The red–ox treatments influence on the structure and properties of M2O3–CeO2–ZrO2 (M=Y, La) solid solutions

The introduction of trivalent cation — Y³⁺ or La³⁺ — into the lattice of CeO₂–ZrO₂ solid solutions allows to stabilise a cubic structure at low ceria content (30 mol%). The reducibility of the samples has been compared in the experiments of temperature-programmed reduction (TPR). The introduction of lanthanum cations decreases the amount of hydrogen consumed during TPR, while the introduction of yttrium ones increases this value. At the same time, the value of temperature of the maximum speed of reduction (T_max) is independent on the trivalent dopant. The reducibility of these solid solutions did not change during repeated red–ox treatments at temperature below 1220 K. It is connected with the high thermostability of all systems in this temperature interval. TPR up to 1470 K causes a significant shift of T_max value to higher temperature and a slight decrease of hydrogen consumption in two to three cycles. It is suggested that this alterations are connected with the sharp decrease of the specific surface area of all samples and partially phase decomposition of CeO₂–ZrO₂ and Y₂O₃–CeO₂–ZrO₂ solid solutions. Raman characterisation of the oxygen sublattice of the fresh samples and of the samples after TPR has been carried out.     

Oxidation entropies and enthalpies of ceria–zirconia solid solutions

The thermodynamic redox properties for a series of ceria–zirconia solid solutions have been measured by determining their oxidation isotherms between 873 and 1073 K. Isotherms were obtained using Coulometric titration and using O₂ titration of samples equilibrated in flowing mixtures of H₂ and H₂O. Samples having the following compositions were studied after calcinations at 973 and 1323 K: CeO₂, Ce_0.92Zr_0.08O₂, Ce_0.81Zr_0.19O₂, Ce_0.59Zr_0.41O₂, Ce_0.50Zr_0.50O₂, Ce_0.25Zr_0.75O₂, Ce_0.14Zr_0.86O₂, and ZrO₂. While the oxidation enthalpy for CeO₂ was between −750 and −800 kJ/mol O₂, the oxidation enthalpies for each of the solid solutions were between −500 and −550 kJ/mol O₂ and essentially independent of the extent of reduction. The shapes of the isotherms for the solid solutions were affected by the oxidation entropies, which depended strongly on the sample composition and the extent of reduction. With CeO₂, Ce_0.92Zr_0.08O₂, and Ce_0.14Zr_0.86O₂, the samples remained single-phase after calcination at 1323 K and the thermodynamic redox properties were unaffected. By contrast, Ce_0.59Zr_0.41O₂ formed two phases following calcination at 1323 K, Ce_0.78Zr_0.22O₂ (71 wt.%) and Ce_0.13Zr_0.87O₂ (29 wt.%); the isotherm changed to that which would be expected for a physical mixture of the two phases. A model is presented which views reduction of the solid solutions in terms of the local atomic structure, with the formation of “pyrochlore-like” clusters causing the increased reducibility of the solid solutions. Some of the changes in reducibility are associated with the number of sites from which oxygen can be removed in order to form pyrochlore-like clusters.     

New Si–C bond forming reactions over solid-base catalysts

The reactions of silanes with carbanions generated on the surface of solid bases bring about the nucleophilic substitution at the Si atom to form Si–C bonds. The reaction of alkynes with silanes afforded alkynylsilanes. For example, the reaction of tert-BuCCH or n-BuCCH with Et₂SiH₂ in the presence of KNH₂/Al₂O₃ gave tert-BuCCSiEt₂H and n-BuCCSiEt₂H in a 77% and 67% yield, respectively, at 329 K. Toluene also reacted with Et₂SiH₂ at 329 K to yield benzyldiethylsilane in a 85% yield. The reactions of 1-alkynes with Me₃SiCCH in the presence of KNH₂/Al₂O₃ or KF/Al₂O₃ resulted in a novel type of metathesis reaction between the two alkynes. For example, the reaction of PhCCH with Me₃SiCCH afforded PhCCSiMe₃ and HCCH in a high yield. These new types of base-catalyzed reactions provide new synthetic routes for Si–C bond formation.     

The role of molybdenum in Mo-doped V–Mg–O catalysts during the oxidative dehydrogenation of n-butane

A detailed study on the influence of the addition of molybdenum ions on the catalytic behaviour of a selective vanadium–magnesium mixed oxide catalyst in the oxidation of n-butane has been performed. The catalysts have been prepared by impregnation of a calcined V–Mg–O mixed oxides (23.8 wt% of V₂O₅) with an aqueous solution of ammonium heptamolybdate, and then calcined, and further characterised by several physico-chemical techniques, i.e. S_BET, XRD, FTIR, FT-Raman, XPS, H₂-TPR. MgMoO₄, in addition to Mg₃V₂O₈ and MgO, have been detected in all the Mo-doped samples. The incorporation of molybdenum modifies not only the number of V⁵⁺-species on the catalyst surface and the reducibility of selective sites but also the catalytic performance of V–Mg–O catalysts. The incorporation of MoO₃ favours a selectivity and a yield to oxydehydrogenation products (especially butadiene) higher than undoped sample. In this way, the best catalyst was obtained with a Mo-loading of 17.3 wt% of MoO₃ and a bulk Mo/V atomic ratio of 0.6. From the comparison between the catalytic properties and the catalyst characterisation of undoped and Mo-doped V–Mg–O catalysts, the nature of selective sites in the oxidative dehydrogenation of n-butane is also discussed.     

Fischer–Tropsch synthesis over Co–SiO2 catalysts prepared by the sol–gel method

Fischer–Tropsch synthesis was carried out in slurry phase over uniformly dispersed Co–SiO₂ catalysts prepared by the sol–gel method. When 0.01–1 wt.% of noble metals were added to the Co–SiO₂ catalysts, a high and stable catalytic activity was obtained over 60 h of the reaction at 503 K and 1 MPa. The addition of noble metals increased the reducibility of surface Co on the catalysts, without changing the particle size of Co metal significantly. High dispersion of metallic Co species stabilized on SiO₂ was responsible for stable activity. The uniform pore size of the catalysts was enlarged by varying the preparation conditions and by adding organic compounds such as N,N-dimethylformamide and formamide. Increased pore size resulted in decrease in CO conversion and selectivity for CO₂, a byproduct, and an increase in the olefin/paraffin ratio of the products. By modifying the surface of wide pore silica with Co–SiO₂ prepared by the sol–gel method, a bimodal pore structured catalyst was prepared. The bimodal catalyst showed high catalytic performance with reducing the amount of the expensive sol–gel Co–SiO₂.     

Ferroelectric and ferromagnetic properties of Mn-doped 0.7BiFeO3–0.3BaTiO3 solid solution

Binary solid solutions 0.7BiFeO₃–0.3BaTiO₃–x wt.% MnO₂ (x = 0, 0.2, 0.3, and 0.5) were prepared by a traditional ceramic process. All ceramic samples show single perovskite phase. The effect of manganese doping on structure, dielectric, ferroelectric and ferromagnetic properties, and resistivity was investigated. Results show that Mn-dopant can improve the sintering ability of the materials when MnO₂ content is below 0.3 wt.%. When MnO₂ content exceeds 0.3 wt.%, the sintering ability is weakened and the phase structure of 0.7BiFeO₃–0.3BaTiO₃ solid solution changes from rhombohedral into tetragonal phase. With increasing concentration of MnO₂, the resistivity increases at first and then decreases. Whereas the coercive electric field decreases at first and then increases, the remanent magnetization M_r increases and the coercive magnetic field decreases.     

Effects of alumina incorporation in coprecipitated NiO–Al2O3 catalysts

The effect of Al₂O₃ levels on the properties of NiO in coprecipitated NiO–Al₂O₃ samples were investigated, using samples with up to 60.7 wt.% Al₂O₃ that had been calcined in the range 300–700°C. Characterization techniques included BET surface area of fresh and reduced catalysts, X-ray diffraction analysis of structure and crystallite size, magnetic susceptibility measurements, oxidizing power, and reducibility in H₂. Only NiO was detected in samples with up to 4.1 wt.% Al₂O₃ for all sample calcination temperatures. Surface areas were similar for all fresh samples but decreased rapidly after calcination at high temperatures. The surface area loss was less for the higher Al₂O₃-containing samples. Nickel oxide crystallite sizes increased at higher calcination temperatures, but remained approximately the same for each Al₂O₃ level.

The NiO was nonstoichiometric (NiO_1+x), with x decreasing at higher calcination temperatures and increasing with small amounts of added Al₂O₃ through a maximum at about 3 wt.% Al₂O₃. However, this did not correlate well with microstrain in the NiO crystallites nor with reducibility, which decreased with Al₂O₃ addition. At higher levels of Al₂O₃ (13.6 wt.% and above), surface areas increased with higher Al₂O₃ loadings, but NiO crystallite sizes remained approximately the same, independent of both Al₂O₃ content and calcination temperature. X-ray diffraction patterns were very diffuse, and it was not possible to rule out the presence of pseudo-spinel combinations of NiO and Al₂O₃. Reducibility was more difficult than with low Al₂O₃ levels, and nonstoichiometry was low and independent of Al₂O₃ content.

Reducibilities of all samples calcined at 300°C correlated well with the final BET surface area of the reduced samples, indicating that more dispersed NiO crystallites are more difficult to reduce, a conclusion that supports a model for reduction proposed previously.     

Epoxidation of styrene over mesoporous Zr–Mn-MCM-41

Epoxidation of styrene with t-butyl hydroperoxide (TBHP) as an oxidizing agent has been conducted under liquid phase reaction conditions over Zr–Mn-MCM-41 with different n_Si/(n_Zr + n_Mn) ratios and Mn-MCM-41(31) catalysts for selective synthesis of styrene oxide. The influences of various reaction parameters such as temperature, time, oxidants, and solvents, styrene to TBHP mmol ratios and acetonitrile (MeCN) to N,N-dimethylformamide (DMF) volume ratios on the conversion of styrene and the selectivity of styrene oxide have also been studied. With the decrease of the n_Si/(n_Zr + n_Mn) ratios of Zr–Mn-MCM-41 catalysts from 327 to 49, the conversion of styrene as well as the yield and selectivity of styrene oxide increase due to the increase of the number of Lewis acid sites on the surface of catalysts. Moreover, the conversion and selectivity in Zr–Mn-MCM-41(49) is higher as compared to that of Mn-MCM-41(31). The Zr–Mn-MCM-41(49) is found to be reusable for the epoxidation of styrene with TBHP for selective synthesis of styrene oxide.     

Fischer–Tropsch synthesis on monolithic catalysts of different materials

Monolithic structures made of cordierite, γ-Al₂O₃ and steel have been prepared as catalysts and tested for Fischer–Tropsch activity. The monoliths made of cordierite and steel were washcoated with a 20 wt.% Co–1 wt.% Re/γ-Al₂O₃ Fischer–Tropsch catalyst whereas the γ-Al₂O₃ monoliths were made by direct impregnation with an aqueous solution of the Co and Re salts resulting in a loading of 12 wt.% Co and 0.5 wt.% Re. The activity and selectivity of the different monoliths were compared with the corresponding powder catalysts.

Higher washcoat loadings resulted in decreased C₅₊ selectivity and olefin/paraffin ratios due to increased transport limitations. The impregnated γ-Al₂O₃ monoliths also showed similar C₅₊ selectivities as powder catalysts of small particle size (38–53 μm). Lower activities were observed with the steel monoliths probably due to experimental problems.     

Direct decomposition of nitric oxide over Ba catalysts supported on CeO2-based mixed oxides

The direct decomposition of nitric oxide (NO) over barium catalysts supported on various metal oxides was examined in the absence and presence of O₂. Among the Ba catalysts supported on single-component metal oxides, Ba/Co₃O₄ and Ba/CeO₂ showed high NO decomposition activities, while Ba/Al₂O₃, Ba/SiO₂, and Ba/TiO₂ exhibited quite low activities. The effect of an addition of second components to Co and Ce oxides was further examined, and it was found that the activities were significantly enhanced using Ce–Mn mixed oxides as support materials. XRD results indicated the formation of CeO₂–MnO_x solid solutions with the cubic fluorite structure. O₂-TPD of the CeO₂–MnO_x solid solutions showed a large desorption peak in a range of relatively low temperature. The BET surface areas of the CeO₂–MnO_x solid solutions were larger than those of pure CeO₂ and Mn₂O₃. These effects caused by the addition of Mn are responsible for the enhanced activities of the Ba catalysts supported on Ce–Mn mixed oxides.     

Studies on structural properties, surface acidity and benzene isopropylation activity of sulphated ZrO2–TiO2 mixed oxide catalysts

A series of sulphated ZrO₂–TiO₂ mixed oxide with different nominal sulphate loadings in the range of 2–15 wt.% was prepared and characterized for their structural properties, surface acidity and benzene isopropylation activity. The catalyst with 10 wt.% nominal sulphate loading showed highest surface area and uniform pore size distributions. Surface acidity, measured by NH₃–TPD method, showed increase in acidity with sulphate loading and the 10 wt.% sulphate loaded catalyst showed highest acidity. The activities of these catalysts were tested for isopropylation of benzene to cumene using 2-propanol as the alkylating agent. The 10 wt.% sulphate-loaded catalyst also showed highest activity for this reaction with 97% cumene selectivity. The higher activity of this catalyst was attributed to its higher acidity.     

Decolorization of reactive brilliant red X-3B by heterogeneous photo-Fenton reaction using an Fe–Ce bimetal catalyst

Decolorization of reactive brilliant red X-3B was studied by using an Fe–Ce oxide hydrate as the heterogeneous catalyst in the presence of H₂O₂ and UV. The decolorization rate was in the order of UV–Fe–Ce–H₂O₂ > UV–Fe³⁺–H₂O₂ > UV–H₂O₂ > UV–Fe–Ce ≥ Fe–Ce–H₂O₂ > Fe–Ce. Under the conditions of 34 mg l⁻¹ H₂O₂, 0.500 g l⁻¹ Fe–Ce, 36 W UV and pH 3.0, 100 mg l⁻¹ X-3B could be decolorized at efficiency of more than 99% within 30 min. The maximum dissolved Fe during the reaction was 1 mg l⁻¹. From the fact that the decolorization rate of the UV–Fe–Ce–H₂O₂ system was significantly higher than that of the UV–Fe³⁺–H₂O₂ system at Fe³⁺ = 1 mg l⁻¹, it is clear that the Fe–Ce functioned mainly as an efficient heterogeneous catalyst. UV–vis, its second derivative spectra, and ion chromatography (IC) were employed to investigate the degradation pathway. Fast degradation after adsorption of X-3B is the dominant mechanism in the heterogeneous catalytic oxidation system. The first degradation step is the breaking down of azo and CN bonds, resulting in the formation of the aniline- and phenol-like compounds. Then, the breaking down of the triazine structure occurred together with the transformation of naphthalene rings to multi-substituted benzene, and the cutting off of sulphonic groups from the naphthalene rings. The last step includes further decomposition of the aniline structure and partial mineralization of X-3B.     

Effect of boron source on the catalyst reducibility and Fischer–Tropsch synthesis activity of Co/TiO2 catalysts

A series of Co/B/TiO₂ (B=ammoniumborate, boric acid, o-carborane, 0.01–1.5 wt.% B) catalysts were synthesized. The addition of boron decreased the reducibility of the Co as determined from temperature-programmed reduction studies and H₂ reduction/O₂back titration studies. This in turn decreased the FT activity but not the turnover frequency of the Co catalyst.     

Influence of the acid–base/redox properties of TiOx-sepiolite supported vanadium oxide catalysts in the gas-phase selective oxidation of toluene

Catalytic behaviour in the selective oxidation of toluene of a series of vanadium systems supported on TiO_x-coated sepiolite (6, 12 and 25 wt.% TiO₂) with a vanadia loading around the theoretical monolayer (10 wt.%) has been investigated. The surface acid–base/redox properties of the solids were also evaluated by using 2-propanol conversion and pyridine chemisorption. The reducibility of surface vanadia species was studied by H₂-TPR. Surface properties of vanadia species and, consequently, their catalytic behaviour were influenced by titania loading on sepiolite. Thus, the vanadium systems with the highest titania loading were the most active and selective in toluene oxidation. Furthermore, this behaviour seems to be mainly related to the density of the active sites capable of being reduced and producing propanone in the vanadium systems.     

Novel utilization of MCM-22 molecular sieves as supports of cobalt catalysts in the Fischer–Tropsch synthesis

Cobalt catalysts (2–10 wt% Co) supported on silica-rich MCM-22 zeolites have been prepared by impregnation with aqueous Co(NO₃)₂ solutions. The catalysts are characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), nitrogen adsorption, solid state nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The catalytic properties for the Fischer–Tropsch synthesis (FTS) at 280 °C, 12.5 bar and H₂/CO = 2 are evaluated. The catalysts supported on MCM-22 exhibit the highest selectivity to long-chain (C₅₊) hydrocarbons when MCM-22 supports are synthesized with the appropriate Si/Al ratio.     

Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

Nano-structured CeO2 supported Cu-Pd bimetallic catalysts for the oxygen-assisted water–gas-shift reaction

The present work focuses on the development of novel Cu-Pd bimetallic catalysts supported on nano-sized high-surface-area CeO₂ for the oxygen-assisted water–gas-shift (OWGS) reaction. High-surface-area CeO₂ was synthesized by urea gelation (UG) and template-assisted (TA) methods. The UG method offered CeO₂ with a BET surface area of about 215 m²/g, significantly higher than that of commercially available CeO₂. Cu and Pd were supported on CeO₂ synthesized by the UG and TA methods and their catalytic performance in the OWGS reaction was investigated systematically. Catalysts with about 30 wt% Cu and 1 wt% Pd were found to exhibit a maximum CO conversion close to 100%. The effect of metal loading method and the influence of CeO₂ support on the catalytic performance were also investigated. The results indicated that Cu and Pd loaded by incipient wetness impregnation (IWI) exhibited better performance than that prepared by deposition–precipitation (DP) method. The difference in the catalytic activity was related to the lower Cu surface concentration, better Cu–Ce and Pd–Ce interactions and improved reducibility of Cu and Pd in the IWI catalyst as determined by the X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) studies. A direct relation between BET surface area of the CeO₂ support and CO conversion was also observed. The Cu-Pd bimetallic catalysts supported on high-surface-area CeO₂ synthesized by UG method exhibited at least two-fold higher CO conversion than the commercial CeO₂ or that obtained by TA method. The catalyst retains about 100% CO conversion even under extremely high H₂ concentration.     

Competition between NO reduction and NO decomposition over reduced V–W–O catalysts

The SCR of NO and NO decomposition were investigated over a V–W–O/Ti(Sn)O₂ catalyst on a Cr–Al steel monolith. The conversions of NO and NH₃ over the reduced and oxidised catalysts were determined. The higher conversion of NO than of NH₃ was observed in SCR over the reduced catalyst and very close conversions of both substrates were found over the oxidised one. The increase of the pre-reduction temperature was found to cause an increase in catalyst activity and its stability in direct NO decomposition. The surface tungsten cations substituted for vanadium ones in vanadia-like active species are considered to be responsible for the direct NO decomposition. The results of DFT calculations for the 10-pyramidal clusters: V₁₀O₃₁H₁₂ (V–V) and V₉WO₃₁H₁₂ (V–W) modelling (0 0 1) surfaces of vanadia and WO₃–V₂O₅ solid solution (s.s.) active species, respectively, show that preferable conditions for NO adsorption exist on W sites of s.s. species and that reduction causes an increase in their ability for electron back donation to the adsorbed molecule. Electron back donation is believed to be responsible for the electron structure reorganisation in the adsorbed NO molecule resulting in its decomposition. The high selectivity of NO decomposition to dinitrogen was considered to be connected with the formation of the tungsten nitrosyl complexes solely via the W–N bond.     

The influence of reaction parameters on the free Si and C contents in the synthesis of nano-sized SiC

Uniform nano-sized beta-silicon carbide (β-SiC) powder was synthesized from the reaction of silicon (Si) and carbon black (C). Mixed Si and C-black powder were pressed into pellets and the influence of four parameters, temperature (1250, 1300 and 1350 °C), heating rate (20 and 50 °C/min), soaking time (1 and 3 h) and atmosphere (vacuum and argon), were tested. It was found that higher temperatures, higher heating rates and longer soaking times in a vacuum system lead to lower free Si content in the SiC powder created. Temperature was the parameter with the greatest influence on the Si content of the SiC powder. This study also found that the Si–C reaction occurs through gas–solid (SiO–C) and solid–solid (Si–C) reactions that occur simultaneously.     

Synthesis, characterization and catalytic properties of NiMo/Al2O3–MCM-41 catalyst for dibenzothiophene hydrodesulfurization

Ni–Mo/Al₂O₃–MCM-41 supported catalysts have been investigated for modification of MCM-41 by using sol–gel alumina incorporation method. Different catalysts were synthesized with variation of Si/Al molar ratios of 10, 50, 100 and 200. High specific surface area ordered meso-porous solid (MCM-41) was synthesized by using organic template method. In order to modify the low acidity of silica solid, the surface of MCM-41 was modified by incorporation of alumina. The surface acidity of solids modified significantly with variation of alumina content in the supports. The sol–gel method of alumina incorporation was used, which does not modify extensively the pore characteristics of MCM-41 material during the preparation of Al₂O₃–MCM-41. The X-ray diffraction intensities indicated that alumina as well as MCM-41 were present in the synthesized supports. Additionally, the hydrothermal stability of the Al₂O₃–MCM-41 materials was maintained up to 873 K using sever conditions like 100% water vapor stream. The catalytic activity of the catalysts was tested in the hydrodesulfurization (HDS) of dibenzothiophene (DBT). Selectivity was oriented mainly to the production of biphenyl (BP) and for high Si/Al ratios toward cyclohexylbenzene (CHB) and showed a higher conversion and better selectivity to hydrogenation (cyclohexylbenzene).