13 Search Results

Brucite [Mg(OH)₂] is a promising sorbent for carbon dioxide removal (CDR) due to its availability and low calcination temperatures. However, natural and synthetic brucites tend to contain metal impurities, such as iron or manganese, and how these impurities affect the interfacial chemical reactivity is uncertain. Here, in this study, the impact of low concentrations of iron and manganese impurities on the carbonation efficiency of Mg(OH)₂ was examined. Mg(OH)₂ with small amounts (1–5 mol %) of Fe and Mn was synthesized. The increasing substitution of Fe into Mg(OH)₂ was accompanied by the oxidation of Fe. The phase transformation sequence during themore » carbonation was found to be brucite [Mg(OH)₂] → amorphous magnesium carbonate (MgCO₃·nH₂O) → nesquehonite (MgCO₃·3H₂O), regardless of impurity concentration. Both the Fe- and Mn-doped Mg(OH)₂ samples were more reactive than endmember Mg(OH)₂, possibly due to their higher surface areas and lower stabilities. During carbonation, 3 mol % Fe- and Mn-doped Mg(OH)₂ showed the highest reactivity. The variance in reactivity for Mn-doped Mg(OH)₂ was less than that of Fe-doped Mg(OH)₂. These results suggest that natural or industrial waste Mg(OH)₂ with less than 5 mol % Fe and Mn impurities may be targeted as more effective CDR sorbents than endmember Mg(OH)₂.« less

AMX Zintl compounds with the hexagonal ZrBeSi structure have gained significant attention for their remarkable vacancy tolerance and low thermal conductivity. Their 2D honeycomb sublattice, composed of M–X covalent bonds, is believed to contribute to high anharmonicity and unusual thermal transport properties. In this study, we explore the temperature-dependent polymorphism of YbCuBi as a model system to investigate the relationship between the structure and elastic and thermal transport properties in AMX Zintls. YbCuBi undergoes a structural transition from the “flat” Cu–Bi layers in the ZrBeSi structure to corrugated layers in the LiGaGe structure below 410 K, resulting in a distortionmore » of its centrosymmetric structure. To probe the effects of this crystallographic transition, we employ inelastic neutron scattering and temperature-dependent resonant ultrasound spectroscopy. These experimental findings, coupled with first-principles calculations and thermal conductivity measurements, allow us to elucidate a direct relationship between corrugation of the honeycomb lattice and the observed changes in elastic and thermal transport properties. These insights can be extended to other Zintl phases with similar structure types, providing a platform for the rational design of functional materials with tailored thermal properties.« less

We provide experimental evidence for the absence of a magnetic moment in bulk RuO₂, a candidate altermagnetic material, by using a combination of Mössbauer spectroscopy, nuclear forward scattering, inelastic X-ray and neutron scattering, and density functional theory calculations. Using complementary Mössbauer and nuclear forward scattering, we determine the Ru magnetic hyperfine splitting to be negligible. Inelastic X-ray and neutron scattering-derived lattice dynamics of RuO₂ are compared to density functional theory calculations of varying flavors. Comparisons among theory with experiments indicate that electronic correlations, rather than magnetic order, are key in describing the lattice dynamics.

Large spin-orbit-coupled cations in geometrically frustrated crystal structures have the most suitable setting for exploring novel exotic states of matter. Spinel oxides (AM₂O₄) are well-known examples of geometrically frustrated systems. In this study, we report for the first time the synthesis of compositions LiRhRu_1-xIr_xO₄ (x = 0–0.5), LiFeIr_1-xRu_xO₄ (x = 0–0.5), and LiCoIr_1-xRu_xO₄ (x = 0–0.3) containing precious metal cations on edge-sharing octahedral M-sites, and systematically investigate their magnetic and electrical properties. ⁵⁷Fe Mössbauer spectroscopy revealed that iron is trivalent in all LiFeIr_1-xRu_xO₄ solid solutions. Magnetic measurements indicate deviations from theoretical spin-only magnetic moment values, indicating the influence of spin-orbitmore » coupling owing to the presence of 4d and 5d block elements. The LiFeIr_1-xRu_xO₄ series shows spin-glass-like freezing behavior with T_g ≈ 20 K, and a small frustration index (f ≈ 1-2), indicating that the frustration originates from site disorder. LiRhRu_1-xIr_xO₄ and LiCoIr_1-xRu_xO₄ exhibit strongly geometrically frustrated magnetism. Electrical resistivity measurements as a function of temperature indicate that all phases are semiconducting. Seebeck coefficient measurements show that LiRhRu_1-xIr_xO₄ and LiFeIr_1-xRu_xO₄ are p-type semiconductors with holes as the major charge carriers. A sign reversal of the Seebeck coefficient indicates both holes and electrons as carriers for LiCoIr_1-xRuxO₄ (x = 0–0.2), but only holes as major carriers for x = 0.3. Here, the Seebeck coefficient and power factor increase drastically in the LiRhRu_1-xIr_xO₄ solid solution with Ir substitution, reaching a maximum of ≈ +125 μV/K and ≈2.3×10^-6 W/mK² at ∼650 K for x = 0.5.« less

The hexagonal antiferromagnet MnTe has attracted enormous interest as a prototypical example of a spin-compensated magnet in which the combination of crystal and spin symmetries lifts the spin degeneracy of the electron bands without the need for spin-orbit coupling, a phenomenon called nonrelativistic spin splitting (NRSS). Subgroups of NRSS are determined by the specific spin-interconverting symmetry that connects the two opposite-spin sublattices. In MnTe, this symmetry is rotation, leading to the subgroup with spin splitting away from the Brillouin zone center, often called altermagnetism. MnTe also has the largest spontaneous magnetovolume effect of any known antiferromagnet, implying strong coupling betweenmore » the magnetic moment and volume. This magnetostructural coupling offers a potential knob for tuning the spin-splitting properties of MnTe. Here, we use neutron diffraction with in situ applied pressure to determine the effects of pressure on the magnetic properties of MnTe and further explore this magnetostructural coupling. We find that applying pressure significantly increases the Néel temperature, but decreases the ordered magnetic moment. We explain this as a consequence of strengthened magnetic exchange interactions under pressure, resulting in higher 𝑇_N, with a simultaneous reduction of the local moment of individual Mn atoms, described here via density functional theory. This reflects the increased orbital hybridization and electron delocalization with pressure. In conclusion, these results shed light on the competition between magnetic exchange interactions and the strength of individual magnetic moments and show that the magnetic properties of MnTe can be controlled by pressure, opening the door to improved properties for spintronic applications through tuning via physical or chemical pressure.« less

Soft ferrites are materials of interest for magnetic cores, as used for wireless charging transformers. Their low permeabilities, high resistivity, and magnetic polarization make them interesting for high-power electric vehicle charging and drive systems. The nickel-zinc-doped ferrites are of particular interest; however, the compositional space is quite large with respect to dopant concentrations, stoichiometric ratios and synthesis technique. Nickel-zinc spinel ferrites with varying nickel-zinc ratios prepared by a self-combustion reaction followed by heat treatment exhibit good crystallinity, and their low-temperature Mössbauer spectra show local magnetism and site occupation in agreement with materials prepared by solid-state reaction. Thus, the combustion synthesismore » method offers a facile tunability of compositions, which, combined with the possibility of rapid characterization of atomic-scale magnetism by Mössbauer spectroscopy, enables advances in the compositional and processing space at a fast pace. Low-temperature Mössbauer spectroscopy data for samples with increasing nickel content reveals a systematic increase in average hyperfine field (2.8 T/Ni) and decrease in average isomer shift (−0.036 mm/s/Ni) that can determine the nickel/zinc content, even in the absence of applied magnetic field data. Furthermore, a gradual evolution of color is also observed with increasing nickel content, albeit trends in color depend on sintering conditions.« less

Quaternary oxychlorides derived from Ruddlesden–Popper 3d transition metal oxides offer a route to cleavable crystals with bulk antiferromagnetic ordering temperatures reaching at least 550 K. Here, we study the magnetic, optical, and mechanical behavior of Sr₂FeO₃Cl, Ca₂FeO₃Cl, Ca₃Fe₂O₅Cl₂, and Sr₃Fe₂O₅Cl₂. Through optical absorption measurements, we show that these antiferromagnetic semiconductors have optical band gaps of ≈2.1(1) eV. The magnetic ordering symmetries and temperatures were probed by neutron powder diffraction and Mössbauer spectroscopy on polycrystalline samples, demonstrating Néel temperatures (T_N) near room temperature in the single layer Sr₂FeO₃Cl (T_N ≈ 311 K) and Ca₂FeO₃Cl (T_N ≈ 360 K), and the double-layermore » compound Sr₃Fe₂O₅Cl₂ has T_N ≈ 545 K. The high-spin moments of Fe³⁺ lie within the basal plane and the magnetic structures are compensated within each magnetic layer and characterized by magnetic propagation vectors k = ($$\frac{1}{2}$$ $$\frac{1}{2}$$ 0). Magnetization results demonstrate the quasi-2D nature of the magnetism, with a broad maximum in the susceptibility near 2T_N for Sr₂FeO₃Cl. Scotch tape tests and mechanical exfoliation onto SiO₂ confirm the micaceous nature of these crystals with cleavage down to a single unit cell (two magnetic layers) achieved for Sr₃Fe₂O₅Cl₂. In conclusion, this paper highlights strong antiferromagnetic interactions, semiconducting band gaps, and cleavability of quaternary Fe-based oxychlorides and motivates future work on crystals and exfoliated flakes of these and related oxyhalide systems.« less

MgO (periclase) is a promising material for direct air capture of CO₂ using a mineral looping process, but it is unknown how impurities in the environment will affect the CO₂ uptake and hence process economics. Here, we investigated the effects of dissolved iron on the extents of MgO hydroxylation and subsequent carbonation reactions to determine if this has a beneficial or detrimental effect. On single-crystal MgO, dissolved iron prevented hydration of MgO to Mg(OH)₂ (brucite) and instead formed a shell of lepidocrocite (γ-FeOOH). This did not passivate the MgO as dissolution below the shell was observed. During hydroxylation of MgOmore » powders in the presence of dissolved iron, formation of brucite containing Fe(II) was observed. In addition, formation of nanoscale iron oxides containing Fe(III) was observed using magnetometry and Mössbauer spectroscopy. Subsequent carbonation experiments showed increased carbonation of MgO hydroxylated in the presence of iron. Our results indicate that the presence of dissolved solute impurities during hydroxylation may be beneficial for carbonation of hydroxylated MgO.« less

Manganese telluride (MnTe) is a prospective platform for ultrafast carrier dynamics, spin-based thermoelectrics, and magnon-drag transport due to its unique electronic and magnetic properties. We use inelastic neutron scattering to study both pure and lithium-doped MnTe, focusing on the influence of doping in opening a magnon gap. We use neutron powder diffraction to determine critical exponents for the phase transition in both pure and Li-doped MnTe and complement this information with muon spin rotation/relaxation. In conclusion, the opening of the magnon gap and spin reorientation in Li-doped MnTe is mainly due to increased magnetic anisotropy along the [001] axis, amore » feature not present in pure MnTe.« less

We report spin diode is important prerequisite to practical manifestation of spin electronics. Yet, a functioning magnetic diode at room temperature is still illusive. Here, we reveal diode-type phenomena due to magnetic charge mediated conduction in artificial honeycomb geometry, made of concave shape single domain permalloy element. We find that honeycomb lattice defies symmetry by populating vertices with low and high multiplicity magnetic charges, causing asymmetric magnetization, in applied current of opposite polarity. High multiplicity units create highly resistive network, thereby inhibiting magnetic charge dynamics propelled electrical conduction. However, practical realization of this effect requires modest demagnetization factor in constitutingmore » element. Concave structure fulfills the condition. Subsequently, magnetic diode behavior emerges across broad thermal range of T = 40 K–300 K. The finding is a departure from the prevailing notion of spin-charge interaction as the sole guiding principle behind spintronics. Consequently, a new vista, mediated by magnetic charge interaction, is envisaged for spintronic research.« less