Oxidative dehydrogenation of 2,3,5-trimethyl-1,4-hydroquinone in the presence of titanium dioxide hydrogel

Liquid-phase oxidative dehydrogenation of 2,3,5-trimethyl-1,4-hydroquinone in the presence of titanium dioxide hydrogel was studied by a kinetic method. Associative interactions between the substrate, oxidant, and gel were detected by voltammetry and ESR and IR spectroscopy.Russian Foundation for Basic Researc

Dimerization and low-dimensional magnetism in nanocrystalline TiO2 semiconductors doped by Fe and Co

The report is devoted to an analysis of the structural and magnetic state of the nanocrystalline diluted magnetic semiconductors based on TiO2 doped with Fe and Co atoms. Structural and magnetic characterization of samples was carried out using X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR) spectroscopy, SQUID magnetometry, and the density functional theory (DFT) calculations. Analysis of the experimental data suggests the presence of non-interacting paramagnetic Fe3+ and Co2+ ions in the high-spin state and negative exchange interactions between them. The important conclusions is that the distribution of dopants in the TiO2 matrix, even at low concentrations of 3d-metal dopant (less than one percent), is not random, but the 3d ions localization and dimerization is observed both on the surface and in the nanoparticles core. Thus, in the paper the quantum mechanical model for describing the magnetic properties of TiO2:(Fe, Co) was suggested. The model operates only with two parameters: paramagnetic contribution of non-interacting 3d-ions and dimers having different exchange interactions between 3d magnetic carriers. © Published under licence by IOP Publishing Ltd

Unconventional magnetism of non-uniform distribution of Co in TiO2 nanoparticles

High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) analysis, electron paramagnetic resonance (EPR), X-ray absorption spectroscopy (XAS), magnetic methods, and density-functional theory (DFT) calculations were applied for the investigations of Co-doped anatase TiO2 nanoparticles (∼20 nm). It was found that high-spin Co2+ ions prefer to occupy the interstitial positions in the TiO2 lattice which are the most energetically favourable in compare to the substitutional those. A quantum mechanical model which operates mainly on two types of Co2+ – Co2+ dimers with different negative exchange interactions and the non-interacting paramagnetic Co2+ ions provides a satisfactorily description of magnetic properties for the TiO2:Co system. © 2020 Elsevier B.V.Russian Foundation for Basic Research. Ministry of Science and Higher Education of the Russian Federatio

Synthesis of Cu(II)-containing TiO2-SiO2 binary xerogels by hydrolysis of a mixture of tetrabutoxytitanium, tetraethoxysilane, and copper(II) chloride in a water-ammonia atmosphere

A Cu(II)-containing binary xerogel TiO2-SiO2 was synthesized by joint hydrolysis of tetrabutoxytitanium, teraethoxysilane and copper(II) chloride dissolved in their mixture. The synthesis was performed in a vapor of 10% aqueous ammonia under static conditions. EPR spectroscopy was used to examine the state of Cu(II) in the xerogel matrix. Data on specific features of the behavior of saccharose within xerogel pores under heating were obtained. The catalytic activity of the xerogel was tested by the kinetic method on model reactions of hydrogen peroxide decomposition and oxidative dehydrogenation of trimethylhydroquinone. © 2013 Pleiades Publishing, Ltd

Magnetic properties and structure of TiO2-Mn (0.73 %) nanopowders: The effects of electron irradiation and vacuum annealing

Nanopowder TiO2-0.73 % Mn was synthesized by the sol-gel method. Thermal treatment of the samples was carried out in vacuum at a temperature of 500°C. Magnetic properties were studied in the temperature range from 2 to 850 K. The effects of electron irradiation and vacuum annealing on the EPR spectra and magnetic properties of TiO2-Mn powder are discussed. It was established that a part of manganese ions in the anatase crystal lattice interacts antiferromagnetically, which causes a decrease in magnetization as compared to the result of the calculation for non-interacting ions. Vacuum annealing leads to the formation of oxygen vacancies and, at the same time, to a noticeable increase in the ferromagnetic contribution to magnetization, especially, after preliminary electron irradiation. We assume that the ferromagnetic contribution to the magnetization appears either due to incomplete compensation of antiferromagnetically directed moments of manganese ions, or due to positive exchange interactions of Mn ions via defects in the TiO2 lattice. It is shown that the temperature of magnetic disordering in samples with a spontaneous magnetic moment exceeds 600°C. © 2019, Institute for Metals Superplasticity Problems of Russian Academy of Sciences. All rights reserved

Dimerization and low-dimensional magnetism in nanocrystalline TiO2 semiconductors doped by Fe and Co

The report is devoted to an analysis of the structural and magnetic state of the nanocrystalline diluted magnetic semiconductors based on TiO2 doped with Fe and Co atoms. Structural and magnetic characterization of samples was carried out using X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR) spectroscopy, SQUID magnetometry, and the density functional theory (DFT) calculations. Analysis of the experimental data suggests the presence of non-interacting paramagnetic Fe3+ and Co2+ ions in the high-spin state and negative exchange interactions between them. The important conclusions is that the distribution of dopants in the TiO2 matrix, even at low concentrations of 3d-metal dopant (less than one percent), is not random, but the 3d ions localization and dimerization is observed both on the surface and in the nanoparticles core. Thus, in the paper the quantum mechanical model for describing the magnetic properties of TiO2:(Fe, Co) was suggested. The model operates only with two parameters: paramagnetic contribution of non-interacting 3d-ions and dimers having different exchange interactions between 3d magnetic carriers. © Published under licence by IOP Publishing Ltd

Magnetism and temperature dependence of nano-TiO2: Fe EPR spectra

Nanocrystalline TiO2 samples of various compositions (up to 5 at.% Fe) with anatase structure and an average particle size of about 20 nm were synthesized using sol-gel technology. The magnetic properties of nano-TiO2: Fe was studied by electron paramagnetic resonance (EPR) and Faraday balance. The existence of an inhomogeneous magnetic state in TiO2: Fe samples of different compositions were revealed by EPR spectroscopy in a wide temperature range. The analysis of the EPR spectra in the L -, X - and Q-bands allowed us to calculate the quadratic fine structure (D, E) parameters, “axial” and “rhombic” ones, respectively. The value of D turned out to be quite small, which indicates an insignificant anisotropy, which can be ignored describing the magnetic properties of TiO2:Fe. It was shown that the temperature behavior of different separate components of the integral EPR spectra can be qualitatively interpreted in the model of coexistence in the TiO2: Fe system, mainly, dimers with a strong negative exchange interaction and isolated paramagnetic centers. No ferromagnetic state in TiO2: Fe-based samples after etching of aE-prepared state were detected. © 202

Electrostatic properties of inner nanopore surfaces of anodic aluminum oxide membranes upon high temperature annealing revealed by EPR of pH-sensitive spin probes and labels

Anodic aluminum oxide (AAO) membranes are versatile nanomaterials that combine the chemically stable and mechanically robust properties of ceramics with homogeneous nanoscale organization that can be tuned to desirable pore diameters and lengths. The AAO substrates feature high surface area that is readily accessible to large and small molecules, making these nanostructures uniquely suited for many possible applications. Examples include templated self-assembly of macroscopically aligned biological membranes and substrates for heterogeneous catalysis. For further development of such applications, one would like to characterize and tune the electrostatic properties of the inner pore surface as well as the local acidity within the nanochannels. Here, we employed electron paramagnetic resonance (EPR) spectroscopy of a small molecule – ionizable nitroxide – as a reporter of the average local acidity in the nanochannels and the local electrostatic potential in the immediate vicinity of the pore surface. The former was achieved by measuring EPR spectra of this molecular probe diffusing in an aqueous phase confined in the AAO nanochannels while for the latter the nitroxide was covalently attached to the hydroxyl group of the alumina surface. We show that the local acidity within the nanochannels is increased by as much as ≈1.48 pH units vs. the pH of bulk solution by decreasing the pore diameter down to ca. 31 nm. Furthermore, the positive surface charge of the as-prepared AAO could be decreased and even switched to a negative surface charge upon annealing the membranes first to 700 °C and then to 1200 °C. For as-prepared AAO, the local electrostatic potential reaches ψ= (163 ± 5) mV for the nitroxide label covalently attached to AAO and located about 0.5 nm away from the surface. Overall, we demonstrate that the acid-based properties of the aqueous volume confined by the AAO nanopores pores can be tuned by either changing the pore diameter from ca. 71 to 31 nm or by thermal annealing to switch the sign of the surface charge. These observations provide a simple and robust means to tailor these versatile high-surface-area nanomaterials for specific applications that depend on acid-base equilibria. © 2020 Elsevier B.V.Russian Foundation for Basic Research. Government Council on Grants, Russian Federation. U.S. Department of Energy. Ministry of Science and Higher Education of the Russian Federation. National Science Foundation. North Carolina State Universit

MAGNETISM AND EPR OF COBALT-DOPED TIO2 NANOPOWDERS, IN VARIOUS TREATMENTS

The existence of different nature defects and carriers of a magnetic moment, based on Ti3+ or Co2+ on the surface of a nanoparticle, is a necessary condition for the realization of exchange interactions leading to the appearance of a spontaneous magnetic moment.Авторы выражают благодарность Российскому научному фонду за финансовую поддержку исследований (грант № 16-12-10004)