structures and observed optical properties confirmed that compounds 1-4 are semiconductors with direct band gaps of 1.70-1.76 eV, which correspond to their intense red color. It was shown that the cations do not affect the optical properties, and the optical absorption is primarily associated with the charge transfer from the I 5p orbitals at the top of the valence band to the Bi 6p orbitals at the bottom of the conduction band. Based on their properties and facile synthesis, the title compounds are proposed as promising light-harvesting materials for all-solid solar cells.

Chemical tuning of adsorption properties of titanate nanotubes

A conventional hydrothermal method widely used for the preparation of titania-based nanotubes still generates many unsolved questions. One of them is definitely connected with the influence of a posthydrothermal treatment of titania nanotubes on their micromorphology, structure, and adsorption characteristics. Here, it was analyzed systematically by a group of methods including nitrogen adsorption and temperature-programmed desorption of ammonia and carbon dioxide. It is proved that adsorption characteristics and the surface state of titania nanotubes correlate with a sodium content, since sodium ions act as Lewis acid sites and shield Ti4+ acid sites of the nanotubes. To obey a balance between chemical and heat treatments of the nanotubes to design their functional properties has been suggested.

Synthesis of colloidal solutions of SrFe12O19 plate-like nanoparticles featuring extraordinary magnetic-field-dependent optical transmission

Hard-magnetic plate-like nanoparticles of SrFe12O19 were synthesised hydrothermally. The particles, fixed in a polymer, exhibited a coercivity in the range 0.9–1.8 kOe, and the saturation magnetization values reached 64 emu g−1. Electrostatically stabilized aqueous colloidal solutions of the plate-like particles with average thickness of 5–8 nm and average diameter of 30–80 nm were prepared. The nanoparticles readily oriented when applying a weak magnetic field as low as a few Oe, and due to the linear dichroism phenomena a strong change in the optical transmittance of the solution took place. The extinction coefficient ratio for the perpendicular and the parallel lights electric field vector relative to the magnetic field direction was found to be up to 4.5. The experimental results were compared with a theoretical model, in which the optical absorption of the nanoparticles was calculated from the polarizability of oblate ellipsoids.

Synthesis, structure, and properties of vanadium pentoxide nanotubes

Vanadium oxide nanotubes are synthesized by the hydrothermal method with the use of polycrystalline vanadium oxide V2O5 and 1-hexadecylamine as a structural template. The structure of the vanadium oxide nanotubes is investigated using small-angle X-ray diffraction and transmission electron microscopy. It is demonstrated that the structure of the vanadium oxide nanotubes is characterized by a combination of fragments with different interlayer distances associated with the twisting of oxide layers in the form of “nanorolls.” The thermal stability, morphology, and surface properties of the nanotubes, as well as the role of the organic template in the formation of their structure, are discussed.

Effect of preparation conditions on the ordering of structural elements in vanadium pentoxide xerogels

Vanadium(V) oxide xerogels with an ordered laminar structure are of considerable interest in modern inorganic chemistry [1]. They combine the ease of intercalation of inorganic ions [2] or organic molecules [3] into the interlayer space and the presence of a transition metal ions with variable oxidation states, giving rise to nonlinear electrical and, in some cases, magnetic characteristics. Hybrid inorganic‐organic materials based on xerogels of vanadium(V) oxide and its nanotubular forms [4] attract considerable attention due to their unique physical and unusual physicochemical and rheological properties, which enable their use as cathode materials for lithium batteries [5], chemical sensors [6], electrochromic materials [7], and catalysts [8]. Vanadium(V) oxide xerogels can be prepared by hydrolysis of organic derivatives of vanadic acid, by polycondensation of vanadates in an aqueous solution in an acid medium, and by decomposition of peroxovanadium(V) compounds upon dissolution of the crystalline oxide in hydrogen peroxide [1, 9, 11]. The mechanisms of these processes are essentially different; therefore, it is important to elucidate the structural features of the xerogels as a function of the preparation method. Small-angle X-ray scattering, which is a standard method for measuring the kinetics of gel condensation in solutions [10], can also be used rather efficiently to study the structural features of xerogels. This study reveals the correlation between the chemical prehistory and the structural organization of samples obtained. Complex analysis of small-angle X-ray scattering (SAXS) patterns of xerogel films synthesized by different methods was carried out for the first time and possible models for description of their structure were considered. Colloid solutions of vanadium(V) oxide for the formation of xerogel films were prepared by three procedures (table). According to method A, analytical grade crystalline V 2 O 5 (0.5 g) was dissolved in 15% H 2 O 2 (30 mL) by slow addition of V 2 O 5 powder to the hydrogen peroxide solution [11]. After the oxygen evolution ceased, the solution became yellow. Heating the solution to ~40°C gave a dark red solution, which was kept under ambient conditions for 7 days until a xerogel film formed. According to method B, the gel was obtained by hydrolysis of tert -butyl metavanadate VO(OC(CH 3 ) 3 ) 3 . The ester was synthesized [11] by refluxing a mixture of calcined vanadium(V) oxide with excess tert -butyl alcohol in the presence of a desiccant (silica gel) for 7 h. The resulting mixture was separated by distillation at 81°C . Hydrolysis was carried out by mixing the ester with an equal volume of water (an excess) for the preparation of bulk samples or under ambient conditions. In method C, polycondensation of V took place in an aqueous solution of sodium vanadate on acidification. A colloid solution of V 2 O 5 · n H 2 O was obtained by

From Isolated Anions to Polymer Structures through Linking with I2: Synthesis, Structure, and Properties of Two Complex Bismuth(III) Iodine Iodides

We report the synthesis, crystal structures, and optical properties of two new compounds, K18Bi8I42(I2)0.5·14H2O (1) and (NH4)7Bi3I16(I2)0.5·4.5H2O (2), as well as the electronic structure of the latter. They crystallize in tetragonal space group P4/ mmm with the unit cell parameters a = 12.974(1) and c = 20.821(3) Å for 1 and a = 13.061(3) and c = 15.162(7) Å for 2. Though 1 and 2 are not isomorphous, their crystal structures display the same structural organization; namely, the BiI6 octahedra are linked by I2 units to form disordered layers in 1 and perfectly ordered chains in 2. The I-I bond distances in the thus formed I-I-I-I linear links are not uniform; the central bond is only slightly longer than in a standalone I2 molecule, whereas the peripheral bonds are significantly shorter than longer bonds typical for various polyiodides, which is confirmed by Raman spectroscopy. The analysis of the electronic structure shows that the atoms forming the I-I-I-I subunits transfer electron density from their occupied 5p orbitals onto their vacant states as well as onto 6s orbitals of bismuth atoms that center the BiI6 octahedra. This leads to low direct band gaps that were found to be 1.57 and 1.27 eV for 1 and 2, respectively, by optical absorption spectroscopy. Luminescent radiative relaxation was observed in the near-IR region with emission maxima of 1.39 and 1.24 eV for 1 and 2, respectively, in good agreement with the band structure, despite the strong quenching propensity of I2 moieties.

The defining role of pH in the green synthesis of plasmonic gold nanoparticles using Citrus limon extract

The effect of pH on the growth pathways and final morphology of the plasmonic gold nanoparticles (AuNPs) synthesized using natural Citrus limon extract was in the spotlight. In acidic medium (pH 2.5–5), the growth of AuNPs is fast and involves an intermediate aggregation stage, whereas pH 7–9 results in much slower nucleation-growth route. The synthesis at pH 5 was shown to be the most appropriate for preparation of 8-nm gold nanospheres with narrow size distribution and amazingly bright surface plasmon resonance. The reported findings contribute to better understanding of the processes in “green” AuNP synthesis using C. limon extract and can promote its implementation in sustainable industry. Pronounced plasmonic properties and eco-friendly precursors of the AuNPs make them an essential material for biological tagging and cell visualization.

Correction: Inkjet printing of silver rainbow colloids for SERS chips with polychromatic sensitivity

Correction for ‘Inkjet printing of silver rainbow colloids for SERS chips with polychromatic sensitivity’ by K. E. Yorov et al., RSC Adv., 2016, 6, 15535–15540.

FM-AFM crossover in vanadium oxide nanomaterials

The magnetic properties of nanomaterials based on vanadium oxide (multiwall nanotubes, nanorods, and nanolayers) have been investigated in the temperature range of 1.8–220 K by high-frequency (60-GHz) EPR. A transition from a ferromagnetic temperature dependence to an antiferromagnetic temperature dependence has been observed in nanorods and nanotubes with a decrease in the temperature. The FM-AFM crossover observed near TC ∼ 110 K is accompanied by a low-temperature increase in the Curie constant by a factor of 2.7–7. The comparison of the experimental data for various VOx nanoparticles indicates that the most probable cause of the change in the type of magnetic interaction is a change in the concentration of V4+ magnetic ions.

Inkjet printing of silver rainbow colloids for SERS chips with polychromatic sensitivity

Pristine and artificially mixed silver colloids of diverse anisotropic silver nanoparticles were used as “rainbow” colloidal silver inks for inkjet printing of cellulose-based active elements with polychromatic sensitivity for surface-enhanced Raman spectroscopy optical sensors. Platelet silver nanocrystallites possessing different plasmonic bands in the visual spectral range were grown in water–polyol liquors of different viscosities to prevent nanoparticle agglomeration and provide colloidal stability for at least one year. SERS tests of model photostable dyes revealed bright enhanced signals under several standard wavelengths of laser irradiations thus demonstrating better practical applications of such substrates.