Synthesis and characterization of nanoscale composite particles formed by 2D layers of Cu-Fe sulfide and Mg-based hydroxide

We introduce here a multifunctional material composed of alternating atomic sulfide sheets close to CuFeS2 and Mg-based hydroxide ones (valleriite), which are assembled due to their electric charges of opposite sign. Valleriite particles of 50-200 nm in the lateral size and 10-20 nm thick were synthesized via a simple hydrothermal pathway using various concentrations of precursors and dopants, and examined with XRD, TEM, EDS, X-ray photoelectron spectroscopy, reflection electron energy loss spectroscopy (REELS), Mössbauer, Raman and UV-vis-NIR spectroscopies, magnetic, dynamic light scattering, zeta potential measurements. The electronic, magnetic and optical characteristics are found to be critically dependent of the charge (electron density) at the narrow-gap sulfide layers containing Cu+ and Fe3+ cations, and can be tuned via the composition of hydroxide part. Particularly, substitution of Mg2+ with Al3+ increases the negative charge of the hydroxide layers and reduces the content of Fe3+-OH centers (10-45% of total iron); the effects of Cr and Co dopants entering both layers are more complicated. Mössbauer doublets of paramagnetic Fe3+ detected at room temperature transform to several Zeeman sextets at 4.2 K; the hyperfine fields up to 500 kOe and complex magnetic behavior, but not pure paramagnetism or antiferromagnetism, were observed for valleriites with the higher positive charge of the sulfide sheets, probably due to the depopulation of the minority-spin 3d states of S-bonded Fe3+ ions. Aqueous colloids of valleriite show optical absorption at 500 - 750 nm, which, along with the peaks at the same energies in REELS, may arise due to quasi-static dielectric resonance involving the vacant Fe 3d band and being dependent on the composition of both layers too. These and other findings call attention to the of valleriites as a new rich family of 2D materials for a variety of potential applications.

Synthesis and characterization of nanoscale composite particles formed by 2D layers of Cu-Fe sulfide and Mg-based hydroxide

Two-dimensional phenomena are attracting enormous interest at present and the search for novel 2D materials is very challenging. We propose here the layered material valleriite composed of altering atomic sheets of Cu-Fe sulfide and Mg-based hydroxide synthesized via a simple hydrothermal pathway as particles of 50-200 nm in the lateral size and 10-20 nm thick. The solid products and aqueous colloids prepared with various precursor ratios were examined using XRD, TEM, EDS, X-ray photoelectron spectroscopy (XPS), reflection electron energy loss spectroscopy (REELS), Raman, Mössbauer, UV-vis-NIR spectroscopies, magnetic, dynamic light scattering, zeta potential measurements. The material properties are largely determined by the narrow-gap (less than 0.5 eV) sulfide layers containing Cu+ and Fe3+ cations, monosulfide and minor polysulfide anions but are strongly affected by the hydroxide counterparts. Particularly, Fe distribution between sulfide (55-90%) and magnesium hydroxide layers is controlled through insertion of Al into the hydroxide part and by Cr and Co dopants entering both layers. Room-temperature Mössbauer signals of paramagnetic Fe3+ transformed to several Zeeman sextets with hyperfine magnetic fields up to 500 kOe in the sulfide layers at 4 K. Paramagnetic or more complicated characters were observed for valleriites with higher and lower Fe concentrations in hydroxide sheets, respectively. Valleriite colloids showed negative zeta potentials, suggesting negative electric charging of the hydroxide sheets, and optical absorption maxima between 500 nm and 700 nm, also depended on the Fe distribution. The last features observed also in the REELS spectra may be due to localized surface plasmon or, more likely, quasi-static dielectric resonance. The tunable composition, electronic, magnetic, optic and surface properties highlight valleriites as a rich platform for novel 2D composites promising for numerous applications.

Structural and dielectric properties of sol–gel processed Ce-doped BaTi0.97Y0.03O3 ceramics

Structural and dielectric properties of Ce-doped BaTi[Formula: see text]Y[Formula: see text]O3 powders, with the chemical formulation (Ba[Formula: see text]Ce[Formula: see text](Ti([Formula: see text]- Y[Formula: see text]O3 such as [Formula: see text] = 0%, 1%, 3%, 5%, 7% and 9%, produced by the sol–gel method, have been investigated. X-ray diffraction analysis showed that Ce[Formula: see text] ions incorporated Ba sites until [Formula: see text]= 7% indicating that this concentration represents a solubility limit of Ce[Formula: see text] ions in BaTi[Formula: see text]Y[Formula: see text]O3 matrix. Scanning electron microscopy (SEM) analysis showed a decrease in grain size down to the same concentration of 7%. Raman spectroscopy analysis showed the appearance of A[Formula: see text] mode, which we attributed to the effect of incorporation of Ce[Formula: see text] and Y[Formula: see text] in BaTiO3 matrix. Dielectric measurements revealed that doping with cerium lowers the temperature of permittivity maximum at the ferroelectric-to-paraelectric transition (FPT) of the BaTi[Formula: see text]Y[Formula: see text]O3 sample, and reaches a value that should be below 40[Formula: see text]C for [Formula: see text]= 9%. Moreover, the phenomenon of dielectric resonance was observed on all Ce-doped samples, which was not the case with other dopants as reported in the literature.