Magnetic anisotropy of epitaxial (Ga,Mn)As on (113)A GaAs

The temperature dependence of magnetic anisotropy in (113)A (Ga,Mn)As layers grown by molecular beam epitaxy is studied by means of superconducting quantum interference device (SQUID) magnetometry as well as by ferromagnetic resonance (FMR) and magnetooptical effects. Experimental results are described considering cubic and two kinds of uniaxial magnetic anisotropy. The magnitude of cubic and uniaxial anisotropy constants is found to be proportional to the fourth and second power of saturation magnetization, respectively. Similarly to the case of (001) samples, the spin reorientation transition from uniaxial anisotropy with the easy along the [-1, 1, 0] direction at high temperatures to the biaxial anisotropy at low temperatures is observed around 25 K. The determined values of the anisotropy constants have been confirmed by FMR studies. As evidenced by investigations of the polar magnetooptical Kerr effect, the particular combination of magnetic anisotropies allows the out-of-plane component of magnetization to be reversed by an in-plane magnetic field. Theoretical calculations within the p-d Zener model explain the magnitude of the out-of-plane uniaxial anisotropy constant caused by epitaxial strain, but do not explain satisfactorily the cubic anisotropy constant. At the same time the findings point to the presence of an additional uniaxial anisotropy of unknown origin. Similarly to the case of (001) films, this additional anisotropy can be explained by assuming the existence of a shear strain. However, in contrast to the (001) samples, this additional strain has an out-of-the-(001)-plane character.Comment: 13 pages, 9 figure

Role of decomposition products in the oxidation of cyclohexene using a manganese(III) complex

Metal complexes are extensively explored as catalysts for oxidation reactions; molecular-based mechanisms are usually proposed for such reactions. However, the roles of the decomposition products of these materials in the catalytic process have yet to be considered for these reactions. Herein, the cyclohexene oxidation in the presence of manganese(III) 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine chloride tetrakis(methochloride) (1) in a heterogeneous system via loading the complex on an SBA-15 substrate is performed as a study case. A molecular-based mechanism is usually suggested for such a metal complex. Herein, 1 was selected and investigated under the oxidation reaction by iodosylbenzene or (diacetoxyiodo)benzene (PhI(OAc)2). In addition to 1, at least one of the decomposition products of 1 formed during the oxidation reaction could be considered a candidate to catalyze the reaction. First-principles calculations show that Mn dissolution is energetically feasible in the presence of iodosylbenzene and trace amounts of water

Aggregated manganese complex-nanolayered manganese oxide: a new hybrid molecular-inorganic material

Layered materials such as clays, layered double hydroxides, and layered hydroxides are promising compounds for material science applications because, in addition to their structural and functional properties, the aggregation of these compounds with others results in new structural and functional characteristics. Notably, the aggregation of a metal complex and nanolayered material leads to new structures and properties. Mn oxides and complexes are different compounds, which show promising properties. Herein, a new hybrid molecular-inorganic material was synthesized by the aggregation of a manganese complex with a 2,4,6-tris(2-pyridyl)-1,3,5-triazine ligand and monolayers of Mn oxide. This new hybrid molecularinorganic material was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis, microanalysis, UV-Vis spectroscopy, nitrogen adsorption–desorption isotherm, magnetic properties, and electron paramagnetic resonance spectroscopy. All these methods showed that the aggregation of the manganese complex and layered Mn oxide occurred. A larger extent of aggregation for this hybrid molecular-inorganic material was observed compared to monolayered Mn oxide. The new material constitutes a new family of hybrid molecular-inorganic materials, in which transition metal complexes could be placed in a new environment

Reaction between Nickel Hydroxide and Cerium(IV) Ammonium Nitrate in Aqueous Solution

Cerium(IV) ammonium nitrate (CAN) has been extensively used as a sacrificial oxidant to study water-oxidation catalysts (WOCs). Although nickel hydroxide has been extensively investigated as WOCs, the water-oxidation reaction (WOR) and mechanistic studies in the presence of CAN and nickel hydroxide were rarely performed. Herein, using in situ Raman spectroscopy, in situ X-ray absorption spectroscopy, and in situ electron paramagnetic resonance spectroscopy, WOR in the presence of CAN and β-Ni(OH)2 was investigated. The proposed WOR mechanism involves the oxidation of β-Ni(OH)2 by CAN, leading to the formation of γ-NiO(OH). γ-NiO(OH), in the presence of acidic conditions, evolves oxygen and is reduced to Ni(II). In other words, the role of β-Ni(OH)2 is the storage of four oxidizing equivalents by CAN, and then a four-electron reaction could result in a WOR with low activation energy. β-Ni(OH)2 in CAN at concentrations of 0.10 M shows WOR with a maximum turnover frequency and a turnover number (for 1000 s) of 5.5 × 10–5/s and 2.0 × 10–2 mol (O2)/mol(Ni), respectively. In contrast to β-Ni(OH)2, Ni(OH2)62+ (aq) could not be oxidized to γ-NiO(OH). Indeed, Ni(OH2)62+ (aq) is the decomposition product of β-Ni(OH)2/CAN

Cryogenic temperature growth of Sn thin films on ferromagnetic Co(0001)

Topological electronic materials hold great promise for revolutionizing spintronics, owing to their topological protected, spin-polarized conduction edge or surface state. One of the key bottlenecks for the practical use of common binary and ternary topological insulator (TI) materials is the large defect concentration which leads a high background carrier concentration. Elemental tin in its α-phase is a room temperature topological semimetal, which is intrinsically less prone to defect-related shortcomings. Recently, the growth of ultrathin α-Sn films on ferromagnetic Co surfaces has been achieved, however, thicker films are needed to reach the 3D topological Dirac semimetallic state. Here, the growth of α-Sn films on Co at cryogenic temperatures was explored. Very low-temperature growth holds the promise of suppressing undesired phases, alloying across the interfaces, as well as the formation of Sn pillars or hillocks. Nevertheless, the critical Sn layer thickness of ∼3 atomic layers, above which the film partially transforms into the undesired β-phase, remains the same as for room-temperature growth. From ferromagnetic resonance studies, and supported by electron microscopy, it can be concluded that for cryogenic Sn layer growth, the interface between Sn and Co remains sharp and the magnetic properties of the Co layer stay intact

Surprisingly low reactivity of manganese oxide toward water oxidation in an ultra-pure electrolyte under alkaline conditions

So far, many studies on the oxygen-evolution reaction (OER) by Mn oxides have been focused on activity; however, the identification of the best performing active site and corresponding catalytic cycles is also of critical importance. Herein, the real intrinsic activity of layered Mn oxide toward OER in Fe/Ni-free KOH is studied for the first time. At pH ≈ 14, the onset of OER for layered Mn oxide in the presence of Fe/Ni-free KOH happens at 1.72 V (vs reversible hydrogen electrode (RHE)). In the presence of Fe ions, a 190 mV decrease in the overpotential of OER was recorded for layered Mn oxide as well as a significant decrease (from 172.8 to 49 mV/decade) in the Tafel slope. Furthermore, we find that both Ni and Fe ions increase OER remarkably in the presence of layered Mn oxide, but that pure layered Mn oxide is not an efficient catalyst for OER without Ni and Fe under alkaline conditions. Thus, pure layered Mn oxide and electrolytes are critical factors in finding the real intrinsic activity of layered Mn oxide for OER. Our results call into question the high efficiency of layered Mn oxides toward OER under alkaline conditions and also elucidate the significant role of Ni and Fe impurities in the electrolyte in the presence of layered Mn oxide toward OER under alkaline conditions. Overall, a computational model supports the conclusions from the experimental structural and electrochemical characterizations. In particular, substitutional doping with Fe decreases the thermodynamic OER overpotential up to 310 mV. Besides, the thermodynamic OER onset potential calculated for the Fe-free structures is higher than 1.7 V (vs RHE) and, thus, not in the stability range of Mn oxides.</p

Role of decomposition products in the oxidation of cyclohexene using a manganese(III) complex

Abstract Metal complexes are extensively explored as catalysts for oxidation reactions; molecular-based mechanisms are usually proposed for such reactions. However, the roles of the decomposition products of these materials in the catalytic process have yet to be considered for these reactions. Herein, the cyclohexene oxidation in the presence of manganese(III) 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine chloride tetrakis(methochloride) (1) in a heterogeneous system via loading the complex on an SBA-15 substrate is performed as a study case. A molecular-based mechanism is usually suggested for such a metal complex. Herein, 1 was selected and investigated under the oxidation reaction by iodosylbenzene or (diacetoxyiodo)benzene (PhI(OAc)2). In addition to 1, at least one of the decomposition products of 1 formed during the oxidation reaction could be considered a candidate to catalyze the reaction. First-principles calculations show that Mn dissolution is energetically feasible in the presence of iodosylbenzene and trace amounts of water