Determination of oxygen in oxides by carrier gas hot extraction analysis with simultaneous COx detection

The determination of oxygen by carrier gas hot extraction is the most popular method for oxygen analysis, but its application to high oxygen contents in oxides requires a critical look at the basic assumptions of the method. The process was studied for various oxides (Al₂O₃, Bi₂O₃, Cr₂O₃, Fe₂O₃, MoO₃, NiO, TiO₂, WO₃, Y₂O₃, and ZrO₂) using a modern analyser with IR-detectors for CO₂ and CO. There was a difference specific to oxides that must be known to get the required analytical results with high precision and accuracy. High amounts of CO₂ were formed particularly from Bi₂O₃, Fe₂O₃, MoO₃, NiO, and WO₃. The reaction rate can be controlled with delayed heating of the furnace, so that an oxide sample weight of up to 100 mg can be used. Received: 13 April 1999 / Revised: 24 June 1999 / Accepted: 28 June 1999     

Dehydrogenation of piperazine to pyrazine on oxide surfaces under chromatographic conditions

The conversion of piperazine under pulse-chromatographic conditions on catalysts — anhydrides of polyvalent acids and metal oxides of variable valence (P₂O₅, Cr₂O₃, MoO₃, WO₃, CuO, CoO, NiO, MoO₃ + P₂O₅ andWO₃ + B₂O₃ + CoO) —applied on Chromsorb W was investigated. The principal reaction direction in all cases is dehydrogenation of piperazine to pyrazine (90–94% yields). The most selective catalyst is CuO. The dehydrogenation is accompanied by slight hydrogenolysis to give ethylamine, diethylamine, methylpyrazine, and N-ethylpiperazine. The conversion of piperazine to P₂O₅ is characterized by the lowest activation energy on metal oxides.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1414–1419, October, 1974.     

Novel Bi2WO6‐coupled Fe3O4 Magnetic Photocatalysts: Preparation,Characterization and Photodegradation of Tetracycline Hydrochloride

Novel Bi₂WO₆‐coupled Fe₃O₄ magnetic photocatalysts with excellent and stable photocatalytic activity for degrading tetracycline hydrochloride and RhB were successfully synthesized via a facile solvothermal route. Through the characterization of the as‐prepared magnetic photocatalysts by X‐ray diffractometry, scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy, UV–Vis diffuse reflectance spectra, it was found that the as‐prepared magnetic photocatalysts were synthesized by the coupling of Bi₂WO₆ and Fe₃O₄, and introduction of appropriated Fe₃O₄ can improve nanospheres morphology and visible‐light response. Among them, BFe2 (0.16% Fe₃O₄) exhibited the best photocatalytic activity for degradation of tetracycline hydrochloride (TCH), reaching 81.53% after 90 min. Meanwhile, the as‐prepared magnetic photocatalysts showed great separation and recycle property. Moreover, the results of electrochemical impedance spectroscopy demonstrated that the well conductivity of Fe₃O₄ can promote photogenerated charge carriers transfer and inhibit recombination of electron–hole pairs, so that Bi₂WO₆/Fe₃O₄ exhibited enhanced photocatalytic activity on degradation of TCH and RhB. Hence, this work provides a principle method to synthesize Bi₂WO₆/Fe₃O₄ with excellent photocatalytic performance for actual application, in addition, it showed that introduction of Fe₃O₄ not only can provide magnetism, but also can enhance photocatalytic activity of Bi₂WO₆/Fe₃O₄ magnetic photocatalysts.     

Bi2WO6量子点(QDs)修饰Bi2MoO6-xF2x异质结的构筑及其催化活性增强机理

采用简单沉积-沉淀法合成了Bi₂WO₆@Bi₂MoO_6-xF_2x（BWO/BMO6-xF2x）异质结,借助XRD、XPS、TEM、SEM、EDS、UV-Vis-DRS、PC和EIS等测试技术对其组成、形貌、光吸收特性和光电化学性能等进行系统表征,并以模型污染物罗丹明B（RhB）的光催化降解作为探针反应来评价Bi₂WO₆@Bi₂MoO_6-xF_2x异质结的光催化活性增强机制。形貌分析表明,所得Bi₂MoO₆微球由大量厚度为20~50 nm的纳米片组成;FE-SEM和HR-TEM分析表明,尺寸约为10 nm的Bi₂WO₆量子点均匀沉积在Bi₂MoO_6-xF_2x微球表面,形成新颖的Bi₂WO₆@Bi₂MoO_6-xF_2x异质结;与纯Bi₂MoO₆或者Bi₂WO₆相比,1∶1Bi₂WO₆@Bi₂MoO_6-xF_2x异质结表现出更好的光催化活性和光电流性质,其对RhB光催化降解的表观速率常数分别为纯BMO和BWO的6.4和11.6倍。PC和EIS图谱分析表明,Bi₂WO₆量子点表面沉积显著提高Bi₂MoO_6-xF_2x光生电子/空穴的分离效率和迁移速率;活性物种捕获实验证明了·O₂^-和h⁺是主要的活性物种。根据实验结果,探讨了F^-掺杂和Bi₂WO₆量子点之间的协同效应对Bi₂MoO₆的光催化活性的影响机制。     

Bi2WO6量子点(QDs)修饰Bi2MoO6-xF2x异质结的构筑及其催化活性增强机理

采用简单沉积-沉淀法合成了Bi_2WO_6@Bi_2MoO_(6-x)F_(2x)(BWO/BMO_(6-x)F_(2x))异质结,借助XRD、XPS、TEM、SEM、EDS、UV-Vis-DRS、PC和EIS等测试技术对其组成、形貌、光吸收特性和光电化学性能等进行系统表征,并以模型污染物罗丹明B(Rh B)的光催化降解作为探针反应来评价Bi_2WO_6@Bi_2MoO_(6-x)F_(2x)异质结的光催化活性增强机制。形貌分析表明,所得Bi_2MoO_6微球由大量厚度为20~50 nm的纳米片组成;FE-SEM和HR-TEM分析表明,尺寸约为10 nm的Bi_2WO_6量子点均匀沉积在Bi_2MoO_(6-x)F_(2x)微球表面,形成新颖的Bi_2WO_6@Bi_2MoO_(6-x)F_(2x)异质结;与纯Bi_2MoO_6或者Bi_2WO_6相比,1∶1Bi_2WO_6@Bi_2MoO_(6-x)F_(2x)异质结表现出更好的光催化活性和光电流性质,其对RhB光催化降解的表观速率常数分别为纯BMO和BWO的6.4和11.6倍。PC和EIS图谱分析表明,Bi_2WO_6量子点表面沉积显著提高Bi_2MoO_(6-x)F_(2x)光生电子/空穴的分离效率和迁移速率;活性物种捕获实验证明了·O_2~-和h~+是主要的活性物种。根据实验结果,探讨了F-掺杂和Bi_2WO_6量子点之间的协同效应对Bi_2MoO_6的光催化活性的影响机制。     

A Large Family of Iron Ruddlesden‐Popper Relatives: from Oxides to Oxycarbonates and Oxyhydroxides

Iron oxides, oxyhydroxydes and oxycarbonates derived from the layered Ruddlesden‐Popper (RP) structure form a large family of layered compounds. Besides the classical RP oxides Sr_n+1Fe_nO_3n+1, single intergrowths with the generic formulation (A,Sr)_n+2Fe_nO_3n+2 and (A,Sr)_n+3Fe_nO_3n+3 (A = Tl, Pb, Bi…) can be generated by increasing the multiplicity of the rock salt layers, and multiple intergrowths of these single intergrowths can be synthesized. Starting from oxygen deficient RP oxides such as n = 3 member Sr₃NdFe₃O_9?δ, oxyhydroxydes hydrates and oxyhydroxydes such as Sr₃NdFe₃O_7.5(OH)₂·H₂O and Sr₃NdFe₃O_7.5(OH)₂ can be created topotactically. Carbonate groups can also replace FeO₆ octahedra in the n = 3 member Sr₄Fe₃O₁₀, leading to layered oxycarbonates Sr₄Fe_3?x(CO₃)_xO_10?4x with 0 < × ≤ 1. Shearing mechanism applied transversally to the layers allows collapsed structures to be generated such as the [Bi₂Sr₃Fe₂O₉]_n [Bi₄Sr₆Fe₂O₁₆] family and the ferrite Bi₁₃Ba₂Sr₂₅Fe₁₃O₆₆. Finally the replacement of rock salt SrO layers in the intergrowth Sr₂FeO₄ allows a new series of modulated structures [Sr₈Fe₁₂O₂₆]·[Sr₃Fe₂O₆]_n to be generated, built up of layers of FeO₅ bipyramids and tetragonal pyramids intergrown with perovskite layers.     

Rationally Designed Bi2M2O9 (M = Mo/W) Photocatalysts with Significantly Enhanced Photocatalytic Activity

Novel Bi₂W₂O₉ and Bi₂Mo₂O₉ with irregular polyhedron structure were successfully synthesized by a hydrothermal method. Compared to ordinary Bi₂WO₆ and Bi₂MoO₆, the modified structure of Bi₂W₂O₉ and Bi₂Mo₂O₉ were observed, which led to an enhancement of photocatalytic performance. To investigate the possible mechanism of enhancing photocatalytic efficiency, the crystal structure, morphology, elemental composition, and optical properties of Bi₂WO₆, Bi₂MO₆, Bi₂W₂O₉, and Bi₂Mo₂O₉ were examined. UV-Vis diffuse reflectance spectroscopy revealed the visible-light absorption ability of Bi₂WO₆, Bi₂MO₆, Bi₂W₂O₉, and Bi₂Mo₂O₉. Photoluminescence (PL) and photocurrent indicated that Bi₂W₂O₉ and Bi₂Mo₂O₉ pose an enhanced ability of photogenerated electron–hole pairs separation. Radical trapping experiments revealed that photogenerated holes and superoxide radicals were the main active species. It can be conjectured that the promoted photocatalytic performance related to the modified structure, and a possible mechanism was discussed in detail.     

Methanol oxidation on semiconducting oxides

Correlations between reaction rates and selectivities vs. Egap (eV) of the semiconducting oxides Co₃O₄, CuO, NiO, Cr₂O₃, -Fe₂O₃, TiO₂ and MoO₃ were obtained for the catalytic air oxidation of methanol at 573 K. Higher and lower selectivities to formaldehyde for Egap>2 n-type, and Egap >2 p-type semiconducting oxides, are observed, respectively.     

The Mechanism of Action of a Multicomponent Co-Mo-Bi-Fe-Sb-K-O Catalyst for the Partial Oxidation of Propylene to Acrolein: II. Changes in the Phase Composition of the Catalyst under Reaction Conditions

The structures of a complex multicomponent Co-Mo-Fe-Bi-K-Sb-O catalyst for the oxidation of propylene to acrolein and simpler catalysts from which some catalyst components were absent were studied by X-ray diffraction analysis. The phases of α-CoMoO₄, β-CoMoO₄, Fe₂(MoO₄)₃, Bi₂O₃ ⋅ MoO₃, Bi₂O₃ ⋅ 2MoO₃, Bi₂O₃ ⋅ 3MoO₃, oxidized molybdenum oxide, and reduced molybdenum oxide are the main components of the catalyst. Ternary compounds were not detected. Under catalytic reaction conditions, the relative amounts of the phases changed; this change suggests the occurrence of redox transformations with the participation of these phases, probably, at the interface.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 580–584.Original Russian Text Copyright © 2005 by Shashkin, Udalova, Shibanova, Krylov.     

Selectivity in photocatalysis by particulate semiconductors

TiO₂, Fe₂O₃, CuO, ZnO, ZnS, Nb₂O₅, MoO₃, CdO, CdS, Sb₂O₃, CeO₂, HgO, Pb₂O₃, PbO₂ and Bi₂O₃ microparticles exhibit band gap excitation with UV-A light but they are selective to photodegrade phenols. While TiO₂ anatase and ZnO photocatalyze the degradation of phenol, o-aminophenol, m-aminophenol, p-aminophenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-nitrophenol, p-nitrophenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol and quinol, MoO₃ does not photodegrade any of the fifteen phenols. Fe₂O₃, CuO, ZnS, Nb₂O₅, CdO, CdS, Sb₂O₃, CeO₂, HgO, Pb₂O₃, PbO₂ and Bi₂O₃ are selective in photodegrading the fifteen phenols; however, the phenols get adsorbed over all sixteen particulate semiconductors.      

Five-component reciprocal systems Na,K∥Cl,CO<Subscript>3</Subscript>,MoO<Subscript>4</Subscript>,WO<Subscript>4</Subscript> and Na,K∥F,CO<Subscript>3</Subscript>,MoO<Subscript>4</Subscript>,WO<Subscript>4</Subscript>

Five-component reciprocal systems Na,K∥Cl,CO₃,MoO₄,WO₄ and Na,K∥F,CO₃,MO₄,WO₄ have been studied by differential thermal analysis (DTA) and X-ray powder diffraction (XPD). The systems have been triangulated to phase simplexes. The main reciprocal and complex-formation reactions have been revealed. The stability of [Na,K]₂CO₃, Na₂[Mo,W]O₄, and K₂[Mo,W]O₄ binary solid solutions and the nonexistence of quintuple invariant points in the title systems have been verified.     

TG and DTA study of oxygen depletion and reoxidation of bismuth molybdates (2∶1;2∶3)

Oxygen depletion and reoxidation of bismuth molybdates (2∶1; 2∶3) have been studied by means of isothermal thermogravimetry and DTA measurements. From the isothermal curves, Arrhenius energies were obtained between 411 and 683 K. The activation energies for oxygen depletion from Bi₂O₃·MoO₃ were lower than those for Bi₂O₃·3MoO₃. Two kinetically different types of oxygen release were identified for both molybdates. Arrhenius plots were also obtained from reoxidation experiments: Bi₂O₃·MoO₃ was more easily reoxidable than Bi₂O₃·3MoO₃. The substantial closeness of the respective activation energies suggests that depletion and reoxidation follow the same mechanistic steps. Some DTA measurements confirm the existence of at least two types of reoxidation sites for both oxysalts.     

Determination of the maximum monolayer dispersion and dispersed state for WO3 on γ-Al2O3

The maximum monolayer dispersion (the threshold) for WO₃ on γ-Al₂O₃ calcined at 500°, 550°, 600°, and 640°C has been determined quantitatively by XRD (amount of crystalline phase) and XPS (intensity ratios I_w4f/I_Al2). The results show that if the amount of WO₃ loaded is lower than the maximum monolayer dispersion, WO₃ will react with γ-Al₂O₃ to form surface compound due to mutual ionic interaction, and will be dispersed on γ-Al₂O₃ surface as monolayer then. In case the amount is higher than this value, the residual crystalline WO₃ will remain. The maximum monolayer dispersion (threshold) is 0.21 g and 0.20 g WO₃/100 m² γ-Al₃O₃ by XRD and XPS respectively. It agrees with the value (0.189 g WO₃/100 m² or 4.90 × 10^?18 W atoms/m²) calculated from the model on assumption that the WO₃ is dispersed as a closed-packed monolayer on γ-Al₂O₃ surface. Inasmuch as WO₃/γ-Al₂O₃ system is stable up to higher temperature, e.g. 700°C, than MoO₃/γ-Al₂O₃ system, WO₃ seems unfavorable to form new bulk compound with γ-Al₂O₃ at that temperature. However, Al₂(MoO₄)₃ forms perceptibly in MoO₃/γ-Al₂O₃ system at 500°C. Besides, the size of residual crystalline WO₃ in WO₃/γ-Al₂O₃ is much smaller than that of MoO₃ in MoO₃/γ-Al₂O₃. It might be the reason that WO₃/γ-Al₂O₃ catalyst is superior to MoO₃/γ-Al₂O₃ in hydrodesulfurization (HDS) or hydrodenitrogenation (HDN) in some cases.     

The Mechanism of Low-Temperature Ammonia Oxidation on Metal Oxides According to the Data of Spectrokinetic Measurements

Low temperature ammonia oxidation on MoO₃, Fe₂O₃, Cr₂O₃, and ZnO is studied by the spectrokinetic method. It is shown that the following adsorbed species are intermediates in this reaction: NH₃ and N₂O on Fe₂O₃ and ZnO; NH₃, N₂O, and NO on Cr₂O₃. All of the detected intermediates are used to construct the mechanism of the process. In the framework of the proposed mechanism, stationary and nonstationary spectral and kinetic data are quantitatively processed. The dependence of the rate constants of the same steps on different oxides on their physicochemical properties is discussed.     

Enhanced electrochemical reduction of rare earth oxides in simulated oxide fuel via co-reduction of NiO in Li2O–LiCl salt

Rare earth oxides in spent oxide fuel from nuclear plants have poor reducibility in the electrochemical reduction process due to their high oxygen affinity and thermodynamic stability. Here, we demonstrate that the extent of their reduction can be enhanced via co-reduction of NiO in a Li₂O–LiCl electrolyte for the electrochemical reduction of a simulated oxide fuel (simfuel). First, the electrochemical behaviors of Nd₂O₃, NiO, and Nd₂O₃–NiO were studied by cyclic voltammetry and voltage control electrolysis. Then, the electrochemical reduction of the simfuel containing UO₂ and rare earth oxides (Nd₂O₃, La₂O₃, and CeO₂) was conducted in molten LiCl salt with 1 wt.% Li₂O via the co-reduction of NiO. The extent of reduction of the rare earth oxides was found to be significantly improved.     

Phosphorus modified MoO<Subscript>3</Subscript>–Bi<Subscript>2</Subscript>SiO<Subscript>5</Subscript>/SiO<Subscript>2</Subscript> catalyst for gas-phase epoxidation of propylene by molecular oxygen

The phosphorus (P) modified MoO₃–Bi₂SiO₅/SiO₂ catalyst was prepared by a simple co-impregnation method and investigated in the epoxidation of propylene by molecular oxygen. The catalyst was characterized by X-ray diffraction (XRD), N₂ adsorption–desorption analysis, NH₃-temperature-programmed desorption (NH₃-TPD), transmission electron microscopy, and Raman spectroscopy. It was found that the P-modified MoO₃–Bi₂SiO₅/SiO₂ catalyst with a P/Mo molar ratio of 0.5 exhibits the best catalytic performance for epoxidation of propylene by O₂, the TOFs for propylene oxide (PO) formation was four times higher than that of the unmodified one at 633 K. The modification by P could promote the dispersion of MoO₃ nanoparticles and increase the number of weak and moderate acid sites with respect to the phosphorus-free MoO₃–Bi₂SiO₅/SiO₂ catalyst, which were beneficial to the formation of PO. Moreover, the introduction of P also could protect the mesoporous structure by inhibiting the formation of Bi₂Mo₃O₁₂, which was beneficial to the dispersion of active species. We suppose that the phosphorus, bismuth and molybdenum species of P-modified MoO₃–Bi₂SiO₅/SiO₂ catalyst play important roles for propylene epoxidation by molecular oxygen.     

X-ray photoelectron spectroscopic investigation on the elemental chemical shifts in multiferroic BiFeO3 and its valence band structure

A phenomenological rule based on the charge transfer, exists to predict the ionic/covalent character of the bonds in mixed oxides and is widely used to explain the binding-energy shifts of cations in mixed oxides compared to their simple oxides. Here, we have verified the above rule in the multiferroic BiFeO₃ and have applied the same to explain the X-ray photoelectron spectra of BiFeO₃ and its parent oxides Fe₂O₃ and Bi₂O₃. Ionic charges on Fe, Bi and O were calculated from density functional theory (DFT) within the local density approximation. Measured chemical shifts of O 1s, Fe 2p_3/2 and Bi 4f_5/2 were compared with the chemical shifts evaluated theoretically considering different contributions such as charge transfer, Madelung potential (initial state effect) and extra-atomic relaxation (final state effect). The chemical shift in the binding energy of O 1s photoelectron was used to build a covalence scale among Fe₂O₃, Bi₂O₃ and BiFeO₃. The effect of charge transfer on the valence band spectra of BiFeO₃ was also investigated.     

Metal-Organic Framework Glass Catalysts from Melting Glass-Forming Cobalt-Based Zeolitic Imidazolate Framework for Boosting Photoelectrochemical Water Oxidation

Sluggish oxygen evolution kinetics and serious charge recombination restrict the development of photoelectrochemical (PEC) water splitting. The advancement of novel metal–organic frameworks (MOFs) catalysts bears practical significance for improving PEC water splitting performance. Herein, a MOF glass catalyst through melting glass-forming cobalt-based zeolitic imidazolate framework (Co-a_gZIF-62) was introduced on various metal oxide (MO: Fe₂O₃, WO₃ and BiVO₄) semiconductor substrates coupled with NiO hole transport layer, constructing the integrated Co-a_gZIF-62/NiO/MO photoanodes. Owing to the excellent conductivity, stability and open active sites of MOF glass, Co-a_gZIF-62/NiO/MO photoanodes exhibit a significantly enhanced photoelectrochemical water oxidation activity and stability in comparison to pristine MO photoanodes. From experimental analyses and density functional theory calculations, Co-a_gZIF-62 can effectively promote charge transfer and separation, improve carrier mobility, accelerate the kinetics of oxygen evolution reaction (OER), and thus improve PEC performance. This MOF glass not only serves as an excellent OER cocatalyst on tunable photoelectrodes, but also enables promising opportunities for PEC devices for solar energy conversion.     

The role of some metal ions in enhancement of photocatalytic activity of Fe2O3–V2O5 binary oxide

Fe₂O₃-V₂O₅ mixed oxides were synthesized with solid-state dispersion (SSD) and coprecipitation methods. In addition, transition metal oxides such as CuO, NiO, and CO₃O₄ were successfully loaded on the synthesized catalyst (Fe₂O₃-V₂O₅) using the SSD method. The composite catalysts were inspected for their photocatalytic activities in degrading 2,4-dichlorophenol under UV light enforcement. The produced samples were analyzed using X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, diffuse reflectance spectroscopy, scanning electron microscopy, photoluminescence, and the Brunauer–Emmett–Teller method. The addition of transition metal oxides improved the photocatalytic activity of Fe₂O₃-V₂O₅ (SSD). 1CuO wt% Fe₂O₃-V₂O₅ exhibited the highest percentage of 2,4-dichlorophenol degradation (100%) and the highest reaction rate (1.83 mg/L min) in 30 min. This finding is attributed to the distribution of CuO.     

Phase relations and crystal structures in the systems (Bi,Ln)2WO6 and (Bi,Ln)2MoO6 (Ln=lanthanide)

Several outstanding aspects of phase behaviour in the systems (Bi,Ln)₂WO₆ and (Bi,Ln)₂MoO₆ (Ln=lanthanide) have been clarified. Detailed crystal structures, from Rietveld refinement of powder neutron diffraction data, are provided for Bi_1.8La_0.2WO₆ (L-Bi₂WO₆ type) and BiLaWO₆, BiNdWO₆, Bi_0.7Yb_1.3WO₆ and Bi_0.7Yb_1.3WO₆ (all H-Bi₂WO₆ type). Phase evolution within the solid solution Bi_2−xLa_xMoO₆ has been re-examined, and a crossover from γ(H)-Bi₂MoO₆ type to γ-R₂MoO₆ type is observed at x∼1.2. A preliminary X-ray Rietveld refinement of the line phase BiNdMoO₆ has confirmed the α-R₂MoO₆ type structure, with a possible partial ordering of Bi/Nd over the three crystallographically distinct R sites.