Rare earth oxides as carbon oxidation catalysts

The behavior of a number of rare earth oxides as catalysts for the oxidation of graphite in air has been investigated by the methods of thermal analysis. Of the oxides studied, only CeO₂ showed significant activity in accelerating the gasification of graphite by oxygen between 500 and 1000°C. Cerium salts, which decompose to a finely dispersed oxide phase at low temperatures, e.g. Ce (III) nitrate and ammonium Ce (IV) nitrate, were found to be very active catalysts. The catalytic effect may be due to a redox process involving the cyclic conversion of the oxide from the Ce (IV) to the Ce (III) oxidation state, or the oxide particles may provide sites for the dissociative chemisorption of oxygen.     

Mixed MVSb oxides as oxidehydrogenation catalysts

Mixed MVSb (M = Ni, Co, Bi, Sn) oxides supported by alumina were characterized and evaluated for oxidative dehydrogenations of light paraffins, ethylbenzene and ethanol. The most selective NiVSb catalyst was the most easily reduced that was interpreted on the assumption of reaction redox mechanism. The results of kinetic measurements revealed the concentration of gas-phase oxygen to be a key parameter affecting the dehydrogenation selectivity. To maintain it an optimum along the catalyst bed, a distributed oxygen feed was used.     

Rutile-type Cr/Sb mixed oxides as heterogeneous catalysts for the ammoxidation of propane to acrylonitrile

Cr/Sb mixed oxides with a rutile-type structure were synthesized by calcining (700°C) a mixture of oxohydrates obtained by coprecipitation from an alcohol solution containing the required amount of the components. The samples were characterized using X-ray powder diffraction (XRD), FT-IR spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). In the Cr/Sb/O compound prepared with Cr/Sb 1/0.8 (atomic ratio), an almost stoichiometric CrSbO₄develops (no antimony or chromium oxides are found), which however is characterized by enrichment in Sb in outmost rutile atomic layers, and thus by a non-homogeneous intracrystalline distribution of the two components. For Cr/Sb ratios lower than 1, the amount of Sb in the rutile-type structure exceeds the stoichiometric value. The reactivity of Cr/Sb/O catalysts with increasing Sb contents (from Cr/Sb 1/0.8 to 1/2.8) is slightly affected by the Cr/Sb atomic ratio. In particular, the selectivity increases with increasing Sb content, while the catalytic activity is higher for the samples having higher Cr/Sb ratios. The Cr/Sb/O system presents considerable differences with respect to the V/Sb/O rutile system; these differences are discussed in reference to the properties of the transition metal components of the rutile mixed oxides.     

Mixed oxides as a support for new CoMo catalysts

Interest in bifunctional catalysts, active in reactions such as hydrodesulphurisation (HDS) of hydrocarbon fractions, is growing in the last years. An improvement of CoMo/Al₂O₃ materials can be obtained by the introduction of other oxides during the sol–gel synthesis. This heavily affects the acid–base characteristics of the catalysts, while textural properties are less influenced. The catalytic performances change as well: a relationship between the density of acid sites and HDS activity has been found.     

含铈氧化物储氧材料的合成方法研究进展

含铈氧化物由于其独特的氧化还原性能及较强的储氧能力成为汽车尾气催化净化三效催化剂的关键材料。气相合成法中的气相凝结法和溅射法是制备具有低起燃温度和无团聚的纳米级非化学计量比催化材料最有效的方法;液相化学法有共沉淀法、溶胶-凝胶法、水(溶剂)热法、微乳液法、溶液燃烧法和溶液聚合配合法等,其中共沉淀法是湿化学过程通用的方法,溶胶-凝胶法能在低温条件下合成出均相多组分复合材料,水(溶剂)热晶化法是合成特定纳米晶体催化材料的最好方法;固相法中的高能球磨法可实现多组分的均匀混合,形成高浓度晶格缺陷的固溶体。综述了含铈储氧材料的气-固、液-固和固-固三大类合成技术的进展,探讨了制备方法和材料特性的关系。     

Amorphous microporous mixed oxides as selective redox catalysts

Amorphous microporous homogeneously mixed oxides based on Ti or V in silica can be prepared by an acid catalyzed solgel process. The materials have been characterized by TEM, UV, IR and sorption methods. The glasses can be used for the selective epoxidation of alkenes. The catalytic properties are comparable to those of the well known crystalline Ti-containing zeolites TS-1, Ti-MCM-41 and Ti-Beta. Amorphous microporous homogeneously mixed metal oxides seem to be promising new catalytic materials supplementing the well studied selective zeolites.     

Heterogeneous basic catalysts as alternatives to homogeneous catalysts: reactivity of Mg/Al mixed oxides in the alkylation of m-cresol with methanol

Mg/Al mixed oxides, obtained by decomposition of hydrotalcite-like precursors, represent interesting heterogeneous catalytic systems for basic-catalyzed reactions, as an alternative to environmentally unfriendly homogeneous catalysts. The reactivity of these oxides was evaluated using the methylation of m-cresol as a test reaction and relationships between catalytic performance and chemical–physical features were established. The basicity of the samples was evaluated by CO₂ adsorption and thermal-programmed-desorption. The presence of Al in the mixed oxides considerably affected the density and the strength of the basic sites with respect to MgO. These basic properties in turn influenced the catalytic performance of the materials. Under the reaction conditions used in the present work, medium strength basic sites played the major role in the reaction.     

Ceria‐based nanomaterials as catalysts for CO oxidation and soot combustion: Effect of Zr‐Pr doping and structural properties on the catalytic activity

In this work, we investigated a set of ceria‐based catalysts prepared by the hydrothermal and solution combustion synthesis. For the first time to our knowledge, we synthesized nanocubes of ceria doped with zirconium and praseodymium. The catalysts were tested for the CO and soot oxidation reactions. These materials exhibited different surface reducibility, as measured by H₂‐TPR, CO‐TPR and Soot‐TPR, despite their comparable chemical compositions. As a whole, Soot‐TPR appears a suitable characterization technique for the soot oxidation catalysts, whereas CO‐TPR technique allows to better discriminate among the CO oxidation activities. Praseodymium contributes positively toward the soot oxidation. On the other hand, it has an adverse effect on the CO oxidation over the same catalysts, as compared to pure ceria. The incorporation of zirconium into the ceria lattice does not have a direct beneficial effect on the soot oxidation activity, although it increases the catalyst performances for CO oxidation. © 2016 American Institute of Chemical Engineers AIChE J, 63: 216–225, 2017     

The control of catalytic performance of rutile-type Sn/V/Nb/Sb mixed oxides, catalysts for propane ammoxidation to acrylonitrile

This paper describes the effect of the composition of rutile-type Sn/V/Nb/Sb mixed oxides catalysts on the catalytic performance in the gas-phase ammoxidation of propane to acrylonitrile. The variation in the atomic ratio between components in catalysts is the key for the control of activity and selectivity. In samples with atomic composition Sn/V/Nb/Sb 1/0.2/1/x (0 ≤ x ≤ 5) and 1/0.2/y/3 (0 ≤ y ≤ 3) several compounds formed, i.e., SnO₂, Sb/Nb mixed oxide, Sb₆O₁₃ and non-stoichiometric rutile-type V/Nb/Sb/O; the latter segregated preferentially at the surface of the catalyst. Tin oxide provided the rutile matrix for the dispersion of the mixed oxides. The main role of Sb was shown to generate mixed oxides containing specific sites for the allylic ammoxidation of propylene intermediately formed. The presence of Nb enhanced the activity and selectivity of these sites.     

以类水滑石为前驱体制备的复合氧化物同时吸附烟道气中SO2和NO研究

采用共沉淀法制备NiMgAlO、CuMgAlO、ZnMgAlO和FeMgAlO类水滑石复合氧化物，并用于常压下同时氧化吸附模拟烟道气中的SO2和NO。模拟烟道气中SO₂的摩尔分数为1%, NO的摩尔分数为0.2%，O₂以及He作为载气。研究结果表明，这四种催化剂对烟道气中的SO₂和NO具有良好的同时氧化吸附效果。比较四种催化剂的吸附效果发现，NiMgAlO和CuMgAlO要优于ZnMgAlO和FeMgAlO，且NiMgAlO对SO₂和NO的吸附效果最佳。     

Modeling of the desulfation process in NOx storage and reduction catalysts

One of the major challenges for the NO_x Storage and Reduction Catalysts technology used in automotive exhaust remains the sulfur susceptibility, which calls for efficient desulfation strategies. The sulfation and desulfation processes are systematically studied via measurements and mathematical modeling of the physicochemical processes. The role of oxygen storage which influences the reducing agents availability for desulfation is explained and a respective reaction model is presented. The bulk oxygen storage component appears to be involved in sulfur storage, which further emphasizes the importance of oxygen–sulfur storage interactions. Next, the observed release of sulfur species under lean mode is discussed along with a proposed reaction mechanism which involves SO₂ formation via O₂ reaction with elemental sulfur on the surface. The parameters of the complex reaction model are calibrated in order to reproduce the observed trends at least in a qualitative manner. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2117–2127, 2017     

Non‐Covalent Immobilization of Rare Earth Heterobimetallic Frameworks and their Reactivity in an Asymmetric Michael Addition

Heterobimetallic Lewis acid catalysts are broadly useful and methods to recycle them have immediate applications. However, their immobilization through covalent binding can be challenging. Non‐covalent immobilization of supported asymmetric catalysts is attractive due to ease of preparation and potential for reversible binding. We report a novel non‐covalent binding strategy for Shibasaki’s REMB framework {RE=rare earth metal; M=Li, Na, K; B=BINOL; RE:M:B=1:3:3, [M₃(sol)_n][(BINOLate)₃RE] } and explore the reactivity of the supported catalyst.

     

Modification of the oxygen storage capacity of CeO2–ZrO2 mixed oxides after redox cycling aging

High surface area CeO₂–ZrO₂ mixed oxides were treated at 900–950°C either under wet air or under successive reducing and oxidizing atmospheres in order to study the evolution of the oxygen storage capacity (OSC) of these solids after different aging treatments. Several complementary methods were used to characterize the redox behavior: temperature programmed reduction (TPR) by H₂, TPO, magnetic susceptibility measurements to obtain the Ce³⁺ content, FT-IR spectroscopy of adsorbed methanol and a method to compare the oxygen buffering capacity (OBC) of the oxides.

All the results confirm that the mixed oxides exhibit better redox properties than pure ceria, particularly after aging. The enhancement in the OSC at moderate temperature has to be related to a deeper penetration of the reduction process from the surface into the under-layers. Redox cycling aging promotes the reduction at low temperature of all the mixed oxides, the improvement being much more important for low surface area aged samples. The magnitude of this effect does not depend on the BET surface areas which have similar values after cycling. This underlines the critical influence that the preparation and activation procedure have on the final OSC behaviors of the ceria–zirconia mixed oxides.     

MoVW mixed metal oxides catalysts for acrylic acid production: from industrial catalysts to model studies

(MoVW)₅O₁₄-type oxides were identified as the active and selective components in industrial acrylic acid catalysts. Tungsten is suggested to play an important role as a structural promoter in the formation and stabilization of this oxide. Vanadium is responsible for high catalytic activities but is detrimental for the stability of this oxide at the necessary high concentrations for optimum catalytic performance. The activity of mixed MoVW oxide catalysts for methanol, propene, and acrolein partial oxidation could be considerably improved, when the amount of the (MoVW)₅O₁₄-type oxide was increased by thermal annealing. A model is proposed on the basis of the correlation between Raman wavenumber and bond order and degree of reduction, which explains the observed different selectivities of MoO_3−x and the (MoVW)₅O₁₄-type oxides in terms of metal–oxygen bond strengths, i.e. oxygen basicity and oxygen lability, respectively. According to this model, the (MoVW)₅O₁₄ mixed oxide catalyses partial oxidation because of its intermediate C–H activation and oxygen releasing oxygen functionalities. However, these (MoVW)₅O₁₄-type industrial oxidation catalysts are heterogeneous and highly complex systems. Their physicochemical characterization also revealed that their chemical bulk and surface compositions vary with thermal activation and oxygen potential. A core-shell model is suggested to describe the active catalyst state, the shell providing a high number of active centers, the core high electronic conductivity and ion mobility. The fact that the surface composition of such catalysts is considerably different from their bulk compositions, most probably implies that the “molecular structure” at their surface differs too considerably from their bulk crystal structure. Hence, the posed question about the active catalyst structure and its relation to its catalytic performance cannot unambiguously be explained by the crystallographic structure, but still remains unsolved.     

Selective reduction of nitrogen oxides with hydrocarbons over solid acid catalysts in oxygen-rich atmospheres

Highly selective reduction of nitrogen oxides to dinitrogen occurs to a high level in oxygen-rich atmospheres by using a small amount of propane as a reducing agent over alumina, silica-alumina, titania and zirconia catalyst. Judging from the data of activity and ammonia TPD measurement on a series of silica-alumina catalysts, acidity is suggested to be one of the main factors that determine catalytic activity.     

MnOx/C composites as electrode materials II. Reduction of oxygen on bifunctional catalysts based on manganese oxides

MnO_x/C composites prepared by the reduction of KMnO₄ by active carbon black and doped with Ca(II), Mg(II), Ni(II), Bi(III), and Cr(III) ions were tested as catalysts of oxygen reduction in alkaline electrolyte. The polarisation curves were analysed by logarithmic wave analysis. MnO_x doped with the transition metal salts are slightly more active than those with Ca(II) and Mg(II).     

Recent advances in automobile exhaust catalysts

Catalysts, which were recently developed by Toyota for the control of automobile exhaust, are reviewed. (1) For use in low emission vehicles, a CeO₂-ZrO₂ solid solution (CZ) with both high oxygen storage capacity and high heat resistance was developed as a support for a high performance three-way catalyst (TWC). (2) A novel three-way catalyst named the NO_x storage-reduction catalyst (NSR) was developed for automotive lean-burn engines. The NSR catalyst can store NO_x in an oxidizing atmosphere and then reduce stored NO_x at stoichiometric or reducing conditions. Also, it has high tolerance to sulfur poisoning which is the most stringent problem for the NSR catalyst.     

Mo–V–Nb mixed oxides as catalysts in the selective oxidation of ethane

Mo–V–Nb–O mixed metal oxides, obtained by heat-treatment in N₂ at 425 °C, have been studied as catalysts in the oxidative dehydrogenation of ethane. They present higher catalytic activity, while maintaining the same selectivity to ethylene, than the corresponding metal oxides calcined under air. Both amorphous and crystalline phases are present on active and selective catalysts. The implications of the presence of these phases as well as their physicochemical characteristics on the nature of active and selective sites are discussed.     

非晶态Ni-B和Ni-P合金催化剂改性研究进展

介绍了非晶态合金催化剂的结构特点,比较了载体、添加金属或稀土元素等改性对催化剂热稳定性能和催化性能的影响。分析了镍基非晶态催化剂硫中毒的机理,综述了载体以及添加稀土元素对催化剂抗硫性能的影响,并对非晶态合金催化剂的研究和应用前景进行了展望。     

The role of Sb and Nb in rutile-type Sn/V/Nb/Sb mixed oxides, catalysts for propane ammoxidation to acrylonitrile

This paper describes the role of Sb and Nb, components of Sn/V/Nb/Sb mixed oxides catalysts for the gas-phase ammoxidation of propane to acrylonitrile. In samples without Nb and with atomic ratios Sn/V/Sb 1/0.2/x (x = 0 to 3), Sb in the form of amorphous oxide is necessary in order to obtain an active and selective catalyst. However, during reaction the dispersed Sb oxide segregates to α-Sb₂O₄, and the yield to acrylonitrile decreases considerably. The addition of Nb gives rise to the formation of Nb-containing SbO_x and non-stoichiometric rutile-type V/Nb/Sb mixed oxides. The presence of these compounds enhances the catalytic activity and the selectivity to acrylonitrile. Moreover, the catalyst shows a stable catalytic performance, with no segregation of α-Sb₂O₄.