Combined effect of 2D nature and structural glass behaviour and true magnetic contribution to the low-temperature heat capacity of layered double hydroxides

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science Pub Date : 2025-01-09 DOI:10.1016/j.clay.2024.107695

V. Tkáč , Yu.G. Pashkevich , E.L. Fertman , R. Tarasenko , E. Čižmár , A. Feher , A.V. Fedorchenko , C.S. Neves , D.E.L. Vieira , A.N. Salak

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引用次数: 0

Abstract

Heat capacity of cobalt-aluminium and magnesium-aluminium layered double hydroxides (LDH) with the divalent-to-trivalent cations ratio (n) of 2 and 3, and intercalated with NO₃⁻, CO₃²⁻ and OH⁻, was measured as a function of temperature between 2 and 100 K. Magnetic contribution to the heat capacity (C_mag) of Co_nAl LDH was extracted from comparison of the C(T) dependences with the respective reduced dependences of their non-magnetic counterparts, Mg_nAl LDH. At the lowest measured temperatures, the magnetic contribution to the heat capacity (C_mag) of Co-containing LDH was found to be almost two orders of magnitude bigger than their lattice contribution. In a zero magnetic field, the low-temperature C_mag of Co₂Al LDH was measured to be proportional to T^2.6, while for Co₃Al LDH, C_mag ∼ T² was observed. An application of an external magnetic field was revealed to converge these dependences to C_mag ∼ T³ in compounds with both n = 2 and 3. However, the conversion in Co₂Al LDH occurred at lower values of external magnetic field (50 kOe) than that in Co₃Al LDH (90 kOe).

It was revealed from the C(T) behaviour of the non-magnetic LDH at the lowest measured temperatures that they possess the features typical for both a 2D solid and a structural glass. The reduced C(T)/T³ heat capacity of Mg_nAl LDH intercalated with nitrate was found to demonstrate a so-called boson peak, which is a manifestation of a glassy state. The observed low-temperature structural glassy state in LDH was associated with the disorder of the intercalated species.

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来源期刊

Applied Clay Science 地学-矿物学

CiteScore

10.30

自引率

10.70%

发文量

289

审稿时长

39 days

期刊介绍： Applied Clay Science aims to be an international journal attracting high quality scientific papers on clays and clay minerals, including research papers, reviews, and technical notes. The journal covers typical subjects of Fundamental and Applied Clay Science such as: • Synthesis and purification • Structural, crystallographic and mineralogical properties of clays and clay minerals • Thermal properties of clays and clay minerals • Physico-chemical properties including i) surface and interface properties; ii) thermodynamic properties; iii) mechanical properties • Interaction with water, with polar and apolar molecules • Colloidal properties and rheology • Adsorption, Intercalation, Ionic exchange • Genesis and deposits of clay minerals • Geology and geochemistry of clays • Modification of clays and clay minerals properties by thermal and physical treatments • Modification by chemical treatments with organic and inorganic molecules(organoclays, pillared clays) • Modification by biological microorganisms. etc...