Cubic bi-magnetic hard-soft core-shell nanoarchitectures were prepared starting from cobalt ferrite nanoparticles, prevalently with cubic shape, as seeds to grow a manganese ferrite shell. The combined use of direct (nanoscale chemical mapping via STEM-EDX) and indirect (DC magnetometry) tools was adopted to verify the formation of the heterostructures at the nanoscale and bulk level, respectively. The results showed the obtainment of core-shell NPs (CoFe2O4@MnFe2O4) with a thin shell (heterogenous nucleation). In addition, manganese ferrite was found to homogeneously nucleate to form a secondary nanoparticle population (homogenous nucleation). This study shed light on the competitive formation mechanism of homogenous and heterogenous nucleation, suggesting the existence of a critical size, beyond which, phase separation occurs and seeds are no longer available in the reaction medium for heterogenous nucleation. These findings may allow one to tailor the synthesis process in order to achieve better control of the materials' features affecting the magnetic behaviour, and consequently, the performances as heat mediators or components for data storage devices.

• Klíčová slova
• STEM-EDX, cobalt ferrite, core–shell, cubic shape, heterostructures,
• Publikační typ
• časopisecké články MeSH

In this work, the effect of different molecular coatings on the alternating magnetic field-induced heating properties of 15 nm maghemite nanoparticles (NPs) in water dispersions was studied at different frequencies (159-782 kHz) and field amplitudes (100-400 G). The original hydrophobic oleate coating was replaced with dimercaptosuccinic acid (DMSA) or polyethylene glycol trimethoxysilane (PEGTMS), while cetrimonium bromide (CTAB) or stearic acid-poloxamer 188 (SA-P188) was intercalated or encapsulated, respectively, to transfer the dispersions into water. Surface modification, based on intercalation processes, induced clustering phenomena with the formation of spherical-like assemblies (CTAB and SA-P188), while ligand-exchange strategies kept the particles isolated. The clustering phenomenon has detrimental effects on the heating performances compared with isolated systems, in line with the reduction of Brown relaxation times. Furthermore, broader comprehension of the heating phenomenon in this dynamic system is obtained by following the evolution of SPA and ILP with time and temperature beyond the initial stage.

• Publikační typ
• časopisecké články MeSH

Direct consideration for both, the catalytically active species and the host materials provides highly efficient strategies for the architecture design of nanostructured catalysts. The conventional wet chemical methods have limitations in achieving such unique layer-by-layer design possessing one body framework with many catalyst parts. Herein, an innovative physical method is presented that allows the well-regulated architecture design for an array of functional nanocatalysts as exemplified by layer-by-layer adornment of Pd nanoparticles (NPs) on the highly arrayed silica nanorods. This spatially confined catalyst exhibits excellent efficiency for the hydrogenation of nitroarenes and widely deployed Suzuki cross-coupling reactions; their facile separation from the reaction mixtures is easily accomplished due to the monolithic structure. The generality of this method for the introduction of other metal source has also been demonstrated with Au NPs. This pioneering effort highlights the feasibility of physically controlled architecture design of nanostructured catalysts which may stimulate further studies in the general domain of the heterogeneous catalytic transformations.

• Publikační typ
• časopisecké články MeSH

Bi-magnetic core-shell spinel ferrite-based nanoparticles with different CoFe2O4 core size, chemical nature of the shell (MnFe2O4 and spinel iron oxide), and shell thickness were prepared using an efficient solvothermal approach to exploit the magnetic coupling between a hard and a soft ferrimagnetic phase for magnetic heat induction. The magnetic behavior, together with morphology, stoichiometry, cation distribution, and spin canting, were investigated to identify the key parameters affecting the heat release. General trends in the heating abilities, as a function of the core size, the nature and the thickness of the shell, were hypothesized based on this systematic fundamental study and confirmed by experiments conducted on the water-based ferrofluids.

• Publikační typ
• časopisecké články MeSH

In the last few decades, the emission of carbon dioxide (CO2) in the environment has caused havoc across the globe. One of the most promising strategies for fixation of CO2 is the cycloaddition reaction between epoxides and CO2 to produce cyclic carbonates. For the first time, we have fabricated copper-based magnetic nanocatalyst and have applied for the CO2 fixation. The prepared catalyst was thoroughly characterized using various techniques including XRD, FT-IR, TEM, FE-SEM, XPS, VSM, ICP-OES and elemental mapping. The reactions proceeded at atmospheric pressure, relatively lower temperature, short reaction time, solvent- less and organic halide free reaction conditions. Additionally, the ease of recovery through an external magnet, reusability of the catalyst and excellent yields of the obtained cyclic carbonates make the present protocol practical and sustainable.

• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH

Iron(III) oxide shows a polymorphism, characteristic of existence of phases with the same chemical composition but distinct crystal structures and, hence, physical properties. Four crystalline phases of iron(III) oxide have previously been identified: α-Fe2O3 (hematite), β-Fe2O3, γ-Fe2O3 (maghemite), and ε-Fe2O3. All four iron(III) oxide phases easily undergo various phase transformations in response to heating or pressure treatment, usually forming hexagonal α-Fe2O3, which is the most thermodynamically stable Fe2O3 polymorph under ambient conditions. Here, from synchrotron X-ray diffraction experiments, we report the formation of a new iron(III) oxide polymorph that we have termed ζ-Fe2O3 and which evolved during pressure treatment of cubic β-Fe2O3 (Ia3 space group) at pressures above 30 GPa. Importantly, ζ-Fe2O3 is maintained after pressure release and represents the first monoclinic Fe2O3 polymorph (I2/a space group) that is stable at atmospheric pressure and room temperature. ζ-Fe2O3 behaves as an antiferromagnet with a Néel transition temperature of ~69 K. The complex mechanism of pressure-induced transformation of β-Fe2O3, involving also the formation of Rh2O3-II-type Fe2O3 and post-perovskite-Fe2O3 structure, is suggested and discussed with respect to a bimodal size distribution of precursor nanoparticles.

• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH

Methods for the asymmetric transfer hydrogenation (ATH) of ketones and imines are still being intensively studied and developed. Of foremost interest is the use of Noyori's [RuCl(η⁶-arene)(N-TsDPEN)] complexes in the presence of a hydrogen donor (i-PrOH, formic acid). These complexes have found numerous practical applications and have been extensively modified. The resulting derivatives have been heterogenized, used in ATH in water or ionic liquids and even some attempts have been made to approach the properties of biocatalysts. Therefore, an appropriate modification of the catalyst that suits the specific requirements for the reaction conditions is very often readily available. The mechanism of the reaction has also been explored to a great extent. Model substrates, acetophenone (a ketone) and 6,7-dimethoxy-1-methyl-3,4-dihydroisoquinoline (an imine), are both reduced by this Ru catalytic system with almost perfect selectivity. However, in each case the major product is a different enantiomer (S- for an alcohol, R- for an amine when the S,S-catalyst is used), which demanded an in-depth mechanistic investigation. Full-scale molecular modelling of this system enabled us to visualize the plausible 3D structures of the transition states, allowing the proposition of a viable explanation of previous experimental findings.

• MeSH
• hydrogenace MeSH
• iminy chemie   MeSH
• katalýza MeSH
• ketony chemie   MeSH
• molekulární struktura MeSH
• stereoizomerie MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• přehledy MeSH
• Názvy látek
• iminy MeSH
• ketony MeSH