Chemical and structural transformations in manganese aluminum spinel of the composition Mn1.5Al1.5O4 during heating and cooling in air

Single phase cubic spinel of the composition Mn_1.5Al_1.5O₄ is synthesized. Its crystal structure refinement shows that 0.4Mn+0.6Al are in the octahedral sites and 0.7Mn+0.3Al are in the tetrahedral sites. High temperature X-ray diffraction is used to analyze Mn_1.5Al_1.5O₄ behavior during heating and cooling in air. In a temperature range of 600°C to 700°C, initial spinel splits into layers, and the sample represents a twophase system: cubic spinel Mn_0.4Al_2.4O₄ and a phase based on β-Mn₃O₄. Above 900°C the sample again turns into single phase cubic spinel. The role of oxidizing processes in the decomposition of Mn_1.5Al_1.5O₄ caused by oxygenation and partial oxidation of Mn²⁺ to Mn³⁺ is shown. A scheme of structural transformations of manganese aluminum spinel during heating from room temperature and cooling from 950°C is proposed.     

High-Temperature X-Ray Diffraction Investigation of the Decomposition Process in Manganese-Gallium Spinel Mn<Subscript>1.5</Subscript>Ga<Subscript>1.5</Subscript>O<Subscript>4</Subscript>

The stability of spinel-type mixed Mn_1.5Ga_1.5O₄ oxide prepared in an inert medium (1000 °C, Ar) is studied by thermogravimetry and high-temperature X-ray diffraction in air in a wide temperature range 30–1000 °C. On heating, reversible decomposition processes of initial spinel are observed. From 30 °C to 600 °C oxygen atoms attach to the surface layer of initial Mn_1.5Ga_1.5O₄ spinel to form a new phase distinct from parent oxide by the oxygen stoichiometry (cation vacancies are formed). The product of decomposition is two oxides: Mn_1.5Ga_1.5O₄ and Mn_1.5–xGa_1.5–x[·]_xO₄. On the contrary, above 600 °C a loss of oxygen occurs, the concentration of cation vacancies decreases in Mn_1.5–xGa_1.5–x[·]_xO₄, and the reverse process of single phase oxide crystallization takes place. At 1000 °C the spinel phase forms again whose composition is similar to that of the initial parent phase Mn_1.5Ga_1.5O₄. On cooling the decomposition of this phase is again observed due to oxygen attachment.     

One-step synthesis of nitrogen-doped few-layer graphene structures decorated with Mn1.5Co1.5O4 nanoparticles for highly efficient electrocatalysis of oxygen reduction reaction

A nanocomposite consisting of nitrogen-doped few-layer graphene structures, the surface of which is decorated with nanocrystallites of Mn_1.5Co_1.5O₄ spinel oxide, was prepared by a single-stage method of plasma-assisted electrochemical exfoliation of graphite in a solution of 1 M NaNO₃ + 0.005 M MnSO₄ + 0.005 M CoSO₄ + 0.01 M melamine. The high catalytic activity of the synthesized catalyst in the oxygen reduction reaction is due to pyridine nitrogen atoms and Mn_1.5Co_1.5O₄ spinel nanoparticles.     

Electrochemical properties of nano-crystalline LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> synthesized by polymer-pyrolysis method

LiNi_0.5Mn_1.5O₄ powders were prepared through polymer-pyrolysis method. XRD and TEM analysis indicated that the pure spinel structure was formed at around 450 °C due to the very homogeneous intermixing of cations at the atomic scale in the starting precursor in this method, while the well-defined octahedral crystals appeared at a relatively high calcination temperature of 900 °C with a uniform particle size of about 100 nm. When cycled between 3.5 and 4.9 V at a current density of 50 mA/g, the as prepared LiNi_0.5Mn_1.5O₄ delivered an initial discharge capacity of 112.9 mAh/g and demonstrated an excellent cyclability with 97.3% capacity retentive after 50 cycles.     

High-temperature X-ray study of the formation and delamination of manganese-alumina spinel Mn<Subscript>1.5</Subscript>Al<Subscript>1.5</Subscript>O<Subscript>4</Subscript>

The behavior of the manganese-alumina system with Mn:Al = 1:1 on heating in air and vacuum was studied. The starting samples were mixtures of β-Mn₃O₄, α-Mn₂O₃, and γ-Al₂O₃. On heating to 950°C in air, the samples were partially oxidized into α-Mn₂O₃, and corundum α-Al₂O₃ formed along with mixed manganese-alumina cubic spinel, whose composition was close to Mn₂AlO₄. In vacuum at 1200°C, the starting sample with a ratio of Mn:Al = 1:1 transformed into the manganese-alumina spinel Mn_1.5Al_1.5O₄, which retained its cubic structure after slow cooling in vacuum. When cooled in air, this solid solution delaminated, and a nanocrystalline Mn_2.8Al_0.2O₄ phase formed, whose structure was β-Mn₃O₄ type tetragonal spinel.     

High performance LiNi0.5Mn1.5O4 cathode materials synthesized by a combinational annealing method

High performance LiNi_0.5Mn_1.5O₄ was prepared by a combinational annealing method. All samples were characterized by X-ray diffraction, infrared, and cell measurements. With increasing the annealing time at 600 °C, LiNi_0.5Mn_1.5O₄ showed a decreased lattice parameter and an enhanced Ni-ordering. The electrochemical property of LiNi_0.5Mn_1.5O₄ was optimized by controlling the annealing time. It was found that after annealing at 600 °C for 8 h, LiNi_0.5Mn_1.5O₄ can discharge up to 138 mA h g⁻¹ with a superior cycling performance at the rate of 5/7 C. High-rate test indicated that LiNi_0.5Mn_1.5O₄ exhibited excellent electrochemical performance when charged and discharged at 1.2 C and 2.5 C, respectively. The findings reported in this work are expected to pave the way for the practical application of LiNi_0.5Mn_1.5O₄.     

Enhancements of rate capability and cyclic performance of spinel LiNi0.5Mn1.5O4 by trace Ru-doping

The rate capability and cyclic performance of the LiNi_0.5Mn_1.5O₄ under high current density have been significantly improved by doping a small amount of ruthenium (Ru). Specifically, Li_1.1Ni_0.35Ru_0.05Mn_1.5O₄ and LiNi_0.4Ru_0.05Mn_1.5O₄ synthesized by solid state reaction can respectively deliver a discharge capacity of 108 and 117 mAh g^?1 at 10 C rate between 3 and 5 V. At 10 C charge/discharge rate, Li_1.1Ni_0.35Ru_0.05Mn_1.5O₄ and LiNi_0.4Ru_0.05Mn_1.5O₄ can respectively maintain 91% and 84% of their initial capacity after 500 cycles, demonstrating that Ru-doping could be a way to enhance the electrochemical performance of spinel LiNi_0.5Mn_1.5O₄.     

Comprehensive reinvestigation on the initial coulombic efficiency and capacity fading mechanism of LiNi0.5Mn1.5O4 at low rate and elevated temperature

The effect of different membranes and aluminum current collectors on the initial coulombic efficiency of LiNi_0.5Mn_1.5O₄/Li was investigated, and the cycling performance at different rates and temperatures and the storage performance at 60 °C for a week are discussed for LiNi_0.5Mn_1.5O₄/Li. The results show that the lower initial coulombic efficiency is associated with the lower decomposition voltage of the commercial membrane and electrolyte, and the instability of aluminum current collector under the higher voltage. In addition, both versions of LiNi_0.5Mn_1.5O₄ can deliver about 115 mA?h g^?1 of initial discharge capacity at 1 C at 25 °C and 60 °C; however, it retains only 61.57 % of its initial capacity after the 130th cycles at 60 °C, which is much lower than the 94.46 % rate observed for LiNi_0.5Mn_1.5O₄ at 25 °C, and the cycling performance of the material at 1 C is better than that at 0.5 C. Meanwhile, the initial discharge capacity at 0.1 C after storing at 60 °C is 119.3 mA?h g^?1, which is only a little lower than 121.5 mA?h g^?1 recorded before storing; moreover, the spinel structure and surface state of LiNi_0.5Mn_1.5O₄ after storing at 60 °C has not been changed basically. These results indicate that the electrochemical stability of electrolyte is also related to the temperature. The serious capacity fading of LiNi_0.5Mn_1.5O₄ at 60 °C is attributed to the severe oxidation decomposition and the thermal decomposition in the range of cut-off voltage of the materials, and then the decomposition products interact with active materials to form a solid interface phase, leading to the larger electrode polarization and irreversible capacity loss. Meanwhile, the worse cycling performance at 0.5 C than that at 1 C is attributed to the longer interaction time between the electrolyte and the active materials. However, the storage performance of LiNi_0.5Mn_1.5O₄ corresponds to the thermal stability of electrolyte to a certain extent.     

Utilizationof dta for two-step synthesisof Cu–Mn–Cr spinel

The novel two-step synthesis method decreasing the calcining temperature necessary for formation of spinel lattice and as well for reaching of bright and clear hue of the pigments prepared were investigated. This work aims to utilization of DTA for synthesis monitoring. Influence of raw materials and temperature of calcination on color properties were observed. The characterization of the samples was performed by X-ray diffraction and colorimetry in the CIE L*a*b* system. It was proved that the black spinel pigment Cu_2.3Mn_2.8Cr_4.9O_x can be prepared at finally temperature 700°C as one-phase system with high quality black hue.     

Dimethyl Ether—Reforming Catalysts for Hydrogen Production

This article reviews our recent works on dimethyl ether steam reforming (DME SR) over nanocomposite catalysts of copper-based spinel oxide and solid-acid catalyst. A series of Cu-based spinels was prepared by citric acid complexation method and their catalytic performance was studied in terms of activity, selectivity, and stability. The influence of preparation conditions, such as calcination temperature, reduction temperature, and chemical composition, and reforming conditions, such as steam-to-carbon ratio and reaction temperature, was systematically studied. Effect of type of solid-acid catalyst was also reported. Zeolite-based composites and alumina-based ones are highly active in temperature ranges of <300 °C and >300 °C, respectively. The composite of CuFe₂O₄ and alumina treated thermally in air at 700–800 °C exhibited excellent activity and stability in DME SR. Upon H₂ reduction, phase separation of copper spinel to metallic copper nanoparticles and host oxides proceeds. The high dispersion of the Cu particles (Cu¹⁺-rich surface of ca. 70%) on the hosts, and the strong chemical interaction between them could be observed. The H₂-rich reformate (>70% H₂) could be attained for longer than 800 h at 375 °C, showing the good potential for practical use in H₂ and fuel cell applications. Doping Ni to CuFe₂O₄ significantly enhanced the stability of the catalyst, in accordance with the alloying effect. Regeneration of the degraded catalysts could be obtained by simple heat-treatment since carbon deposits were removed, and spinel structures were reconstructed.     

Synthesis,characterization and photocatalytic properties of Mg1−xZnxAl2O4 spinel nanoparticles

Mg_1−xZn_xAl₂O₄ spinel nanoparticles with x = 0, 0.05, 0.10, 0.15 and 0.20 were prepared via the chemical coprecipitation method. The obtained samples were characterised by thermal gravimetric and differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectroscopy, UV–Vis diffuse reflection spectrum, transmission electron microscopy and ²⁷Al MAS-NMR spectroscopy. Mg_1−xZn_xAl₂O₄ spinel powders with the mean crystallite size of around 11 nm–14 nm were obtained. The crystallinity of the MgAl₂O₄ samples increases with the increase in the calcination temperature. At the same calcination temperature, higher amount of Zn²⁺ substitution leads to the higher level of crystallinity, but has no apparent influence on the mean crystallite size of the samples. The photocatalytic activity of the obtained Mg_1−xZn_xAl₂O₄ spinel nanoparticles was evaluated by monitoring the degradation of methylene blue under UV light. The degradation rates of methylene blue using the MgAl₂O₄ nanoparticles prepared at the calcination temperatures of 700 °C and 800 °C are much higher than those prepared at 900 °C and 1000 °C. The photocatalytic activities of the spinel powders with lower level of Zn²⁺ substitution such as Mg_0.95Zn_0.05Al₂O₄ are inferior to that of MgAl₂O₄. Results of ²⁷Al MAS-NMR spectroscopy analysis and the first principle total density of state calculations reveal that this is probably due to the substitutions of Zn²⁺ decreasing the degree of Al³⁺ ions inversion over the sites of tetrahedral and octahedral coordination. With the increase in the amounts of Zn²⁺ substitution, the effects of Zn²⁺ additions on the photocatalytic activities become gradually predominant, leading to the increases in the degradation rates. The methylene blue degraded by 99% within 4 h using the Mg_0.8Zn_0.2Al₂O₄ spinel powders.     

Direct-methane solid oxide fuel cells with Cu1.3Mn1.7O4 spinel internal reforming layer

Cu_1.3Mn_1.7O₄ spinel oxide has been synthesized and characterized as anode internal reforming layer for Ni–SDC anode-supported solid oxide fuel cells (SOFCs) directly operating on methane fuel. XRD and Cu mapping image results of Cu_1.3Mn_1.7O₄ oxide after in-situ reduction by methane show that a highly dispersed nano-Cu metal network has been obtained. By adopting Cu_1.3Mn_1.7O₄ as an internal reforming layer, the cell demonstrated maximum power densities of 242 and 311 mW cm^?2 at 650 and 700 °C, respectively using methane as fuel and ambient air as oxidant. More importantly, Cu_1.3Mn_1.7O₄ internal reforming layer has significantly improved the cell performance stability. The cell with the Cu_1.3Mn_1.7O₄ internal reforming layer has demonstrated reasonably stable performance while the cell without it degraded very rapidly.     

Effect of anions on the structure and catalytic properties of a La-doped Cu-Mn catalyst in the water-gas shift reaction

Effects of the anion type on the structure, thermal stability, and catalytic performance of La-doped Cu-Mn catalysts prepared by co-precipitation were characterized by X-ray diffraction, Brunauer-Emmett-Teller, temperature-programmed reduction, temperature-programmed reduction of oxidized surfaces, and temperature-programmed desorption. The Cu-Mn catalyst was tested for the water-gas shift (WGS) reaction. The main crystalline phase of samples prepared with sulfate, acetate, chloride, and nitrate as the starting materials was a Cu_1.5Mn_1.5O₄ spinel structure, following the WGS reaction, the main crystalline phases were transformed into Cu and MnO. The sample prepared with acetate as the starting material showed the most obvious MnCO₃ characteristic diffraction peaks, with better synergistic effects of Cu and MnO, increased adsorption of CO₂ and improved dispersion of Cu on the catalyst surface; also, the best thermal stability and the highest low temperature catalytic activity were observed. The sample prepared with nitrate as the starting material maintained high thermal stability and catalytic performance in the range of 400°C to 450°C, but CO conversion decreased below 350°C. Catalytic performance of the sample prepared with sulfate and chloride as the starting materials was poor, ranging from 200°C to 450°C.     

Synthesis and electrochemical properties of high-voltage LiNi0.5Mn1.5O4 electrode material for Li-ion batteries by the polymer-pyrolysis method

A submicron LiNi_0.5Mn_1.5O₄ cathode was synthesized via the pyrolysis of polyacrylate salts as precursor polymerized by reaction of the metal salts with acrylate acid. The structure and morphology of the resulting compound was characterized by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results reveal that the prepared LiNi_0.5Mn_1.5O₄ cathode material has a pure cubic spinel structure and submicron-sized morphology even if calcined at 900 °C and quenched to room temperature. The LiNi_0.5Mn_1.5O₄ electrodes exhibited promising high-rate characteristics and delivered stable discharge capacity (90 mAh/g) with excellent retention capacity at the current density of 50 mA/g between 3.5 and 4.9 V. The capacity of the LiNi_0.5Mn_1.5O₄ electrodes remains stable even after 30 cycles at low or high current density. This polymer-pyrolysis method is simple and particularly suitable for preparation of the spinel LiNi_0.5Mn_1.5O₄ cathode material compared to the conventional synthesis techniques.     

Synthesis and characterisation of cobaltite and ferrite spinels using thermogravimetric analysis and X-ray crystallography

The synthesis for a series of ferrite (M^IIFe₂O₄) and cobaltite (M^IICo₂O₄) spinels was investigated where M^II is Mg, Co, Ni, Cu or Zn. The ferrites were prepared at a calcination temperature of 800 °C; the cobaltites at 500 °C. TG–MS indicated that reduction of Co^III to Co^II occurs at ca. 800 °C, hence, the lower calcination temperature. For both the ferrites and the cobaltites, the evolution of water and CO₂ during the calcination suggests the presence of both species in the precipitates. The observed mass losses indicated that the precursor basic carbonate precipitates for the cobaltite synthesis were predominantly carbonate, while the precursor basic carbonate precipitates for ferrite synthesis were predominantly hydroxide in character. XRD data showed successful synthesis of the ferrites with minimal contamination from the parent oxides, while the cobaltites were observed to be predominantly of the spinel structure.     

Preparation and characterization of Bi0.75Er0.25O1.5 and Bi0.75Er0.125Y0.125O1.5 nanocrystalline ceramics by SPS

Nanopowders of Bi_0.75Er_0.25O_1.5 and Bi_0.75Er_0.125Y_0.125O_1.5 were prepared by a reverse titration chemical coprecipitation method under controlled pH conditions. After calcination at 500 °C for 3 h, powders with grain size in the order of 10 nm were obtained. In order to keep the nanosize of grains, these powders were densified by spark plasma sintering. Samples with relative density higher than 96% were prepared in only 10 min up to 500 °C with an average grain size of 15 and 11 nm for Bi_0.75Er_0.25O_1.5 and Bi_0.75Er_0.125Y_0.125O_1.5, respectively. Impedance spectroscopy revealed slightly higher conductivity for the Bi_0.75Er_0.125Y_0.125O_1.5 composition compared to Bi_0.75Er_0.25O_1.5 nanoceramic, but performances remained lower than the corresponding Bi_0.75Er_0.25O_1.5 microcrystalline sample. However, mechanical properties of both nanocrystalline ceramics are improved when compared to microcrystalline samples.     

凝胶燃烧法合成5V级正极材料LiNi_(0.5)Mn_(1.5)O_4及其高倍率放电性能

采用聚乙烯吡咯烷酮(PVP)作为络合剂和燃料以凝胶燃烧法制备了具有优异高倍率放电性能的亚微米LiNi0.5Mn1.5O4材料.用热重/差热分析(TG/DTA)研究了凝胶的燃烧过程,用X射线衍射(XRD)、扫描电镜(SEM)和循环伏安(CV)研究了LiNi0.5Mn1.5O4材料的结构和形貌.结果表明材料为结晶良好的纯尖晶石相结构,由5μm左右的二次颗粒组成,颗粒大小分布均匀,一次晶粒发育良好,粒径在500nm左右.充放电测试表明材料的倍率性能和循环性能十分优异.在3.5至4.9V进行充放电测试,0.5C、1C、4C、8C和10C倍率下放电容量分别为131.9、127.6、123.4、118.4和113.7mAh·g-1.在10C大倍率放电条件下循环100、500和1000次的容量保持率分别为91.4%、80.9%和73.5%.     

Effects of gamma-irradiation on physicochemical state of surface and catalytic properties of CuO/MgO and NiO/MgO systems

Copper and nickel oxide samples supported on MgO were prepared by wet impregnation method. The obtained solids were heated at 350 °C and 450 °C. The extent of copper and nickel oxides was fixed at 16.7 mol%. The effect of g-irradiation (0.2-1.6 MGy) on the surface and catalytic properties of the solids were investigated. The techniques employed were XRD, nitrogen adsorption at -196 °C and H₂O₂ decomposition. The results revealed that the g-irradiation up to 0.8 MGy of CuO/MgO-450 °C effected a measurable decrease in the crystallite size of CuO phase with subsequent increase in its degree of ordering. Irradiation at a dose of 1.6 MGy brought about a complete conversion of MgO into Mg(OH)₂ during its cooling from 450 °C to room temperature via interacting with atmospheric water vapor. The S _BET and total pore volume of CuO/MgO precalcined at 350 °C and 450 °C increased progressively as a function of g-ray dose reached a maximum limit at 0.8 MGy. Gamma-irradiation of NiO/MgO-450 °C solids up to 0.8 MGy increased the degree of ordering of MgO and NiO phases without changing their crystallite size. The exposure of these solids to 1.6 MGy led to an effective transformation of some of NiO (not dissolved in MgO lattice) into Ni(OH)₂ via interacting with atmospheric water vapor during cooling from 450 °C to room temperature. Gamma-irradiation led to a measurable increase in the S _BET and V _p of NiO/MgO system. Gamma-irradiation of the two investigated systems resulted in both increase and decrease in their catalytic activities in H₂O₂ decomposition depending mainly on the irradiation dose and calcination temperature. This treatment, however, did not modify the mechanism of the catalytic reaction, but changed the catalytic active sites without changing their energetic nature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and characterization of a novel washcoat material and supported Pd catalysts

A nanosized Ce_0.5Mn_0.5O_1.5 powder was successfully synthesized by macromolecule surfactant modified method and then it was used as the cordierite honeycomb washcoat of VOCs combustion catalysts. The effect of Ce-Mn-O powder with different Ce/Mn molar ratio on the catalytic activity and the cohesive ability of washcoat on the cordierite honeycomb substrate was also investigated. The structure and catalytic properties of Ce_0.5Mn_0.5O_1.5 washcoat were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM), differential thermal analysis and thermo-gravimetric analysis (TG/DTA), and N₂ adsorption and desorption techniques. The results indicated that the Ce_0.5Mn_0.5O_1.5 powder belongs to a novel washcoat with the advantages of strong cohesiveness, high surface area and without agglomeration even after 1000°C calcination. The total oxidation temperature for toluene, acetone and ethyl acetate over the 0.1 wt % Pd/Ce_0.5Mn_0.5O_1.5/cordierite honeycomb catalysts was at 200, 220 and 220°C, respectively. Compaired with the catalysts without Ce_0.5Mn_0.5O_1.5 washcoat, the catalyst with Ce_0.5Mn_0.5O_1.5 as washcoat on the cordierite honeycomb could improve the dispersion of PdO and shows a good catalytic activity for toluene, acetone and ethyl acetate.     

Solid-state reactions in the system Cu—Sb—O; Formation of a new copper(I) antimony oxide

The solid-state reactions in the system Cu—Sb—O were investigated by thermogravimetry and X-ray diffraction. Equimolar mixtures of CuO and Sb₂O₃ form Cu(II)Sb₂O₆ when slowly heated in air up to 1000°C. The firt step in this reaction is the oxidation of Sb₂O₃ to Sb₂O₄ at 380–500°C, followed by further oxidation of Sb₂O₄ and the formation of CuSb₂O₆ at 500–1000°C. Thermal decomposition of CuSb₂O₆ in a flowing nitrogen atmosphere occurs in three stages; the first, with an activation energy of 356 kJ mole^?1, results in the formation of a new copper(I) antimony oxide, with a composition of Cu₄SbO_4.5, as determined by atomic absorption analysis and X-ray fluoresecence. Confirmation of predominantly monovalent copper and pentavalent antimony in the new compound was by ESR and ESCA, respectively. Two forms of Cu₄SbO_4.5 have been distinguished; one of these (form II) has a structure of lower symmetry, and decomposes when heated in air at 600°C to a mixture of CuO and another new copper antimony oxide, as yet uncharacterized. On further heating to 1100°C in air, Cu₄SbO_4.5 (form I) gradually reforms. Details of these reactions are summarized and X-ray powder data presented for Cu₄SbO_4.5.