Vertically aligned Mn-doped zinc oxide nanorods by hybrid wet chemical route

Mn-doped zinc oxide (Mn:ZnO) nanorods were synthesized by incorporating manganese in aligned ZnO nanorods. For this, Mn was evaporated onto ZnO nanorods and the composite structure was subjected to rapid thermal annealing. The nanorods were preferentially oriented in (0 0 2) direction as indicated by the XRD measurement. Optical band gap was seen to decrease with increasing amount of Mn incorporation. XPS studies indicated that incorporated Mn was in Mn²⁺ and Mn⁴⁺ states. Mn²⁺ atomic concentration was found to be larger than Mn⁴⁺ concentration in all the samples. The Raman spectra of the Mn:ZnO nanorods indicated the presence of the characteristic peak at ∼438 cm⁻¹ for high frequency branch of E₂ mode of ZnO. The PL peak at ∼376 nm (∼3.29 eV) was ascribed to the band edge luminescence while the peak at ∼394 nm (∼3.15 eV) was assigned to the donor bound exciton (D^oX) and free exciton transition related to Mn²⁺ states.     

Influence of isovalent ion substitution on the electrochemical performance of LiCoPO4

LiCo_1−xM_xPO₄ (M = Mg²⁺, Mn²⁺ and Ni²⁺; 0 ≤ x ≤ 0.2) compounds have been synthesized by solid-state reaction method and studied as cathode materials for secondary lithium batteries. LiCoPO₄ exhibits a discharge plateau at ∼4.7 V with an initial discharge capacity of 125 mAh/g and on cycling capacity falls. Substitution of Co²⁺ with Mg²⁺/Mn²⁺/Ni²⁺ in LiCoPO₄ has an influence on the initial discharge capacity and on cycling behaviour. The capacity retention of LiCoPO₄ is improved by manganese substitution. Among the manganese substituted phases, LiCo_0.95Mn_0.05PO₄ shows good reversible capacity of ∼50 mAh/g.     

One-step through-mask electrodeposition of a porous structure composed of manganese oxide nanosheets with electrocatalytic activity for oxygen reduction

Potentiostatic electrolysis of a mixed aqueous solution of Bu₄NBr and MnSO₄ at +1.0 V (vs. Ag/AgCl) on Pt electrode led to the oxidation of Br⁻ and Mn²⁺ ions. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and X-ray diffraction (XRD) revealed that this anodic process was followed by the deposition of insulating crystals of bromide salt of Bu₄N⁺ and the subsequent formation of layered manganese oxide in the interstitial spaces of the bromide grains already grown. Dissolution of the bromide crystals in water left a well-dispersed porous texture composed of manganese oxide nanosheets. The resulting MnO_x-modified electrode exhibited a larger catalytic current for the reduction of oxygen in alkaline solution, compared to the bare Pt electrode.     

Effect of manganese and cobalt doping on conductivity of ZnO based varistors: a study by complex plane modulus

Effect of manganese and cobalt doping (0.50 mole%) on electrical properties of ZnO based varistors has been studied using complex plane modulus analysis. It is found that total resistivity of Mn doped sample is more as compared to that of Co doped sample. This has been ascribed to existence of Mn in variable valence states viz. Mn²⁺, Mn³⁺ and Mn⁴⁺ which promotes hopping conduction leading to increase in the conductivity as compared to Co doped sample, in which Co exists predominantly in +3 state with traces of Co²⁺ or Co⁺⁴ states. This accounts for its less conductivity. Mechanism of conduction is the same for grains and grainboundaries.     

Coordination and valence state of transition metal ions in alkali-borate glasses

Borate glasses of the 20R₂O·80B₂O₃ type, where R = Li, Na and K, were colored by doping with transition metal ions (Co, Ni, Cr and Mn). The glasses were obtained by melting at the temperature of 1150 °C. For these glasses optical absorption in UV–VIS–NIR range were recorded. Analysis of the spectra allows to be determined the coordination and oxidation states of the doping transition metal ions. Changes of their coordination or oxidation are presented as a function of the optical basicity Λ after Duffy. Cobalt and nickel are present in examined borate glasses as divalent ions (Co²⁺, Ni²⁺) in octahedral coordination mainly, but the tetrahedral coordination state of cobalt is also possible. Chromium and manganese are present in the borate glasses in various oxidation state, though Cr³⁺ and Mn³⁺ ions in the octahedral coordination are probably dominant. A decrease of the electronegativity of the modifiers (Li → Na → K) and an increase of the glass matrix basicity cause a shift of the oxidation/reduction equilibrium towards higher valences of the transition metals (Cr⁶⁺, Mn³⁺).     

Electrochemical behaviors of Li[Li(1−x)/3Mn(2−x)/3Nix/3Cox/3]O2 cathode series (0 < x < 1) synthesized by sucrose combustion process for high capacity lithium ion batteries

A mixed cathode material between Li₂MnO₃ and Li[Mn_1/3Ni_1/3Co_1/3]O₂ for high capacity lithium secondary batteries was introduced in this study. It was prepared using the sucrose combustion process because this is a simple process. The oxidation states of Mn, Co and Ni ions in the pristine Li[Li_(1−x)/3Mn_(2−x)/3Ni_x/3Co_x/3]O₂ compounds were confirmed to be tetravalent, trivalent and divalent, respectively, via XANES measurements. Electrochemical charge/discharge studies showed that the highest first discharge capacity of 224 mAh/g was obtained in composition of x = 0.5 at a 0.2 C rate. The oxidation state of the Co and Ni ions in the Li[Li_1/6Mn_1/2Ni_1/6Co_1/6]O₂ changed to higher oxidation states, but that of the Mn ions did not change.     

Structure and surface morphology of Mn-implanted TiO2

A study of structure and surface morphology together with magnetic properties of Mn-implanted rutile-type TiO₂ single crystals is performed. Homogenous thin films of about 100 nm with different Mn_xTi_1 − xO₂ (x = 0.03; 0.05 and 0.07) chemical formula were obtained. The Mn ion implanted surface exhibited a dense microstructure with a nano grain size. The dependence of c/a axial ratio on manganese content suggests that Mn³⁺ species substituted tetragonal Ti⁴⁺. The annealing at 873 K caused changes in surface structure, morphology and roughness. A migration of manganese ions into the rutile single crystal takes place and in certain conditions Ti₂O phase occurs. Mn-implanted samples exhibit room temperature ferromagnetism and a Curie temperature of 680 K. Electron spin resonance analysis evidenced that manganese is incorporated by substitution as magnetically isolated Mn⁴⁺, Mn³⁺ and Mn²⁺ species. At 0.07% contents the Mn³⁺ species may enter in interstitial sites contributing to extinction of substitutional magnetic moment.     

LiNi1 ? x ? yCoxMnyO2 (x = y = 0.1, 0.2, 0.33) cathode materials prepared using mechanical activation: Structure, state of ions, and electrochemical performance

We have investigated LiNi_{1 − x − y} Co _x Mn _y O₂ (x = y = 0.1, 0.2, 0.33) cathode materials synthesized from mechanically activated mixtures of lithium hydroxide and nickel cobalt manganese hydroxide. The materials have a layered structure (sp. gr. ). Their unit-cell volume and the degree of disordering in their structure decrease with decreasing nickel content. According to x-ray photoelectron spectroscopy data, the major states of the transition-metal ions in the surface layer of the materials are Ni²⁺, Co³⁺, and Mn⁴⁺. With increasing nickel content, the Ni 2p _3/2 and Co 2p _3/2 binding energies increase, attesting to changes in M-O bond covalence. The highest specific electrochemical capacity, ∼170 mA h/g, is offered by LiNi_0.6Co_0.2Mn_0.2O₂. The position of redox peaks in the differential capacity curves of the three materials depends on composition: with increasing nickel content, the peaks shift to lower voltages. Original Russian Text ? N.V. Kosova, E.T. Devyatkina, V.V. Kaichev, 2007, published in Neorganicheskie Materialy, 2007, Vol. 43, No. 2, pp. 227–235.     

Preparation of ultra-fine cobalt-nickel manganite powders and ceramics derived from mixed oxalate

Co_0.30Ni_0.66Mn_2.04O₄ negative temperature coefficient ceramics were derived from mixed oxalate Co_0.30Ni_0.66Mn_2.04(C₂O₄)₃·nH₂O. The mixed oxalate was synthesized by milling a mixture of cobalt acetate, nickel acetate, manganese acetate, and oxalic acid at room temperature. An ultra-fine Co_0.30Ni_0.66Mn_2.04O₄ powder was obtained by calcining the mixed oxalate in air at 800 °C for 3 h. The oxide powder compact was sintered at a relatively low temperature of 1100 °C for 5 h, achieving a relative density of ∼98%. The specific resistivity ρ_25 °C and the thermal constant B_25/85 °C were 765.2 Ω cm and 3604 K, respectively. The resistance drift after aging at 150 °C for 500 h was 1.5%.     

Studying trivalent/bivalent metal ion doped TiO2 as p-TiO2 in bipolar heterojunction devices

Trivalent/bivalent metal ions doped TiO₂ thin films (M_xTi_1−xO₂, M = Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺, Mn²⁺ and x = 0.01, 0.05, 0.1, 0.15, 0.2) were deposited on Indium–tin oxide (ITO) coated glass substrates by spin coating technique. X-ray photoelectron spectroscopy (XPS) showed Ti⁴⁺ oxidation state of the Ti2p band in the doped p-TiO₂. The homogenous M_xTi_1−xO₂ was used to support n-ZnO thin films with thickness ∼40–80 nm and vertically aligned n-ZnO nanorods (NR) with length ∼300 nm and 1.5 μm. Current (I)–voltage (V) characteristics for the Ag/n-ZnO/M_xTi_1−xO₂/ITO/glass assembly showed rectifying behavior with small turn-on voltages (V₀) < 1 V. The ideality factor (η) and the resistances in both forward and reverse bias were calculated. The temperature dependence performance of these bipolar devices was performed and variation of the parameters with temperature was studied.     

Studies on the structure and gas sensing properties of nickel–cobalt ferrite thin films prepared by spin coating

The influence of Co²⁺ ions content on structure and sensing properties of Ni_1−xCo_xFe₂O₄ (x = 0.25, 0.5, 0.75) thin films deposited on glass substrates by spin coating is presented. Structural characterization evidenced thin films with cubic spinel structures and morphologies dependent on cobalt content. Repartition of cations in spinel tetrahedral and octahedral sites was determined and was found that the presence of Co²⁺ ions in octahedral sites favor the formation of Fe²⁺ species. The sensitivity to some reducing vapor gases (acetone, liquefied petroleum gas LPG, ethyl alcohol and methyl alcohol) was investigated and was found that thin films with x = 0.75 exhibit high sensitivity to ethyl alcohol and thin films with x = 0.25 have high sensitivity to acetone. This sensitivity largely depends on the temperature and test gas concentration and was related to the Fe²⁺ species formed in octahedral sites.     

Cobalt oxide (Co3O4) nanorings prepared from hexagonal β-Co(OH)2 nanosheets

Hexagonal cobalt hydroxide (β-Co(OH)₂) nanosheets over a size range from 100 nm to 1 μm were synthesized using a very simple hydrothermal route with cobalt naphthenate as the cobalt source. Additionally, hexagonal cobalt oxide (Co₃O₄) nanorings over a size range from 100 nm to 1 μm consisting of cubic nanocrystals were obtained via a hydrothermal method using as-prepared β-Co(OH)₂ nanosheets as the precursors. A probable mechanism of formation of the hexagonal Co₃O₄ nanorings is proposed on the basis of time-dependent experimental results.     

Porous Cobalt–Nickel Hydroxide Nanosheets with Active Cobalt Ions for Overall Water Splitting

Low‐cost and high‐performance catalysts are of great significance for electrochemical water splitting. Here, it is reported that a laser‐synthesized catalyst, porous Co_0.75Ni_0.25(OH)₂ nanosheets, is highly active for catalyzing overall water splitting. The porous nanosheets exhibit low overpotentials for hydrogen evolution reaction (95 mV@10 mA cm^?2) and oxygen evolution reaction (235 mV@10 mA cm^?2). As both anode and cathode catalysts, the porous nanosheets achieve a current density of 10 mA cm^?2 at an external voltage of 1.56 V, which is much lower than that of commercial Ir/C‐Pt/C couple (1.62 V). Experimental and theoretical investigations reveal that numerous Co³⁺ ions are generated on the pore wall of nanosheets, and the unique atomic structure around Co³⁺ ions leads to appropriate electronic structure and adsorption energy of intermediates, thus accelerating hydrogen and oxygen evolution.     

Thermal stability against reduction of LaMn1−yCoyO3 perovskites

Thermal and reduction-oxidation stability of substituted LaMn_1−yCo_yO₃ perovskite-type oxides (0.0 ≤ y_Co ≤ 1.0) prepared by the citrate route have been studied by means of surface area, X-ray diffraction, FTIR spectroscopy and magnetic properties. The perovskite orthorhombic structure is found for y_Co ≤ 0.5, with the exception of y_Co = 0.1, which corresponds better to rhombohedral LaMnO_3.15. For y_Co > 0.5 the diffraction profiles are quite similar to the cobaltite’s rhombohedral structure. Magnetic iso-field studies (ZFC-FC) reveal that, for y_Co ≤ 0.50, the system presents an antiferromagnetic canted-like ordering of the Mn/Co sublattice, in which the presence of divalent Co ion creates Mn³⁺-Mn⁴⁺ pairs that interact ferromagnetically through the oxygen orbital. This interpretation is confirmed by the magnetization loops, in which the magnetic moment increases when substituting Mn for Co. Therefore, the general trend is: for y_Co ≤ 0.5, the Co ions are inserted in the manganite structure and for y_Co > 0.5, the Mn ions are inserted in cobaltite structure. The enhancement of the ferromagnetic properties and the thermal stability against reduction for y_Co = 0.5 is attributed to optimized Co²⁺-Mn⁴⁺ interactions.     

EPR Study of MnO and MnO2 Doped Barium Aluminoborate Glasses

An off-equilibrium redox condition study of Mn²⁺ and Mn⁴⁺ ions added to the batch is reported for the case of the preparation of the barium aluminoborate glasses, by considering that the out of equilibrium reactions started already on the melt. It is shown that for lower dopant concentrations the relative concentrations of the oxidation states of the manganese are found out of equilibrium up to the added amount of 0.3 mol% of MnO₂, but on doping with MnO, the equilibrium state is achieved at the MnO added amount of 0.07 mol%. The change of the redox condition of the manganese ions toward the equilibrium was studied by tracking the Mn²⁺ amount as a function of the doping concentration in the two cases of MnO and MnO₂.     

Electrical and optical properties of ZnO:Mn thin films grown by MOCVD

Diluted magnetic semiconductor epitaxial thin films of Zn_1 − xMn_xO have been grown on c-sapphire by the MOCVD technique. Variations of a and c lattice parameters follow Vegard's law and attest to the incorporation of substitutional Mn²⁺ ions. Carrier concentration (n-type) and electron mobility were studied versus temperature for different concentrations of manganese. Incorporation of manganese leads to the opening of the band gap, observed as a blue shift in energy regarding pure ZnO.     

First-principle calculations of anomalous spin-state excitation in LaCoO3

We investigate the different spin states of LaCoO₃ employing the state-of-the-art ab initio band structure calculations within a rotationally invariant formulation of local density approximation (LDA) + U approach. The various magnetically ordered spin states of different supercells have been studied, including the low-spin state (LS), intermediate-spin state (IS), high-spin state (HS) Co³⁺ ions, as well as all combinations among these three states. The ground state is correctly predicted to be an insulator nonmagnetic state. Our calculations, together with previous susceptibility measurements for IS excitations in the LS ground state, lead to the conclusion that the nonmagnetic–paramagnetic transition in LaCoO₃ at 90 K is caused by a gradual population of IS Co³⁺ ionic states. Our results show that the first thermally excited spin-state occurs from LS to an LS (Co_LS³⁺ = 87.5%)–IS (Co_IS³⁺ = 12.5%) ordered state, which can be distinguished from the LS–HS or IS state. We find that the mixture of LS–IS, LS–HS, and HS–IS spin states may develop an orbital ordering.     

Mn:SnO2 ceramics as p-type oxide semiconductor

SnO₂-based ceramics substituted with manganese as a new p-type oxide semiconductor were prepared by conventional solid state reaction. The Mn was ranged from 5 to 20 mol%, and the microstructure as well as the physical and chemical properties was characterized. Single-phase rutile of Mn:SnO₂ solid solution was obtained in all compositions. Lattice parameter was decreased with the increase of amount of Mn. The compositional change and electrical properties of the Mn:SnO₂ ceramics were confirmed by X-ray photoelectron spectroscopy and Hall effect measurement. The 5-10 mol% Mn:SnO₂ solid solutions exhibited electrically p-type behavior. The simultaneous presence of Mn²⁺, Mn³⁺ and Mn⁴⁺ states was approved and Sn⁴⁺ in Mn:SnO₂ ceramics was partially substituted with Mn³⁺ which contributes p-type behavior. SnO₂ substituted with higher contents of Mn³⁺ of 50% exhibits p-type semiconductor.     

Spin reversal, magnetic domains and relaxation mechanisms in Er(Co,Mn)O3 perovskites

Substitution of Mn by a divalent metal in rare-earth manganites REMe_xMn_1 − xO₃ results in the simultaneous presence of Mn³⁺ and Mn⁴⁺. The RE sublattice interacts with the local field imposed by the Mn network and may orientate in a parallel direction, or align in the opposite direction resulting in an uncompensated antiferromagnetic structure. We present the magnetic properties of ErCo_xMn_1 − xO₃, in which manganese is substituted by cobalt. Coexistence of different interactions leads to unusual phenomena: a spin reversal, a step-like transition due to a reorientation of domains, a relaxation mechanism connected to the rotation energy of domains, the intersection of increasing and decreasing branches in the magnetization loops.     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.