High performance CuO-CeO2 catalysts for selective oxidation of CO in excess hydrogen： Effect of hydrothermal preparation conditions

High performance CuO-CeO₂ catalysts for selective oxidation of CO in excess hydrogen were prepared by a hydrothermal method under different preparation conditions and evaluated for catalytic activities and selectivities. By changing the n_CTAB/n_Ce ratio and hydrothermal aging time, the catalytic activity of the CuO-CeO₂ catalysts increased and the operating temperature window, in which the CO conversion was higher than 99%, was widened. XRD results showed no peaks of CuO_x species and Cu-Ce-O solid solution were observed. On the other hand, Cu⁺ species in the CuO-CeO₂ catalysts, which was associated with a strong interaction between copper oxide clusters and cerium oxide and could be favorable for improving the selective oxidation performance of CO in excess H₂, were detected by H₂-TPR and XPS techniques.     

Activity of copper–cerium–zirconium catalysts in oxidation of hydrogen

We have studied the catalytic properties in oxidation of hydrogen for copper–cerium oxide systems deposited on supports obtained by calcination of yttrium-stabilized zirconium dioxide at 300–1000 °C. We have shown that the catalytic activity of the samples obtained depends on the specific surface area of the original supports and the amount of reduced copper within the composition of the catalyst. In samples whose support has high specific surface area, the content of reduced metallic copper is greater and the catalytic activity is higher.     

VO<Subscript>x</Subscript>/Zr–SBA-15 catalysts for selective oxidation of ethanol to acetaldehyde

Effect of zirconium presence in the silica framework and content and speciation of vanadium surface oxo-complexes on the catalytic behavior of VO_x/Zr–SBA-15 catalysts in oxidative dehydrogenation of ethanol was investigated. Experimental results bring evidence of successful incorporation of zirconium into ordered mesoporous silica framework with the preservation of ordered mesoporosity by hydrothermal template base synthesis method. The presence of zirconium in the SBA-15 framework increases reducibility of vanadium species and acidity of the catalysts. It is reflected in higher activity of vanadium species expressed as turn-over frequency (e.g., TOF of 20 h^?1 for 5%VO_x/Zr–SBA-15 sample in comparison with TOF of 12 h^?1 for 5%VO_x/SBA-15 sample) and also in significant decrease of selectivity to acetaldehyde (65% in comparison with 90% for mentioned samples) followed by increase in selectivity to ethylene (25% in comparison with 5%). This change in distribution of reaction products is related to stronger acidity character of surface OH groups and inhibition effect of formed water vapours on the oxidative dehydrogenation products (acetaldehyde). Catalytic data also reveal that oligomeric/polymeric tetrahedrally coordinated vanadium species exhibit higher activity in ethanol oxidative dehydrogenation than monomeric complexes. In addition, comparison of the catalytic performance of VO_x/Zr–SBA-15 catalysts with VO_x/SBA-15 catalysts showed that catalytic properties of VO_x/Zr–SBA-15 catalysts can be tuned by incorporation of controlled amount of zirconium into silica framework.     

Kinetic study of oxygen adsorption over nanosized Au/γ-Al₂O₃ supported catalysts under selective CO oxidation conditions

O? adsorption is a key process for further understanding the mechanism of selective CO oxidation (SCO) on gold catalysts. Rate constants related to the elementary steps of O? adsorption, desorption and surface bonding, as well as the respective activation energies, over a nanosized Au/γ-Al?O? catalyst, were determined by Reversed-Flow Inverse Gas Chromatography (RF-IGC). The present study, carried-out in a wide temperature range (50-300 °C), both in excess as well as in the absence of H?, resulted in mechanistic insights and kinetic as well as energetic comparisons, on the sorption processes of SCO reactants. In the absence of H?, the rate of O? binding, over Au/γ-Al?O?, drastically changes with rising temperature, indicating possible O? dissociation at elevated temperatures. H? facilitates stronger O? bonding at higher temperatures, while low temperature binding remains practically unaffected. The lower energy barriers observed, under H? rich conditions, can be correlated to O? dissociation after hydrogenation. Although, H? enhances both selective CO reactant's desorption, O? desorption is more favored than that of CO, in agreement with the well-known mild bonding of SCO reactant's at lower temperatures. The experimentally observed drastic change in the strength of CO and O? binding is consistent both with well-known high activity of SCO at ambient temperatures, as well as with the loss of selectivity at higher temperatures.     

Monolayer V2O5/TiO2–ZrO2 catalysts for selective oxidation of o-xylene: preparation and characterization

A series of TiO₂?CZrO₂ supported V₂O₅ catalysts with vanadia loadings ranging from 4 to 12 wt% were synthesized by a wet impregnation technique and subjected to various thermal treatments at temperatures ranging from 773 to 1,073?K to understand the dispersion and thermal stability of the catalysts. The prepared catalysts were characterized by X-ray powder diffraction (XRD), BET surface area, oxygen uptake, and X-ray photoelectron spectroscopy (XPS) techniques. XRD results of 773?K calcined samples conferred an amorphous nature of the mixed oxide support and a highly dispersed form of vanadium oxide. Oxygen uptake measurements supported the formation of a monolayer of vanadium oxide over the thermally stable TiO₂?CZrO₂ support. The O 1s, Ti 2p, Zr 3d, and V 2p core level photoelectron peaks of TiO₂?CZrO₂ and V₂O₅/TiO₂?CZrO₂ catalysts are sensitive to the calcination temperature. No significant changes in the oxidation states of Ti⁴⁺ and Zr⁴⁺ were noted with increasing thermal treatments. Vanadium oxide stabilized as V⁴⁺ at lower temperatures, and the presence of V⁵⁺ is observed at 1,073?K. The synthesized catalysts were evaluated for selective oxidation of o-xylene under normal atmospheric pressure in the temperature range of 600?C708?K. The TiO₂?CZrO₂ support exhibits very less conversion of o-xylene, while 12 wt% V₂O₅ loaded sample exhibited a good conversion and a high product selectivity towards the desired product, phthalic anhydride.     

Selective oxidation of CO in excess hydrogen on copper—cerium-containing catalysts

Selective oxidation of CO that is in mixtures enriched in H₂ was studied to investigate catalytic properties of the 0.5—80% CuO/Ce_0.7Zr_0.3O₂ system. The catalysts were prepared by the combined decomposition of copper, cerium, and zirconyl nitrates at 300 °C. The systems studied are active and stable under mild conditions of the process (80—160 °C) and at high space velocities (to 100000 h^–1) of the reaction mixture (2% CO, 1% O₂, 40—50% H₂). With an increase in the CuO content in the catalysts up to 20%, the degree of CO removal achieves 60% (120 °C and V = 35000 h^–1) and further does not change appreciably. The contribution of oxygen participation into CO oxidation is virtually independent of the copper concentration in the sample and ranges from 65 to 75%. The dependences of the Arrhenius equation parameters for CO and H₂ oxidation on the catalyst composition were determined, which makes it possible to calculate the conversion of reactants and selectivity of CO conversion under the specified conditions of the process. The addition of CO₂ and H₂O (12—15%) to the reaction mixture decreases the catalyst activity and simultaneously increases the selectivity of CO oxidation to 100%. It is shown by the TPR and X-ray diffraction methods that the combined decomposition of the starting Cu²⁺, Ce³⁺, and ZrO²⁺ nitrates produces solid solutions of oxides with a high content of CuO. The reductive pre-treatment of fresh samples of the studied catalysts results in the destruction of the solid solution and formation of highly dispersed Cu particles on the surface of Ce—Zr—O. These particles are active in CO oxidation.     

Platinum–tin complexes as catalysts for the anodic oxidation of borohydride

Platinum–tin complexes were prepared by the reduction of Pt(IV) with Sn(II) in HCl media and studied by light absorption spectrometry, X-ray photoelectron spectroscopy (XPS), and electron microscopy. The formation of three complexes, H₃[Pt(SnCl₃)₅], H₂[Pt(SnCl₃)₂Cl₂], and H₂[Pt₃(SnCl₃)₈], depending on HCl and SnCl₂ concentrations, has been shown. The glassy carbon (GC) electrode modified in the complexes solutions was found to be an electrocatalyst for borohydride oxidation in a 1.0-M NaOH solution. Comparison of BH₄ ⁻ electrooxidation on Pt and on GC modified with platinum–tin complexes has shown that catalytic hydrolysis of BH₄ ⁻ did not proceed in the latter case in contrast to its oxidation on the Pt electrode, and only direct BH₄ ⁻ oxidation has been observed in the positive potentials scan. The activity of Pt–Sn complexes for BH₄ ⁻ oxidation changes with time and eventually decreases due to Sn(II), bound in the complex with Pt(II), oxidation by atmospheric oxygen. The complexes may be renewed by addition of missing amounts of SnCl₂ and HCl.     

Properties of Pd–Ag/C catalysts in the reaction of selective hydrogenation of acetylene

Samples of Pd/C and Pd–Ag/C, where C represents carbon nanofibers (CNFs), are synthesized by methane decomposition on a Ni–Cu–Fe/Al₂O₃ catalyst. The properties of Pd/CNF are studied in the reaction of selective hydrogenation of acetylene into ethylene. It is found that the activity of the catalyst in hydrogenation reaction increases, while selectivity decreases considerably when the palladium content rises. The obtained dependences are caused by the features of palladium’s interaction with the carbon support. At a low Pd content (up to 0.04 wt %) in the catalyst, the metal is inserted into the interlayer space of graphite and the catalytic activity is zero. It is established by EXAFS that the main share of palladium in catalysts of 0.05–0.1 wt % Pd/CNF constitutes the metal in the atomically dispersed state. The coordination environment of palladium atoms consists of carbon atoms. An increase in the palladium content in a Pd/CNF catalyst up to 0.3 wt % leads to the formation of highly dispersed (0.8–1 nm) Pd particles. The Pd/CNF samples where palladium is mainly in the atomically dispersed state exhibit the highest selectivity in the acetylene hydrogenation reaction. The addition of silver to a 0.1 wt % Pd/CNF catalyst initially probably leads to the formation of Pd–Ag clusters and then to alloyed Pd–Ag particles. An increase in the silver content in the catalyst above 0.3% causes the enlargement of the alloyed particles and the palladium atoms are blocked by a silver layer, which considerably decreases the catalytic activity in the selective hydrogenation of acetylene.     

Synthesis and characterization of two binuclear nickel(II) complexes of thiophenol-based “end-off” compartmental ligands and their application as catalysts for selective oxidation of sulfides

Reaction of the binucleating S-protected ligand precursors 2-(N,N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2′-hydroxy anil (I) and 2-(N,N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2′-hydroxy 5′-methyl anil (II) with nickel(II) acetate tetrahydrate in the presence of pyrazole afforded the binuclear nickel(II) complexes [L^INi₂(pz)] (1) and [L^IINi₂(pz)] (2), respectively. The complexes have been characterized by routine physicochemical studies as well as by X-ray single crystal structure analysis. In both complexes, Ni(II) ions are doubly bridged by the thiophenolic sulfur of the pentadentate Schiff base ligand and a pyrazolate group. Efficient protocols for the oxidation of sulfides to sulfoxides with high selectivities, catalyzed by binuclear μ-thiophenolato-μ-pyrazolatonickel(II) in the presence of urea hydrogen peroxide (UHP) were explored. We obtained predominantly the monooxygenated product. The resulting products are obtained in good to excellent yields within a reasonable time.     

Removal of CO from reformed fuels by selective methanation over Ni-B-Zr-Oδ catalysts

The Ni-B-Oδ andNi-B-Zr-Oδ catalysts were prepared by the method of chemical reduction, and the deep removal of CO by selective methanation from the reformed fuels was performed over the as-prepared catalysts. The results showed that zirconium strongly influenced the activity and selectivity of the Ni-B-Zr-Oδ catalysts. Over the Ni-B-Oδ catalyst, the highest CO conversion obtained was only 24.32% under the experimental conditions studied. However, over the Ni-B-Zr-Oδ catalysts, the CO methanation conversion was higher than 90% when the temperature was increased to 220 oC. Additionally, it was found that the Ni/B mole ratio also affected the performance of the Ni-B-Zr-Oδ catalysts. With the increase of the Ni/B mole ratio from 1.8 to 2.2, the CO methanation activity of the catalyst was improved. But when the Ni/B mole ratio was higher than 2.2, the performance of the catalyst for CO selective methanation decreased instead. Among all the catalysts, the Ni29B13Zr58Oδ catalyst investigated here exhibited the highest catalytic performance for the CO selective methanation, which was capable of reducing the CO outlet concentration to less than 40 ppm from the feed gases stream in the temperature range of 230–250 oC, while the CO2 conversion was kept below 8% all along. Characterization of the Ni-B-Oδ and Ni-B-Zr-Oδ catalysts was provided by XRD, SEM, DSC, and XPS.     

Removal of CO from reformed fuels by selective methanation over Ni-B-Zr-Oδ catalysts

The Ni-B-Oδ and Ni-B-Zr-Oδcatalysts were prepared by the method of chemical reduction, and the deep removal of CO by selective methana-tion from the reformed fuels was performed over the as-prepared catalysts. The results showed that zirconium strongly influenced the activity and selectivity of the Ni-B-Zr-Oδ catalysts. Over the Ni-B-Oδ catalyst, the highest CO conversion obtained was only 24.32% under the experi-mental conditions studied. However, over the Ni-B-Zr-Oδ catalysts, the CO methanation conversion was higher than 90% when the temperature was increased to 220℃. Additionally, it was found that the Ni/B mole ratio also affected the performance of the Ni-B-Zr-Oδ catalysts. With the increase of the Ni/B mole ratio from 1.8 to 2.2, the CO methanation activity of the catalyst was improved. But when the Ni/B mole ratio was higher than 2.2, the performance of the catalyst for CO selective methanation decreased instead. Among all the catalysts, the Ni29B13Zr58Oδcatalyst investigated here exhibited the highest catalytic performance for the CO selective methanation, which was capable of reducing the CO outlet concentration to less than 40 ppm from the feed gases stream in the temperature range of 230-250℃, while the CO2 conversion was kept below 8% all along. Characterization of the Ni-B-Oδ and Ni-B-Zr-Oδ catalysts was provided by XRD, SEM, DSC, and XPS.     

Total oxidation of ethanol and toluene over ceria—zirconia supported platinum catalysts

The effect of platinum loading (0.09–1.00 mass %) on the performance of ceria-zirconia supported catalysts in the total oxidation of ethanol and toluene in air was investigated. The introduction of platinum promoted the reduction of surface cerium and decreased the acidity of the catalysts. In ethanol oxidation, the temperature of 50 % conversion decreased with increasing platinum content. This increase in catalytic performance was more pronounced for the catalysts with 0.59 mass % and 1.00 mass % Pt. On the other hand, higher amount of by-products (mainly acetaldehyde) was observed at increased platinum loadings. For all catalysts, a correlation between their H₂-TPR profiles and catalytic performance was revealed. In toluene oxidation, only the catalysts with 0.59 mass % and 1.00 mass % Pt exhibited a lower temperature of 50 % conversion than pristine ceria-zirconia. The effect of platinum loading was less pronounced than in ethanol oxidation and a correlation between reduction behaviour and catalytic performance was not observed. The superior catalytic performance of the catalysts with 0.59 mass % and 1.00 mass % of Pt in both ethanol and toluene oxidation was ascribed to the presence of large platinum nanoparticles, which were not observed at lower Pt loadings.     

Deep oxidation of methane on granulated and monolith copper—manganese oxide catalysts

Deep oxidation of methane on the granulated Cu—Mn-mixed oxide catalyst and metallic monolith catalysts coated with the same oxide was studied. The experimental kinetic curves for both monolith and granulated catalysts are satisfactorily described by the first-order rate law. The values of activation energies, reaction rate constants, and feed flow rates for the specified conversion almost coincide for both types of the catalysts. The data obtained confirm the possibility of a quantitative comparison of the activities of the granulated and monolith catalysts. The activity of the monoliths is proportional to the concentration of the active component.     

Mechanism into selective oxidation of cinnamaldehyde using β-cyclodextrin polymer as phase-transfer catalyst

Selective oxidation of cinnamaldehyde to benzaldehyde in the presence of bicarbonate and hydrogen peroxide and catalyzed by β-cyclodextrin polymer (β-CDP) was investigated. β-CDP was utilized as the phase-transfer catalyst in this study. The immobilized β-cyclodextrin possessing a hydrophobic host cavity was found to be efficient as mass-transfer promoters for the oxidation of cinnamaldehyde. Benzaldehyde could be obtained in 63% yield under optimal reaction conditions. The results indicate the complex formed between cinnamaldehyde and β-CDP via the intermolecular weak interactions, e.g., hydrogen bond was the reason why the conversion and selectivity could be significantly promoted. Finally, the reusability of the catalyst was also evaluated. Its catalytic activity remained unchanged even after recycled for six times, which suggests it is an efficient catalyst for oxidation of cinnamaldehyde.     

Catalytic reduction of NOx and oxidation of dichloroethane over α-MnO2 catalysts: Properties-Reactivity relationship

The reduction ability of NO to N₂ and the oxidation performance of 1,2-dichloroethane (DCE) over α-MnO₂ catalysts were investigated. The results show that α-MnO₂-3 exhibited the highest catalytic activity in 63.5 % conversion of NO_x reduction by C₃H₈ at 250 °C, and 80 % conversion of DCE combustion by O₂ at 338 °C. It is revealed the active phase of α-MnO₂-3 is tetragonal α-MnO₂ with the selectively exposed plane of (2 1 1). It was proposed the high DCE decomposition of α-MnO₂-3 was ascribed to the redox properties. The overall characterization results revealed that α-MnO₂-3 catalyst preserves more active sites of low valence Mn and higher surface adsorbed oxygen (O_ads) /lattice oxygen (O_latt) at the outermost layers, and lower reduction temperature in H₂-TPR profiles than that of other catalysts. Meanwhile, NH₃-TPD profile of α-MnO₂-3 also shows a large number of acid sites promote NO_x reduction.     

Structural evolution of Pt/ceria–zirconia TWC catalysts during the oxidation of carbon monoxide

The structural evolution of two Pt/ceria–zirconia catalysts, characterized by different amounts of supported Pt, was monitored by in situ X-ray diffraction during the anaerobic oxidation of CO at different temperatures. In a first phase, oxygen coming from the surface layers of the ceria–zirconia mixed oxide is consumed and no structural variation of the support is observed. After this induction time, bulk reduction of Pt/ceria–zirconia takes place as a step-like process, while the CO₂ production continues at a nearly constant rate. This behavior is totally different from that of the metal-free support in similar reaction conditions, that show a gradual bulk reduction. In repeated oxidation–reduction cycles, it was observed that the induction time in Pt/ceria–zirconia is a function of the thermal history, of the amount of supported Pt and of the structural evolution of the samples.     

Pd supported on N-doped-ordered mesoporous carbons’ catalysts for selective hydrodechlorination of 4-chlorophenol

Pd catalysts supported on N-doped-ordered mesoporous carbons (NOMC) have been prepared and tested for selective hydrogenation of 4-chlorophenol (4-CP) with H₂. The difference from the previous methods is that the NOMC was synthesized using urea as nitrogen source via one-pot route. The rate constant of Pd/NOMC for hydrodechlorination of 4-CP was about 135.9 h^?1 which were higher than Pd/OMC (65.6 h^?1) and Pd/AC (20.8 h^?1). It could be attributed to the synergetic effects of mesoporous structure, N-doped supports, and the stabilized small PdNPs. The conversion changed from 100 to 90.2% after the sixth reaction using Pd/NOMC which could be caused by the palladium leaching.     

Base-free aerobic oxidation of glycerol on TiO_2-supported bimetallic Au–Pt catalysts

The aerobic oxidation of glycerol provides an economically viable route to glyceraldehyde, dihydroxyacetone and glyceric acid with versatile applications, for which monometallic Pt, Au and Pd and bimetallic Au–Pt, Au–Pd and Pt–Pd catalysts on Ti O2 were examined under base-free conditions. Pt exhibited a superior activity relative to Pd, and Au–Pd and Pt–Pd while Au was essentially inactive. The presence of Au on the Au–Pt/Ti O2 catalysts led to their higher activities(normalized per Pt atom) in a wide range of Au/Pt atomic ratios(i.e.1/3–7/1), and the one with the Au/Pt ratio of 3/1 exhibited the highest activity. Such promoting effect is ascribed to the increased electron density on Pt via the electron transfer from Au to Pt, as characterized by the temperature-programmed desorption of CO and infra-red spectroscopy for CO adsorption. Meanwhile,the presence of Au on Au–Pt/Ti O2, most like due to the observed electron transfer, changed the product selectivity, and facilitated the oxidation of the secondary hydroxyl groups in glycerol, leading to the favorable formation of dihydroxyacetone over glyceraldehyde and glyceric acid that were derived from the oxidation of the primary hydroxyl groups. The synergetic effect between Au and Pt demonstrates the feasibility in the efficient oxidation of glycerol to the targeted products, for example, by rational tuning of the electronic properties of metal catalysts.