Structure and redox properties of CexPr1−xO2−δ mixed oxides and their catalytic activities for CO, CH3OH and CH4 combustion

A series of Ce_xPr_1−xO_2−δ mixed oxides were synthesized by a sol–gel method and characterized by Raman, XRD and TPR techniques. The oxidation activity for CO, CH₃OH and CH₄ on these mixed oxides was investigated. When the value x was changed from 1.0 to 0.8, only a cubic phase CeO₂ was observed. The samples were greatly crystallized in the range of the value x from 0.99 to 0.80, which is due to the formation of solid solutions caused by the complete insertion of Pr into the CeO₂ crystal lattices. Raman bands at 465 and 1150 cm⁻¹ in Ce_xPr_1−xO_2−δ samples are attributed to the Raman active F_2g mode of CeO₂. The broad band at around 570 cm⁻¹ in the region of 0.3 ≤ x ≤ 0.99 can be linked to oxygen vacancies. The new band at 195 cm⁻¹ may be ascribed to the asymmetric vibration caused by the formation of oxygen vacancies. The TPR profile of Pr₆O₁₁ shows two reduction peaks and the reduction process is followed: . The reduction temperature of Ce_xPr_1−xO_2−δ mixed oxides is lower than those of Pr₆O₁₁ or CeO₂. TPR results indicate that Ce_xPr_1−xO_2−δ mixed oxides have higher redox properties because of the formation of Ce_xPr_1−xO_2−δ solid solutions. The presence of the oxygen vacancies favors CO and CH₃OH oxidation, while the activity of CH₄ oxidation is mostly related to reduction temperatures and redox properties.     

Density functional theory analysis of CaRgn complexes: (Rg=He, Ne, Ar; n=1–4)

CaRg_n⁺ (Rg=He, Ne, Ar) complexes with n=1–4, are investigated by performing using the B3LYP/6-311+G (3df) density functional theory calculations. The CaHe_n⁺ (n=1–4) complexes are found to be stable. In the case of CaNe_n⁺ and CaAr_n⁺, stable structures and stationary point were found only for n=1 and 2. For n=3 in the C_3V and the D_3h point group as well as for n=4 in the T_d (tetrahedral) point group a saddle point (imaginary frequency) is observed and global minimum could be obtained along the potential energy surface.     

A spectroscopic study on the 12-heteropolyacids of molybdenum and tungsten (H3PMo12−nWnO40) combined with cetylpyridinium bromide in the epoxidation of cyclopentene

The epoxidation of cyclopentene with hydrogen peroxide catalyzed by 12-heteropolyacids of molybdenum and tungsten (H₃PMo_12−nW_nO₄₀, n = 1–11), 12-tungstophosphoric acid and 12-molybdophosphoric acid combined with cetylpyridinium bromide as a phase transfer reagent was carried out in acetonitrile. Among 13 heteropolyacids investigated, catalyst of H₃PMo₆W₆O₄₀ showed the highest activity, giving a conversion of 60% and a selectivity of 95% in the epoxidation of cyclopentene. The fresh catalysts and the catalysts under reaction condition were characterized by UV–vis, FT-IR and ³¹P NMR spectroscopy, which has revealed that all of the molybdotungstophosphoric acids were degraded in the presence of hydrogen peroxide to form a considerable amount of phosphorus-containing species. The active species resulted from H₃PMo₆W₆O₄₀ are new kinds of phosphorus-containing species, which is different from {PO₄[WO(O₂)₂]₄}³⁻.     

First principles study of the structure, electronic state and stability of SinCm anions

Structure, electronic state and energy of Si_nC⁻ and Si_nC⁻₂ (n=1–7) anions have been investigated using the density functional theory. Structural optimization and frequency analysis are performed at the level B3LYP/6-311G(d). The charged-induced structural changes in these anions have been discussed. The strong C–C bond is also favored over C–Si bonds in the Si_nC⁻_m anions in comparison with corresponding neutral cluster. Among different Si_nC⁻ and Si_nC⁻₂ (n=1–7) anions, Si₃C⁻, Si₅C⁻ and Si₂C⁻₂ are most stable. Their stability has a decreasing tendency with the increase in the size of these clusters.     

I NQR and spectroscopic investigation of impurity-doped and mixed lithium iodate Li1−xHxIO3 crystals

The ¹²⁷I NQR, IR absorption and Raman spectra of impurity-doped and mixed lithium iodate Li_1−xH_xIO₃ crystals grown from water solutions with different LiIO₃/HIO₃ ratios were investigated depending on the content of the impurity hydrogen x. The NQR results suggested that, at small concentration of doping iodic acid x<0.22, the lattice dynamics of the crystal grown from water solution changes significantly though the crystal retains hexagonal symmetry. Spectroscopic studies are compatible with average hexagonal symmetry of the grown doped crystals. From the results of Raman studies at room temperature and 100 K, the concentration range of hydrogen dopant 0.22<x<0.36 was found where disordered solid solution crystals Li_1−xH_xIO₃ are formed.     

Sub-solidus phase equilibria in CeO2–SrO system

In this communication, we report on the synthesis and characterization of a series of compounds with the general composition Ce_1−xSr_xO_2−x (0.0≤x≤1.0), to establish a detailed phase relation in the CeO₂–SrO system. The X-ray diffraction (XRD) pattern of the each product was refined to determine the solid solubility and the homogeneity range. The solid solubility limit of SrO in CeO₂ lattice, under the slow cooled conditions, is represented as Ce_0.91Sr_0.09O_1.91 (i.e. 9 mol% of SrO). A careful delineation of the phase boundary revealed that the stoichiometric SrCeO₃, in fact, contains a little amount of CeO₂ also. The mono-phasic compound could be obtained at the nominal composition Sr_0.55Ce_0.45O_1.45. The nominal composition Sr₂CeO₄, under the heat treatment used in the present investigation, was a bi-phasic mixture of SrCeO₃ and SrO. No new ordered phases were obtained in this system.     

Molecular motion and phase transition in perovskite-type (CH3)nNH4−nSnCl3 (n=1–4) studied by proton NMR spin–lattice relaxation

Powder X-ray diffraction, ¹¹⁹Sn NMR spectra, and ¹H NMR spin–lattice relaxation times, T₁, were measured for (CH₃)_nNH_4−nSnCl₃ (n=1–4). From the Rietveld analysis, it is shown that all four compounds crystallize into deformed perovskite-type structures at room temperature. The temperature dependence of ¹H T₁ was analyzed in terms of the CH₃ reorientation and other motions of the whole cation. Except for the phase transition in CH₃NH₃SnCl₃, which is from monoclinic to rhombohedral at 331 K, ¹H T₁ was continuously changed at other phase transitions in this compound as well as in the n=2–4 compounds, suggesting that the transitions are not caused by the change of the motional state of the cation but by an instability of the [SnCl₃]_nⁿ⁻ perovskite lattice.     

The electrolyte NRTL model and speciation approach as applied to multicomponent aqueous solutions of H2SO4, Fe2(SO4)3, MgSO4 and Al2(SO4)3 at 230–270 °C

This work presents chemical modeling of solubilities of metal sulfates in aqueous solutions of sulfuric acid at high temperatures. Calculations were compared with experimental solubility measurements of hematite (Fe₂O₃) in aqueous ternary and quaternary systems of H₂SO₄, MgSO₄ and Al₂(SO₄)₃ at high temperatures. A hybrid model of ion-association and electrolyte non-random two liquid (ENRTL) theory was employed to fit solubility data in three ternary systems H₂SO₄–MgSO₄–H₂O, H₂SO₄–Al₂(SO₄)₃–H₂O at 235–270 °C and H₂SO₄–Fe₂(SO₄)₃–H₂O at 150–270 °C. Employing the Aspen Plus™ property program, the electrolyte NRTL local composition model was used for calculating activity coefficients of the ions Al³⁺, Mg²⁺ Fe³⁺ and SO₄²⁻, HSO₄⁻, OH⁻, H₃O⁺, respectively, as well as molecular species. The solid phases were hydronium alunite (H₃O)Al₃(SO₄)₂(OH)₆, hematite Fe₂O₃ and magnesium sulfate monohydrate (MgSO₄)·H₂O which were employed as constraint precipitation solids in calculating the metal sulfate solubilities. A correlation for the equilibrium constants of the association reactions of complex species versus temperature was implemented. Based on the maximum-likelihood principle, the binary interaction energy parameters for the ionic species as well as the coefficients for equilibrium constants of the reactions were obtained simultaneously using the solubility data of the ternary systems. Following that, the solubilities of metal sulfates in the quaternary systems H₂SO₄–Fe₂(SO₄)₃–MgSO₄–H₂O, H₂SO₄–Fe₂(SO₄)₃–Al₂(SO₄)₃–H₂O at 250 °C and H₂SO₄–Al₂(SO₄)₃–MgSO₄–H₂O at 230–270 °C were predicted. The calculated results were in excellent agreement with the experimental data.     

Synthesis and low temperature fluorination of the alkaline-earth palladates Ba2−xSrxPdO3 (x = 0–2)

Since the discovery of superconductivity in Sr₂CuO₂F_2+δ there has been an increased interest in ternary oxide-fluorides. Sr₂CuO₂F_2+δ is prepared via low temperature (T = 220 °C) reaction routes. Low temperature fluorination induces an interesting structural rearrangement in the parent compound Sr₂CuO₃, which is a one-dimensional material containing linear chains of vertex sharing CuO₄ squares along the crystallographic b axis. Upon fluorination, one oxide is substituted by two fluorides and Cu²⁺ becomes octahedrally coordinated by four oxides and two fluorides. The fluorinated compound Sr₂CuO₂F_2+δ displays the T-type structure (La₂CuO₄). Insertion of excess fluorine, δ, also takes place and this fluorine occupies interstitial sites in the T structure. Although the starting material Ca₂CuO₃ is isostructural to Sr₂CuO₃, Ca₂CuO₂F_2+δ displays the T′ (Nd₂CuO₄) structure due to the smaller radius of Ca²⁺ compared to that of Sr²⁺.

The alkaline-earth palladates with the general formula A₂PdO₃ (A = Ba, Sr) are isostructural with the A₂CuO₃(A = Ca, Sr) materials. We prepared the Ba_2−xSr_xPdO₃ (x = 0–2) series and performed low temperature fluorination, which led to the synthesis of the series Ba_2−xSr_xPdO₂F_2+δ (0 ≤ x ≤ 1.5). All the compounds in the Ba_2−xSr_xPdO₂F_2+δ series show T′ structure (Ca₂CuO₂F_2+δ). Similarities and differences with Sr₂CuO₂F_2+δ and Ca₂CuO₂F_2+δ will be discussed.     

High surface area nickel aluminate spinels prepared by a sol–gel method

The oxide spinel NiAl₂O₄ and spinel-type solid solutions Al₂O₃–NiAl₂O₄ (at Ni/Al=1:4, and Ni/Al=1:8) were prepared by controlled hydrolysis of mixed metal alkoxides, followed by calcination of the resulting gels. Powder X-ray diffraction showed that all samples prepared were single phase cubic materials having the spinel-type structure. The cubic lattice parameter, a_o, was found to decrease gradually with increasing aluminium content of the mixed metal oxides. The specific surface area (determined by nitrogen adsorption at 77 K) was found to be in the range of 200–300 m² g⁻¹. The materials were found to be basically mesoporous, the most frequent pore radius being in the range 3.2–6.4 nm. IR spectroscopy of CO adsorbed at liquid nitrogen temperature gave a main band at 2186–2195 cm⁻¹, which was assigned to the C---O stretching vibration of surface Al³⁺CO adducts where coordinatively unsaturated Al³⁺ ions act as Lewis acid centres.     

Evidence of lanthanum–chromium mixed oxides formed in CrOx/La2O3 model catalysts

CrO_x/La₂O₃ mixed oxides, prepared by impregnating La₂O₃ with appropriate aqueous solutions of (NH₄)₂CrO₄ and calcining at 600 °C for 4 h, have been investigated by means of XRD, TPR, XPS, DRIFTS, and Raman spectroscopy (RS). The formation of the compounds La₂CrO₆, La(OH)CrO₄ and LaCrO₄ under these conditions was evidenced. Strong peaks at 864, 884, 913, and 921 cm⁻¹, as well as weak peaks at 136, 180, 354, 370, and 388 cm⁻¹ in the RS spectrum of CrO_x/La₂O₃ have been assigned to La₂CrO₆.     

Global minima of (C60)nCa, (C60)nF and (C60)nI clusters

Likely candidates for the lowest potential energy minima of (C₆₀)_nCa²⁺, (C₆₀)_nF⁻ and (C₆₀)_nI⁻ clusters are located using basin-hopping global optimisation. In each case, the potential energy surface is constructed using the Girifalco form for the C₆₀ intermolecular interaction, an averaged Lennard–Jones C₆₀–ion interaction, and a polarisation potential, which depends on the first few non-vanishing C₆₀ multipole polarisabilities. We find that the ions generally occupy the interstitial sites of a (C₆₀)_n cluster, the coordination shell being tetrahedral for Ca²⁺ and F⁻. The I⁻ ion has an octahedral coordination shell in the global minimum for (C₆₀)₆I⁻, however for 12  n  8 the preferred coordination geometry is trigonal prismatic.     

EPR and UV–visible spectroscopic studies of alumina-supported chromium oxide catalysts

The oxidation state, the mobility and the molecular structure of chromium species present on CrO_x–Al₂O₃ catalysts have been studied by combined diffuse reflectance spectroscopy, EPR and reduction–extraction by ethane 1,2 diol. CrO₄²⁻ species exist on the alumina surface in the form of loosely-interacting species on hydrated surface (species A) and in the form of strongly bonded species on dehydrated Al₂O₃ surface (species B). The CrO₄²⁻ species show high mobility and are probably responsible for the formation of CrO_x clusters.     

Properties of Ce–Zr–La–O nano-system with ruthenium modified surface

Structural peculiarities of Ce–Zr–La–O and Ce–Zr–La–O/Ru samples in mean of catalytic properties are compared. The samples (Ce:Zr = 1:1, La = 10÷30 mol.%, Ru = 1.5 wt.%) were obtained by sol–gel method (X-samples) and co-precipitation (P-samples). It is shown that Ce_0.45Zr_0.45La_0.1O_2−δ/Ru X-samples are characterized by high thermal stability and the highest catalytic activity in partial methane oxidation reaction. According to XRD, BET, FTIR, EPR and XPS data it is concluded that the difference in the samples catalytic activity is caused by various disposition of Ru-containing phase on the support surface. The distinction in the dimension of Ru-containing particles (3D or 2D) is conditioned by structural peculiarities of Ce_0.45Zr_0.45La_0.1O_2−δ and Ce_0.35Zr_0.35La_0.3O_2−δ P- and X-samples.     

Hydrothermal synthesis, crystal structure and characterization of [Zn(H2O)4]2 [H2As6V15O42(H2O)]·2H2O

The compound [Zn(H₂O)₄]₂[H₂As₆V₁₅O₄₂(H₂O)]·2H₂O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å³, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H₂As₆V₁₅O₄₂(H₂O)]⁴⁻ anions and [Zn(H₂O)₄]²⁺ cations linked through hydrogen bonds into a network. The [H₂As₆V₁₅O₄₂(H₂O)]⁶⁻ cluster consists of 15 VO₅ square pyramids linked by three As₂O₅ handle-like units.     

Relationship between temperature-programmed reduction profile and activity of modified ferrite-based catalysts for WGS reaction

A series of modified ferrites were prepared by doping iron oxide with various transition/non-transition/inner-transition metal ions [M = Cr, Mn, Co, Ni, Cu, Zn and Ce] in situ during synthesis. All the modified ferrites thus obtained exhibit remarkably high surface areas, greater than that of pure iron oxide (Fe₂O₃) sample. The efficacy of the dopant ions in modifying the resultant specific surface area, could be directly related to variations in the rate of crystal growth. The nature and concentration of the foreign cations present in the system govern this variation. Interestingly all the modified ferrites, exhibit a narrow pore size distribution in the range of 4.9–25 nm. XRD analysis revealed the existence of hematite (Fe₂O₃) phase in all the as-prepared samples. The X-ray diffraction experiments performed on activated catalysts, confirmed the existence of magnetite (Fe₃O₄) phase with a nominal composition of Fe_2.73M_0.27O₄. These inverse or mixed spinels with general formula A_(1−δ)B_δ[A_δB_(2−δ)]O₄, possess highly facile Fe³⁺  Fe²⁺ redox couple, the degree of facileness depends on the extent of synergistic interaction between iron and the other substitutent metal ion. The rapid electron hopping between Fe³⁺  Fe²⁺ in the Fe₃O₄ lattice system is essential to catalyze WGS reaction. From TPR it was observed that, incorporation of metal cations into the hematite (-Fe₂O₃) crystal structure alters the reducibility of the hematite particles, which in turn depends on the nature of the incorporated metal cation. A plausible explanation for the WGS activity over various modified ferrites has been attempted with the help of TPR analysis.     

Catalytic decomposition of H2O2 on Co3O4 doped with MgO and V2O5

The effects of doping of Co₃O₄with MgO (0.4–6 mol%) and V₂O₅ (0.20–0.75 mol%) on its surface and catalytic properties were investigated using nitrogen adsorption at −196°C and decomposition of H₂O₂ at 30–50°C. Pure and doped samples were prepared by thermal decomposition in air at 500–900°C, of pure basic cobalt carbonate and basic carbonate treated with different proportions of magnesium nitrate and ammonium vanadate. The results revealed that, V₂O₅ doping followed by precalcination at 500–900°C did not much modify the specific surface area of the treated Co₃O₄ solid. Treatment of Co₃O₄ with MgO at 500–900°C resulted in a significant increase in the specific surface area of cobaltic oxide. The catalytic activity in H₂O₂ decomposition, of Co₃O₄ was found to suffer a considerable increase by treatment with MgO. The maximum increase in the catalytic reaction rate constant (k) measured at 40°C on Co₃O₄ due to doping with 3 mol% MgO attained 218, 590 and 275% for the catalysts precalcined at 500, 700 and 900°C, respectively. V₂O₅-doping of Co₃O₄ brought about a significant progressive decrease in its catalytic activity. The maximum decrease in the reaction rate constant measured at 40°C over the 0.75 mol% V₂O₅-doped Co₃O₄ solid attained 68 and 93% for the catalyst samples precalcined at 500 and 900°C, respectively. The doping process did not modify the activation energy of the catalyzed reaction but much modified the concentration of catalytically active constituents without changing their energetic nature. MgO-doping increased the concentration of CO³⁺–CO²⁺ ion pairs and created Mg²⁺–CO³⁺ ion pairs increasing thus the number of active constituents involved in the catalytic decomposition of H₂O₂. V₂O₅-doping exerted an opposite effect via decreasing the number of CO³⁺–CO²⁺ ion pairs besides the possible formation of cobalt vanadate.     

球形表面富锰MnxCo3−xO4−ƞ尖晶石型催化剂选择性催化还原NOx研究

采用共沉淀法制备了高比表面积的Mn_xCo_3−xO₄球形催化剂,研究了NH₃选择性催化还原NO_x性能。Mn-Co金属氧化物具有尖晶石结构,随着Co含量的增加,晶体结构由四方相转变为立方相。高浓度的表面活性氧物种和变价元素的强有效电子转移(Co³⁺ + Mn³⁺ ↔ Co²⁺ + Mn⁴⁺)有利于提高Mn_xCo_3−xO₄ (x = 1.0、1.5、2.0)尖晶型石催化剂的氧化还原能力,催化剂表面的Mn富集作用形成了氧缺陷结构和丰富的表面活性位点,进一步促进SCR脱硝反应,呈现出优异的催化性能。Co_tet(CoMn)_octO₄晶体结构中,Mn离子(Mn³⁺和Mn⁴⁺,以三价锰为主)和部分Co离子被配置到八面体中心,这些物种作为活性位点存在着较强的电子转移交互作用,该构型对促进低温脱硝活性和保护活性位点耐受SO₂毒害具有重要的意义。Mn-Co尖晶石表面的NH₃-SCR脱硝反应过程主要遵循Eley-Rideal反应机理,即吸附态NH₃与气态NO (或NO₂)的反应路径。随着反应温度的增加,反应生成的NH₄NO₃中间体很可能转化为NH₄NO₂物种,进而分解为N₂,提高了催化剂的氮气选择性。     

Phase equilibria and crystal structure of the solid solution LaFe1−xNixO3−δ (0 ≤ x ≤ 1)

Phase equilibria in the LaFeO₃–“LaNiO₃” were studied at 1100 °C in air. The samples were synthesized by standard ceramic and/or solution route via nitrate or citrate precursors. According to the results of XRD it was found that the homogeneity ranges of LaFe_1−xNi_xO_3−δ solid solution lay within 0.0 ≤ x ≤ 0.4 (sp.gr. Pbnm) and 0.6 ≤ x ≤ 0.8 (sp.gr. ). The structural parameters (bond lengths, atom coordinates) for the single-phase samples were refined using Rietveld analysis. The unit cell parameters versus LaFe_1−xNi_xO_3−δ composition are presented.     

Coordination geometry of chromium(VI) species. The first example of cis-bridging chromate ions in helically structured catena(μ-CrO4-O,O′)[Ni(HIm)3H2O]

Nickel(II) chromate complex with imidazole (HIm) was isolated from the [Ni²⁺–HIm–CrO₄²⁻] system in various experimental conditions, i.e. reagent molar ratios and nickel(II) salts. The catena(μ-CrO₄-O,O′)[Ni(HIm)₃H₂O] (1) crystallizes in monoclinic crystal system—space group P2₁/n with cell parameters: a=11.784(2), b=8.899(2), c=13.934(3) (Å), β=95.19(3) (°). The unit cell contains two independent helixes, left- and right-handed, stabilized by intrahelical and interhelical hydrogen bonds (HB) and π–π interactions. The cis coordination of the CrO₄²⁻ anions and the HB systems appeared to be the main determinants of the helical architecture. To the best of our knowledge the cis-chromate coordination was observed for the first time. The cis coordination causes the distortion of the nickel octahedron, which was analysed by 4 K single crystal electronic spectra with D_4h symmetry approximation (gaussian resolution and crystal field parameters). This symmetry was also confirmed with the polarised electronic spectra. The magnetic properties of the complex suggest the occurrence of weak intrachain antiferromagnetic interactions between the magnetic Ni^II center. The computational DFT studies of complex 1 assuming three possible isomers mer[(HIm)₃]–cis[(CrO₄²⁻)₂], mer–trans and fac–cis suggested that the main contribution to the stability of 1 might have interhelical and intrahelical hydrogen bonds.