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 the composition of CuFeS 2 and Mg-based hydroxide ones (valleriite), which are assembled due to their electric charges of opposite sign. Valleriite particles 50-200 nm in lateral size and 10-20 nm in...

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Published in:Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2022-05, Vol.1 (17), p.9621-9634
Main Authors: Mikhlin, Yuri L, Borisov, Roman V, Vorobyev, Sergey A, Tomashevich, Yevgeny V, Romanchenko, Alexander S, Likhatski, Maxim N, Karacharov, Anton A, Bayukov, Oleg A, Knyazev, Yuriy V, Velikanov, Dmitriy A, Zharkov, Sergey M, Krylov, Alexander S, Krylova, Svetlana N, Nemtsev, Ivan V
Format: Article
Language:English
Subjects:
Aluminum
Antiferromagnetism
Cations
Chalcopyrite
Charge density
Chromium
Colloids
Composition
Copper
Dopants
Electron density
Electron energy loss spectroscopy
Energy dissipation
Energy loss
Ferric ions
Hyperfine structure
Iron
Light scattering
Magnesium
Magnetic properties
Optical properties
Paramagnetism
Particulate composites
Photoelectron spectroscopy
Photoelectrons
Photon correlation spectroscopy
Reels
Room temperature
Sheets
Spectroscopy
Spectrum analysis
Sulfide
Sulfides
X ray reflection
Zeta potential
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Summary:We introduce here a multifunctional material composed of alternating atomic sulfide sheets close to the composition of CuFeS 2 and Mg-based hydroxide ones (valleriite), which are assembled due to their electric charges of opposite sign. Valleriite particles 50-200 nm in lateral size and 10-20 nm in thickness 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, and magnetization, dynamic light scattering, and zeta potential measurements. The electronic, magnetic and optical characteristics are found to be critically dependent on the charge (electron density) at the narrow-gap sulfide layers containing Cu + and Fe 3+ cations, and can be tuned via the composition of the hydroxide part. Particularly, substitution of Mg 2+ with Al 3+ increases the negative charge of the hydroxide layers and reduces the content of Fe 3+ -OH centers (10-45% of total iron); the effects of Cr and Co dopants entering both layers are more complicated. Mössbauer doublets of paramagnetic Fe 3+ detected at room temperature transform into 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 Fe 3+ 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 valleriites as a new rich family of 2D materials for a variety of potential applications. We propose a simple hydrothermal synthesis of nanoflakes composed of alternating sulfide and hydroxide quasi-monolayers and their aqueous colloids, as a prospective family of novel multifunctional 2D materials.
ISSN:2050-7488
2050-7496
DOI:10.1039/d2ta00877g