Catalytic properties in N2O decomposition of mixed cobalt–iron spinels

The effect of introduction of iron in the Co_3 − xFe_xO₄ on catalytic activity in N₂O decomposition was investigated. The spinel catalysts were characterized by XRD, SEM, RS, BET methods, work function measurements and Mössbauer spectroscopy. Introduction of iron in the Co_3 − xFe_xO₄ spinel catalysts at the level of x < 1 leads to preferential substitution of Fe³⁺ in tetrahedral sites, whereas for x > 1 also octahedral ones are substituted. A strong correlation between deN₂O activity (T_50%) and work function was observed showing that electronic factor controls the catalytic reactivity of Co–Fe spinels. The results revealed that the active centers for N₂O decomposition are cobalt ions and thus even a low level of their substitution by iron leads to substantial decrease of the deN₂O activity of the cobalt spinel.     

Phase diagram of the pseudobinary system Bi–Co–O

Samples with different ratios of Bi₂O₃ and Co₂O₃ were prepared by ceramic route. Based on the results of differential thermal analysis, X-ray powder diffraction, SEM–EDXA and FactSage database the phase diagram of the Bi–Co–O diagram in air atmosphere was assessed and calculated using the FactSage software. The sillenite structure of Bi₂₄Co₂O₃₉ was identified and the single phase homogeneity range of Bi₂₄Bi_2?xCo_xO₃₉, x = 0.9–2.0 was determined by Rietveld analysis and SEM–EDXA. To verify the composition in the various parts of the phase diagram at elevated temperatures, a number of high-temperature annealing experiments was performed followed by rapid quenching to room temperature.     

Hydrothermal synthesis,characterization and magnetic properties of a new 2D arsenic–vanadate layers supported cobalt coordination complex: [Co(en)2(H2O)]{[Co(en)2]2As8V14O42(SO4)} · 3H2O

The title compound [Co(en)₂(H₂O)]{[Co(en)₂]₂As₈V₁₄O₄₂(SO₄)} · 3H₂O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum and thermogravimetric analysis. The single crystal diffraction analysis shows that compound 1 exhibits {[Co(en)₂]₂As₈V₁₄O₄₂(SO₄)}n²ⁿ⁻ layers act as ligand of coordination cations [Co(en)₂]²⁺, and water molecules are inserted in the layers. The magnetic measurement indicates a weak antiferromagnetic exchange coupling within the molecular unit, which is deemed to attribute to the contribution of V^iv and Co²⁺.     

Modulation of selective sites by introduction of N2O,CO2 and H2 as gaseous promoters into the feed during oxidation reactions

Results obtained by adding gaseous promoters (CO₂, N₂O and H₂) into the reaction feed are presented for two different reactions: (i) oxidative dehydrogenation of propane (ODP), and (ii) catalytic combustion of methane (CCM). The ODP is performed on a mixture of NiMoO₄ and CeO₂, by adding 3 vol.% CO₂ into the feed, and on a NiMoO₄/[Si,V]-MCM-41 mesoporous catalyst, in the presence of 1 or 5 vol.% N₂O in the feed. The CCM is carried out (i) on Pd(2 wt.%)/Ce_xZr_1−xO₂ and Pd(2 wt.%)/γ-Al₂O₃ catalysts, on pure CeO₂ and on a mixture of Pd(2 wt.%)/γ-Al₂O₃ and CeO₂ powders, by adding 3 vol.% CO₂ into the feed, and (ii) on a Pd(2 wt.%)/γ-Al₂O₃ catalyst, in the presence of various amounts of H₂ in the feed. It is shown, through all these various examples, that the activity and/or the selectivity of catalysts can be improved by tuning, in a very controlled manner, the oxidation state of active sites via the use of these gaseous promoters.     

Promising high temperature thermoelectric properties of dense Ba2Co9O14 ceramics

Layered cobalt oxides have shown high thermoelectric properties. The n = 1 member of the Ba_n+1Co_nO_3n+3(Co₈O₈) family, Ba₂Co₉O₁₄, a new layered cobalt oxides family with Co(II) and Co(III) in the CdI₂ layers, has been synthesized by solid state reaction and sintered as dense ceramics (relative density ∼ 93%) by Spark Plasma Sintering. It presents promising p-type thermoelectric properties at high temperature. The dimensionless figure of merit ZT is 0.032 at 660 K and 0.04 at 1000 K, which is about one quarter to one third of the ZT value of Ca₃Co₄O₉ ceramics.     

Electrochemical characteristics of LiNi0.5Co0.5O2 synthesized at 800 °C from the different combinations of carbonates,oxides, and hydroxides

LiNi_0.5Co_0.5O₂ cathode materials were synthesized by a solid-state reaction method at 800 °C using Li₂CO₃, LiOH·H₂O; NiO, NiCO₃; CoCO₃, or Co₃O₄ as the sources of Li, Ni, and Co, respectively. The electrochemical properties of the synthesized samples were then investigated. The structure of the synthesized LiNi_0.5Co_0.5O₂ was analyzed, and the microstructures of the samples were observed. The curves of voltage vs. x in Li_xNi_0.5Co_0.5O₂ for first charge–discharge and intercalated and deintercalated Li quantity Δx were studied. Destruction of unstable 3b sites and phase transitions were discussed from the first and second charge–discharge curves of voltage vs. x in Li_xNi_0.5Co_0.5O₂. The LiNi_0.5Co_0.5O₂ sample synthesized from Li₂CO₃, NiCO₃ and Co₃O₄ has the largest first discharge capacity (142 mAh/g). The LiNi_0.5Co_0.5O₂ sample synthesized from Li₂CO₃, NiO and Co₃O₄ has a relatively large first discharge capacity (141 mAh/g) and the smallest capacity deterioration rate (4.6 mAh/g/cycle).     

Low-temperature continuous wet oxidation of trichloroethylene over CoOx/TiO2 catalysts

TiO₂-supported metal oxides such as CoO_x, CuO_x, NiO_x and FeO_x have been used for catalytic wet oxidation of trichloroethylene (TCE) in a continuous flow type fixed-bed reactor system, and the most promising catalyst for this wet catalysis has been characterized using XPS and XRD techniques. All the supported catalysts gave relatively low conversions for the wet oxidation at 36 °C, except for 5 wt% CoO_x/TiO₂ which exhibited a steady-state conversion of 45% via a transient activity behavior up to 1 h on stream. XPS measurements yielded that a Co 2p_3/2 main peak at 779.8 eV appeared with the 5 wt% CoO_x/TiO₂ catalyst after the continuous wet TCE oxidation at 36 °C for ca. 6 h (spent catalyst) and this binding energy value was equal to that of Co₃O₄ among reference Co compounds used here, while the catalyst calcined at 570 °C (fresh catalyst) possessed a main peak at 781.3 eV, very similar to that for CoTiO_x species such as CoTiO₃ and Co₂TiO₄. Only characteristic reflections for Co₃O₄ were indicated upon XRD measurements even with the fresh catalyst sample. The simplest model, based on these XPS and XRD results, for nanosized Co₃O₄ particles existing with the fresh catalyst could reasonably explain the transient activity behavior observed upon the wet TCE oxidation.     

Magnetic and phonon transitions in B-site Co doped BiFeO3 ceramics

Magnetic susceptibility and phonons have been characterized in multiferroic Bi(Fe_1−xCo_x)O_3−δ ceramics for x=0.0, 0.05, and 0.10 (BFO100xCo) as functions of temperature. A preferred (100) crystallographic orientation and increasing average oxygen vacancies were observed in BFO5Co and BFO10Co. The Fe and Co K-edge synchrotron X-ray absorptions revealed mixed valences of Fe³⁺, Fe⁴⁺, Co²⁺, and Co³⁺ ions in BFO5Co and BFO10Co, which exhibit a ferromagnetic (or ferrimagnetic) phase below room temperature due to appearance of ferromagnetic B–O–B (B=Fe and Co) superexchange interactions. Field–cooled (FC) and zero–field–cooled (ZFC) magnetic susceptibilities exhibit a significant spin-glass splitting below room temperature in BFO5Co and BFO10Co. Two Raman-active phonon anomalies at ~170 K (or 200 K) and ~260 K were attributed to the Fe³⁺–O–Co³⁺ and Co³⁺–O–Co³⁺ magnetic orderings, respectively. This work suggests that the low-spin Co²⁺–O–Co²⁺, Fe³⁺–O–Fe³⁺ (or Fe⁴⁺), and high-spin Co²⁺–O–Co²⁺ superexchange interactions are responsible for phonon anomalies at ~290 (or ~300 K), ~400, and ~470 K (or ~520 K) in BFO5Co and BFO10Co.     

The CO methanation over NaY-zeolite supported Ni/Co3O4, Ni/ZrO2, Co3O4/ZrO2 and Ni/Co3O4/ZrO2 catalysts

The CO methanation was studied over zeolite NaY supported Ni, Co₃O₄, ZrO₂ catalysts. The XRD, N₂ physisorption and SEM analysis were used in order to characterize the catalysts. Catalytic activities were carried out under a feed composition of 1% CO, 50% H₂ and 49% He between the 125 °C to 375 °C. Except for the Ni/Co₃O₄/NaY catalyst, all catalysts gave high surface area because of the presence of zeolite NaY. Average pore diameter of the catalysts fell into the mesopore diameter range. The highest CO methanation activity was obtained with Ni/ZrO₂/NaY catalyst at which the CO methanation was started after 175 °C and 100% CO conversion was obtained at 275 °C using the same catalyst.     

Blue-violet ceramic pigments based on Co and Mg Co2−xMgxP2O7 diphosphates

Solid solutions of Co and Mg diphosphates with compositions Co_2?xMg_xP₂O₇ (x = 0, 0.1, 0.2, 0.3, 0.5, 0.7, 1.0, 1.5 and 1.8) have been prepared and characterized for the first time as alternative low-toxicity blue ceramic pigments. The compositions were prepared through the conventional coprecipitation route and calcined up to 1000 °C/2 h. Samples were characterized by thermal analysis, XRD, SEM/EDX, UV–vis-NIR spectroscopy and colour measurements (CIE-L^*a^*b^*). Isostructural Co_2?xMg_xP₂O₇ diphosphate solid solutions (monoclinic system and P21/c spatial group) formed successfully within the studied range of compositions, accompanied only by a minor quantity of residual Co or Mg orthophosphates (M₃(PO₄)₂). Interestingly, the obtained solid solutions developed nice blue-violet colourations even with high Mg doping after enamelling within double-firing (x = 1.5–1.8) and single-firing (x = 1.0–1.5) ceramic glasses. These optimal compositions containing a minimized Co amount (measured values around 7–16 wt%) could be therefore less toxic alternatives to the conventional Co₃(PO₄)₂ blue ceramic pigment.     

Highly active SO2-resistant ex-framework FeMFI catalysts for direct N2O decomposition

Ex-framework FeMFI catalysts, prepared by isomorphous substitution of iron in the aluminosilicate or gallosilicate MFI-type framework and activation by calcination at 823 K and steaming (300 mbar H₂O in N₂) at 873 K, show high activity and stability in N₂O decomposition in the presence of O₂, CO₂, H₂O, and SO₂. The N₂O conversion of the ex-framework catalysts in simulated tail-gas mixtures was >80% at 800 K and 75,000 h⁻¹. The specific activity per mole of Fe (turnover frequency, TOF) of the ex-framework catalysts in N₂O–He is four to nine times higher than observed for catalysts prepared by conventional solid and liquid-ion exchange, and sublimation methods. The stability of ex-framework catalysts for the direct N₂O decomposition, in the absence of any reductant, is remarkable, showing no significant deactivation (at N₂O conversion levels ranging from 20 to 65%) after 600 h on stream. Sublimed and especially ion-exchanged FeZSM-5 catalysts show a strong irreversible deactivation in feed mixtures containing H₂O and SO₂. The effect of SO₂ on the catalytic performance of FeMFI catalysts is discussed, as well as the applicability of the ex-framework FeMFI catalysts in fluid-bed combustion facilities.     

A DFT study of methanol oxidation on Co3O4

By means of spin polarized density functional theory with the GGA + U framework, the reaction mechanism of CH₃OH oxidation on the Co₃O₄ (110)-B and (111)-B surfaces has been investigated. Adsorption situation and a part of reaction cycle for CH₃OH oxidation are clarified. Our results indicated that: i) U value can affect the calculated energetic result significantly; ii) CH₃OH can adsorb with surface lattice oxygen atom (O_2f/O_3f) to form CoO bond directly, and the adsorption of CH₃OH and its decomposition products on (110)-B is more stable than on (111)-B, which means CH₃OH prefers Co^3 + better than Co^2 +; iii) on the (110)-B surface, CH₃OH can form CO₂, H₂O and adsorbed H atom. But on the (111)-B surface, CH₃OH can just form formaldehyde (CH₂O) and adsorbed H atom, this means oxidative capacity of (110)-B (Co^3 +) is higher than (111)-B (Co^2 +). The possible reasons corresponding to the high oxidative of (110)-B come from both Co^3 + and O_2f: Co^3 + tends to bind adsorbed species for further decomposition and O_2f tends to bind more hydrogenation atom involved in methanol due to its low-coordinates number compared to that of O_3f.     

Electrochemical characteristics of LiNi0.9Co0.1O2 synthesized at 800 °C from the different combinations of carbonates and oxides

Cathode active materials with a composition of LiNi_0.9Co_0.1O₂ were synthesized by a solid-state reaction method at 800 °C using Li₂CO₃, NiO or NiCO₃, and CoCO₃ or Co₃O₄ as the sources of Li, Ni, and Co, respectively. The electrochemical properties of the synthesized samples were then investigated. The structure of the synthesized LiNi_0.9Co_0.1O₂ was analyzed, and the microstructures of the samples were observed. The curves of voltage vs. x in Li_xNi_0.9Co_0.1O₂ for the first charge–discharge and the intercalated and deintercalated Li quantity Δx were studied. The LiNi_0.9Co_0.1O₂ sample synthesized from Li₂CO₃, NiCO₃, and Co₃O₄ had the largest first discharge capacity (152 mAh/g), with a discharge capacity deterioration rate of 1.4 mAh/g/cycle.     

Polyoxometalate as co-catalyst of tetrabutylammonium bromide in polyethylene glycol (PEG) for coupling reaction of CO2 and propylene oxide or ethylene oxide

The coupling reaction of CO₂ and propylene oxide or ethylene oxide to produce corresponding cyclic carbonate in the presence of a catalytic system composed of n-Bu₄NBr, α₂-(n-Bu₄N)₉P₂W₁₇O₆₁(Co²⁺ · Br) (abbreviated as P₂W₁₇Co) and PEG (MW 400) has been investigated. The experimental results indicated that the synthesis of propylene carbonate (PC) or ethylene carbonate (EC) achieved with over 98% yield and 100% selectivity within 1 h at 120 °C by using the above catalyst system. When the catalyst system was recycled, the catalytic activity slowly diminished. Moreover, a plausible mechanism was proposed.     

NO SCR with propane and propene on Co-based alumina catalysts prepared by co-precipitation

Homogeneous dispersions and small size of deposited high-content cobalt on alumina were achieved by the co-precipitation method and were well maintained on the cobalt-based binary alumina catalysts with Zn, Ag, Fe, Cu or Ni as modifiers. The component and concentration of deposited cobalt species were characterized by UV–vis, EDX and XPS spectra and found to be greatly related to the Co loading, calcination temperatures and the type of additive metals. The optimal Co loading of 8 wt% and calcination temperatures of 800 °C were demonstrated. With respect to the single cobalt-based alumina catalyst, the surface concentration of Co²⁺ on the binary catalysts with addition of Fe, Cu, Ag or Ni was all reduced and accompanying with part conversion of Co²⁺ to Co₃O₄ on the Fe and Ni-modified catalysts. A slight enhanced surface Co²⁺ concentration was only achieved on the Zn-promoted catalyst. It was also demonstrated that for the case of Cu and Fe the additive metals themselves participated in the activation of propene. The octahedral and tetrahedral Co²⁺ ions were suggested as the common active sites. A maximum deNOx activity of 96% was observed on the 8Co4ZnA800 catalyst at the reaction temperatures of 450 °C, and the catalytic performance on the cobalt-based binary alumina catalysts can be described as fellows: CoZn > CoAg, CoNi > Co Cu > CoFe. Based on the in situ DRIFT spectra, different reaction intermediates R–ONO and –NCO besides –NO₂ were formed on the 8Co4ZnA800 and 8Co4FeA800 samples, respectively, demonstrating their dissimilar reaction mechanisms.     

Synthesis and microwave dielectric properties of Bi2Ge3O9 ceramics for application as advanced ceramic substrate

During the synthesis of Bi₂Ge₃O₉ ceramics using Bi₂O₃ + 3GeO₂ powders, the Bi₄Ge₃O₁₂ phase was formed at low temperature (≤800 °C). Bi₄Ge₃O₁₂ preferentially adopted GeO₂-excess phase, and this phase was consistently present in the sintered Bi₂Ge₃O₉ ceramic as a secondary phase. Therefore, Bi₄Ge₃O₁₂ powder was first calcined and subsequently reacted with GeO₂ powder to obtain the pure Bi₂Ge₃O₉ ceramic through the following reaction: 1/2Bi₄Ge₃O₁₂ + 3/2GeO₂ → Bi₂Ge₃O₉. Formation of the Bi₂Ge₃O₉ phase was initiated at temperature of 850 °C. The pure Bi₂Ge₃O₉ ceramic sintered at 875 °C for 8 h had a dense microstructure with an average grain size of 2.7 μm. Furthermore, the pure Bi₂Ge₃O₉ ceramic exhibited promising microwave dielectric properties for the advanced ceramic substrate: ε_r = 9.7, Q × f = 48,573 GHz and τ_f = −29.5 ppm/°C.     

Enhanced transport critical current density of (Bi,Pb)-2223/Ag superconductor tapes added with nano-sized Bi2O3

Ag sheathed superconductor tapes with starting composition (Bi, Pb)-2223(Bi₂O₃)_0.01 were prepared. Bi₂O₃ with average size 150 nm was used in this work. The Bi₂O₃ amount was chosen based on our initial study on nano-sized Bi₂O₃ added pellets which showed an optimal superconducting property for 0.01 wt% addition. Non-added tapes were also prepared for comparison. The tapes were investigated by X-ray diffraction method, scanning electron microscopy and transport critical current density, J_c measurements (30 K to 77 K). The influence of different sintering times (50, 100, and 150 h) on J_c under applied magnetic field (0–0.75 T at 77 K) parallel and perpendicular to the surface of the tapes was also investigated. J_c of added tapes was found to increase significantly as compared with the non-added tapes. The Bi₂O₃ added tapes sintered for 150 h exhibited the highest J_c at 30 K of 57,900 A/cm² as compared with 19,400 A/cm² for the non-added tapes sintered for 100 h. The improvements in flux pinning and connectivity between grains due to nano Bi₂O₃ addition led to the enhancement of J_c.     

A novel three-dimensional coordination polymer containing tetranuclear [Co4(μ3-OH)2] building blocks: Synthesis,crystal structure and magnetic behavior of {[Co2(btc)(μ3-OH)(H2O)2] · H2O}n

A cobalt coordination polymer {[Co₂(btc)(μ₃-OH)(H₂O)₂] · H₂O}_n 1 (btc = 1,2,4-benzenetricarboxylate) was synthesized hydrothermally and structurally characterized by single-crystal X-ray diffraction method. In 1, the six-coordinated Co(II) ions are held together by two bridging hydroxides to form a tetranuclear [Co₄(μ₃-OH)₂] unit, which are connected further through btc³⁻ ligands in a new μ₇-bridging mode to give a porous three dimensional framework. The study of magnetic properties indicated dominant antiferromagnetic coupling interactions between the adjacent Co(II) sites.     

Preparation of high-performance Ca3Co4O9 thermoelectric ceramics produced by a new two-step method

High-performance Ca₃Co₄O₉ thermoelectric ceramic has been prepared from a Ca_1?xCo_xO/Ca_yCo_1?yO divorced eutectic structure produced by a directional melt-grown using the laser floating zone technique. This material has been grown at very high solidification rate in order to produce a very fine microstructure to reduce the necessary annealing time to recover the Ca₃Co₄O₉ thermoelectric phase as the major one. As-grown and annealed samples were microstructurally characterized to determine the phases and estimate the extent of Ca₃Co₄O₉ formation with time and related with their thermoelectric performances. The optimum annealing time, 72 h, has been determined by the maximum power factor value (about 0.42 mW K^?2m^?1), which is around the best values reported in textured materials (～0.40 mW K^?2m^?1). This high power factor outcome from the high Ca₃Co₄O₉ phase content, apparent density and Co³⁺/Co⁴⁺ relationship determinations performed in the present work.     

Enhanced thermoelectric properties of CNT dispersed and Na-doped Bi2Ba2Co2Oy composites

The thermoelectric properties of Bi₂Ba₂Co₂O_y and Bi_1.975Na_0.025Ba₂Co₂O_y+x wt% carbon nanotubes (CNT; x=0.00, 0.05, 0.10, 0.15, 0.5, and 1.0) ceramic samples synthesised by the solid-state reaction method were investigated from 300K to 950K. Na doping with a small amount played an important role in reducing resistivity and slightly reduced the Seebeck coefficients and the thermal conductivity. The CNT dispersant increased resistivity, but the thermal conductivity was reduced remarkably. In particular, the Bi_1.975Na_0.025Ba₂Co₂O_y+1.0wt% CNT sample exhibited an ultralow thermal conductivity of 0.39 W K⁻¹ m⁻¹ at 923K. This was attributed to the point defects caused by Na doping and the interface scattering caused by the CNT dispersant. The combination of Na doping and CNT dispersion had better effects on thermoelectric properties. The Bi_1.975Na_0.025Ba₂Co₂O_y+0.5wt% CNT sample exhibited a better dimensionless figure of merit (ZT) value of 0.2 at 923K, which was improved by 78.2%, compared with the undoped Bi₂Ba₂Co₂O_y sample.