The Characterization of Tungsten-Oxide-Modified Zirconia Supports for Dual Functional Catalysis

The results of catalytic titration measurements indicated that WO _x /ZrO₂ catalysts prepared by coprecipitation have higher acid site density and strength, and are more active for pentane isomerization, than catalysts prepared by impregnation. The coprecipitated WO _x /ZrO₂ contains 0.004 meq-H⁺/g-catalyst. XPS of chemisorbed 2,6-dimethylpyridine and pyridine revealed the presence of Lewis acid sites as well as strong and weak Brønsted acid sites on the surface of these catalysts. The concentration of strong Brønsted sites was close to the concentration of Lewis sites, suggesting that the high acidity of these materials may originate from a conjugate Brønsted–Lewis site. Pt/WO _x /ZrO₂ undergoes a reversible loss of hydrogen chemisorption capacity with increasing hydrogen pretreatment temperature, accompanied by a reversible loss of pentane isomerization activity. This loss can be attributed to a strong Pt-reduced tungsten oxo species interaction (SMSI). Room temperature hydrogen spillover is observed in the Pt/WO _x /ZrO₂ (16% W) catalyst, consistent with the presence of bulk WO₃ in this material as observed by TPR.     

Partial Oxidation of Ethanol to Hydrogen over Ni–Fe Catalysts

A study has been conducted to identify the influence of zirconia phase and copper to zirconia surface area on the activity of Cu/ZrO₂ catalysts for the synthesis of methanol from either CO/H₂ or CO₂/H₂. To determine the effects of zirconia phase, a pair of Cu/ZrO₂ catalysts was prepared on tetragonal (t-) and monoclinic (m-) zirconia. The zirconia surface area and the Cu dispersion were essentially identical for these two catalysts. At 548 K, 0.65 MPa, and H₂/CO_x= 3 (x = 1, 2), the catalyst prepared on m-ZrO₂ was 4.5 times more active for methanol synthesis from CO₂/H₂ than that prepared on t-ZrO₂, and 7.5 times more active when CO/H₂ was used as the feed. Increasing the surface area of m-ZrO₂ and the ratio of Cu to ZrO₂ surface areas further increased the methanol synthesis activity. In situ infrared spectroscopy and transient-response experiments indicate that the higher rate of methanol synthesis from CO₂/H₂ over Cu/m-ZrO₂ is due solely to the higher concentration of active intermediates. By contrast, the higher rate of methanol synthesis from CO/H₂ is due to both a higher concentration of surface intermediates and the more rapid dynamics of their transformation over Cu/ZrO₂.     

Trimerization of isobutene over WOx/ZrO2 catalysts

Trimerization of isobutene to produce isobutene trimers has been investigated over WO_x/ZrO₂ catalysts that were obtained by wet-impregnation and successive calcination at high temperatures. Very stable isobutene conversion and high selectivity for trimers are attained over a WO_x/ZrO₂ catalyst obtained by calcination at 700 °C. From the XRD study it can be understood that tetragonal ZrO₂ is beneficial for stable performance; however, monoclinic ZrO₂ is not good for trimerization. Nitrogen adsorption and FTIR experiments suggest that amorphous WO_x/ZrO₂ is inefficient catalyst even though it has high surface area and high concentration of acid sites. The observed performance with the increased selectivity and stable conversion demonstrates that a WO_x/ZrO₂ having tetragonal zirconia, even with decreased porosity and acid sites, is one of the best catalysts to exhibit stable and high conversion, high selectivity for trimers and facile regeneration.     

Surface phase transformation of ZrO2 in VOx/ZrO2 catalysts for boosting propane nonoxidative dehydrogenation

The nanocatalysts of VO_x deposited on ZrO₂ supports with single monoclinic (ZrO₂-M), tetragonal (ZrO₂-T), and binary monoclinic-tetragonal (ZrO₂-MT) phase were synthesized. VO_x/ZrO₂-MT catalysts exhibit better performance during propane nonoxidative dehydrogenation than VO_x/ZrO₂-M and VO_x/ZrO₂-T catalysts. Among VO_x/ZrO₂-MT catalysts, the conversion and deactivation rate constant of VO_x/ZrO₂-M₃₁T₆₉ catalyst is 35.2% and 0.22 h⁻¹, respectively. The promoting role of ZrO₂-MT is revealed by experiments and theoretical calculations. The MT-mixed phase structure in VO_x/ZrO₂-MT catalyst improves the structural properties and dispersion of VO_x. The tetragonal-monoclinic transformation on the ZrO₂-MT surface facilitates VO_x reduction and produces additional V³⁺ active sites. The highly dispersed V³⁺ sites on the ZrO₂-MT surface accelerate C H bond breaking and boost the desorption of propylene, which is the key reason for enhancing activity and stability during the reaction, respectively. Insight into the role of surface phase transformation of ZrO₂-MT is expected to obtain high-efficient catalysts further.     

Oxidation of o-Xylene to Phthalic Anhydride on Sb-V/ZrO2 Catalysts

Zirconia-supported and bulk-mixed vanadiumantimonium oxide catalysts were used for the oxidation of o-xylene to phthalic anhydride. X-ray diffraction, Raman spectroscopy and photoelectron spectroscopy were used for characterization. It was found that vanadium promotes the transition of tetragonal to monoclinic zirconia. The simultaneous presence of Sb and V on zirconia at low coverage led to a preferential interaction of individual V and Sb oxides with the zirconia surface rather than the formation of a binary Sb-V oxide, while at higher Sb-V contents the formation of SbVO₄ took place. Sb-V/ZrO₂ catalysts showed high activity for o-xylene conversion and better selectivity to phthalic anhydride as compared to V/ZrO₂ catalysts. However, their selectivity to phthalic anhydride was poor in comparison to a V/TiO₂ commercial catalyst. The improved selectivity of the Sb-containing catalysts is attributed to the blocking of non-effective surface sites of ZrO₂, the decrease of the total amount of acid sites and the formation of surface V-O-Sb-O-V structures.     

Effect of calcium and potassium on V2O5/ZrO2 catalyst for oxidative dehydrogenation of propane: a comparative study

The effect of calcium and potassium on the physiochemical properties and performance of V₂O₅/ZrO₂ catalyst for oxidative dehydrogenation of propane was studied in the temperature range of 385–400 °C. The vanadia loading was kept constant at 5 VO_x/nm² and the atomic ratio A/V (A=Ca, K) was varied from 0.05 to 0.75. The vanadia surface structure was investigated using X-ray diffraction analysis (XRD), electron paramagnetic resonance (EPR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The redox property of the catalysts was studied by temperature programmed reduction (TPR) and temperature programmed oxidation (TPO) whereas surface acidity was measured by temperature programmed desorption (TPD) of ammonia. Calcium and potassium both interact with the surface V=O and stabilize the +5 oxidation state of vanadium. Interaction between calcium and vanadium was more intense though surface concentration of calcium was lower than that of potassium. For doped catalysts, the activity was lower due to an increase in reduction temperature as well as a lower extent of reduction and increased resistance to undergo redox cycles. On the other hand, removal of surface acidic sites by the dopants increased the propene selectivity. Potassium was more effective in decreasing the activity and increasing the propene selectivity.     

Effect of Sulfation on the Acid-Base Properties of Tetragonal Zirconia. A Calorimetric and IR Spectroscopic Study

The RT adsorption of CO₂ was studied in order to compare the surface acid-base properties of yttria-stabilized tetragonal ZrO₂, either plain or variously sulfated. The nature of the species formed upon CO₂ adsorption, as well as their stability upon outgassing, was monitored by IR spectroscopy, whereas the population of the sites and their energy distribution was studied by microcalorimetry. The effect of sulfation on the basicity of cus Zr⁴⁺/O^2- pairs and on the Lewis acidic strength of cus Zr⁴⁺ cations, as well as the influence of calcination on the amount and nature of surface sulfates were studied and correlated with the catalytic activity of SZ systems.     

Study by high-throughput experimentation of the effect of the pretreatment and precursors on the catalytic activity of tungstated zirconia catalysts

High-throughput experimentation (HTE) was used for the synthesis, characterization and catalytic evaluation of tungstated zirconia (WZ) materials doped with manganese. A library with three series of MnO_y–WO_x–ZrO₂ catalysts was prepared by different methods (surfactant-assisted coprecipitation and impregnation), using different precursors and pretreatments (washing and/or aging). These materials were characterized by XRD, Raman and MET (HRTEM and EDS). Different nanostructures were observed depending on the synthesis method. Highly dispersed WO₃ catalysts calcined at 800 °C were obtained by coprecipitation method, while the impregnation method brings the segregation of both, the monoclinic WO₃ and ZrO₂ phases. The catalytic activity of the Pt-promoted MnO_y–WO_x–ZrO₂ catalysts (0.3 wt.% Pt) was evaluated in the n-hexane hydroisomerization reaction. Although, in the coprecipitated catalysts similar WO_x nanostructures were observed, the catalytic activity mainly depends on the zirconia precursor, as well as aging and washing pretreatments, following the order: ZrOCl₂ (coprecipitation) > ZrO(NO₃)₂ (coprecipitation)  Zr(OH)₄ (impregnation). The catalysts with highest activity were pretreated by washing and aging.     

Novel MoO3/CeO2–ZrO2 catalyst for the selective catalytic reduction of NOx by NH3

A series of MoO₃-doped CeO₂–ZrO₂ catalysts were investigated for the selective catalytic reduction of NO_x by NH₃ (NH₃-SCR). It was found that the added MoO₃ significantly enhanced the activity of CeO₂–ZrO₂ catalyst for NH₃-SCR of NO_x in a wide temperature range and the optimum MoO₃ loading is 5%. The highly dispersed MoO₃ not only resulted in more Lewis acid and Brønsted acid sites formed on the catalyst surface, but also increased the redox property of the catalyst, all of which account for the enhanced SCR activity.     

Methane Combustion and CO Oxidation on Zirconia-Supported La,Mn Oxides and LaMnO3 Perovskite

ZrO₂-supported La, Mn oxide catalysts with different La, Mn loading (0.7, 2, 4, 6, 12, and 16 wt% as LaMnO₃) were prepared by impregnation of tetragonal ZrO₂ with equimolar amounts of La and Mn citrate precursors and calcination at 1073 K. The catalysts were characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and BET specific surface area determination. The redox properties were tested by temperature-programmed reduction (TPR), and the catalytic tests were carried out for methane combustion at 650–1050 K and for CO oxidation at 350–800 K. XRD revealed the presence of tetragonal zirconia with traces of the monoclinic phase. LaMnO₃ perovskite was also detected for loading higher than 6%. XAS and TPR experiments suggested that at high loading small crystallites of LaMnO₃, not uniformly spread on the zirconia surface, were formed; while at low loading, La, Mn oxide species interacting with the support, and hard to be structurally defined, prevailed. The catalysis study indicated that the presence of a perovskite-like structure is necessary for the development of highly active sites. Dilute catalysts were in fact poorly active even when considering the activity per gram of La, Mn perovskite-like composition. For methane combustion and CO oxidation, similar trends of the activity as a function of the loading point to a similarity of the active sites for the two reactions on the examined catalytic system.     

Amination of Polyethylene Glycol to Polyetheramine over the Supported Nickel Catalysts

Surface nickel (NiO _x ) species, surface NiAl _x O _y compound, and NiO crystallites are present on the Ni/Al₂O₃ catalysts, and the ratio of these nickel species is dependent on the nickel loading. Surface nickel interacts with the TiO₂ support to form a surface nickel titanate compound (NiTiO _x ) which has a lower reducibility. The weak interaction between the surface nickel and the silica support results in the formation of NiO crystallites on the SiO₂ surface. The Ni/Al₂O₃ and Ni/TiO₂ catalysts contain new surface Lewis acid sites and the amount of surface Lewis acid sites increases with increasing nickel concentration. The Ni/SiO₂ catalysts have no sign of the presence of the surface Lewis acid sites. Only the Ni/Al₂O₃ catalysts have shown the ammonia adsorption at temperature of 200°C. Supported nickel on alumina catalysts possess the highest amination conversion, and the amine yield increases with increasing nickel loading up to 15% and starts to level off. By comparing amination catalysis with quantitatively TPR studies of the H₂ consumed of the Ni/Al₂O₃ catalysts, it appears that the dispersed nickel species are the active sites for amination. In addition, the amination product is mainly the secondary amine due to the presence of water.     

A study of “superacidic” MoO3/ZrO2 catalysts for methane oxidation

A series of zirconia-supported molybdenum oxide catalysts with different molybdenum loadings prepared using conditions reported to generate “superacidity” have been evaluated for their performance as catalysts for methane oxidation. A marked dependence of Mo content on activity has been observed, with the most active material being that with intermediate molybdenum content. 5 wt% MoO₃/ZrO₂ compares favourably with Zr_xCe_1-xO₂ for methane combustion. The presence of MoO₃ is observed to stabilise the tetragonal polymorph of ZrO₂ and, as Mo content is increased, dispersed MoO₃ crystallites are formed as evidenced by Raman spectroscopy. Temperature-programmed reduction studies evidence differences in the reduction behaviour of the materials as a function of loading. The results indicate that molybdenum oxide supported on monoclinic zirconia gives rise to the most active catalyst. It is tentatively suggested that the formation of a MoO₃ monolayer during reaction may be of importance. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of hydrogen treatments on ZrO2 and Pt/ZrO2 catalysts

ZrO₂ and Pt/ZrO₂ catalysts have been investigated by TPR, hydrogen chemisorption, TPDH and in the conversion ofn-hexane. At high temperature, ZrO₂ takes up hydrogen. High temperature hydrogen treatment is a precondition of the catalytic activity in then-hexane conversion. Possibly, catalytically active acid sites are formed by this hydrogen treatment. The high temperature hydrogen treatment induces a strong Pt-ZrO₂ interaction.     

Water-gas shift reaction over supported Pt and Pt-CeOx catalysts

A comparison study was performed of the water-gas shift (WGS) reaction over Pt and ceria-promoted Pt catalysts supported on CeO₂, ZrO₂, and TiO₂ under rather severe reaction conditions: 6.7 mol% CO, 6.7 mol% CO₂, and 33.2 mol% H₂O in H₂. Several techniques—CO chemisorption, temperature-programmed reduction (TPR), and inductively coupled plasma-atomic emission spectroscopy (ICP-AES)—were employed to characterize the catalysts. The WGS reaction rate increased with increasing amount of chemisorbed CO over Pt/ZrO₂, Pt/TiO₂, and Pt-CeO _x /ZrO₂, whereas no such correlation was found over Pt/CeO₂, Pt-CeO _x /CeO₂, and Pt-CeO _x /TiO₂. For these catalysts in the absence of any impurities such as Na⁺, the WGS activity increased with increasing surface area of the support, showed a maximum value, and then decreased as the surface area of the support was further increased. An adverse effect of Na⁺ on the amount of chemisorbed CO and the WGS activity was observed over Pt/CeO₂. Pt-CeO _x /TiO₂ (51) showed the highest WGS activity among the tested supported Pt and Pt-CeO_x catalysts. The close contact between Pt and the support or between Pt and CeO _x , as monitored by H₂-TPR, is closely related to the WGS activity. The catalytic stability at 583K improved with increasing surface area of the support over the CeO₂- and ZrO₂-supported Pt and Pt-CeO _x catalysts.     

Synthesis of bio-additives: Acetylation of glycerol over zirconia-based solid acid catalysts

Acetylation of glycerol with acetic acid was investigated over ZrO₂, TiO₂–ZrO₂, WO_x/TiO₂–ZrO₂ and MoO_x/TiO₂–ZrO₂ solid acid catalysts to synthesize monoacetin, diacetin and triacetin having interesting applications as bio-additives for petroleum fuels. The prepared catalysts were characterized by means of XRD, BET surface area, ammonia-TPD and FT-Raman techniques. The effect of various parameters such as reaction temperature, molar ratio of acetic acid to glycerol, catalyst wt.% and time-on-stream were studied to optimize the reaction conditions. Among various catalysts investigated, the MoO_x/TiO₂–ZrO₂ combination exhibited highest conversion (~ 100%) with best product selectivity, and a high time-on-stream stability.     

Enhancing the Fischer–Tropsch Synthesis Activity of Co-based Catalysts by Adding ZrOx to the SiO2 Support and Chelating Ligands to the Co-precursor

Abstract  

Co/ZrO _x /SiO₂ catalysts with enhanced dispersion of Co⁰ and turnover frequency were successfully prepared combining two different promotion effects, i.e., modifications of SiO₂ surface with ZrO _x by liquid phase deposition and influencing coordination structure of Co species using chelating agents or glycols. The catalysts exhibited ~6.3-fold higher CO conversion than Co/SiO₂ and those promoted by organic additives or ZrO _x alone, indicating activity enhancement was induced by cooperation of these two promoters.     

Biodiesel production from waste cooking oil over alkaline modified zirconia catalyst

Screening and catalytic activity of alkaline modified zirconia i.e. Mg/ZrO₂, Ca/ZrO₂, Sr/ZrO₂, and Ba/ZrO₂ as heterogeneous catalyst in biodiesel production from waste cooking oil (WCO) have been investigated. The catalysts were prepared via wet impregnation of alkaline nitrate salts supported on zirconia. Physico-chemical characteristics of the catalysts were analyzed by BET surface area, XRD, FESEM and CO₂–NH₃–TPD. Among the catalysts screened, Sr/ZrO₂ exhibited higher catalytic activities. Characterization results disclosed Sr/ZrO₂ catalyst possessed balanced basic and acid site concentrations with its pore volume, surface area as well as pore diameters suitable for biodiesel production. The balanced active sites facilitated simultaneous transesterification and esterification of WCO. A plausible mechanism has been suggested for the simultaneous reactions. The effects of operating process conditions such as methanol to oil molar ratio, reaction temperature and catalyst loading on biodiesel production in the presence of Sr/ZrO₂ were investigated. Methyl ester (ME) yield at 79.7% was produced over 2.7 wt.% catalyst loading (Sr/ZrO₂), 29:1 methanol to oil molar ratio, 169 min of reaction time and 115.5 °C temperature.     

The effect of the change of the structure on oxidative dehydrogenation of propane over cerium–zirconium catalysts

A series of pure CeO₂, ZrO₂, and CeZrO_x mixed metal oxide catalysts were prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 500°C and 0.1 MPa. The prepared catalysts were characterized by thermal gravimetric analysis (TGA), Brunauer, Emmett, and Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopes (TEM), Raman spectroscopy, and H₂-TPR. It was observed that the zirconium content of the solid solution of the mixed metal oxide catalyst was 5%–25%, while the zirconium content of the material with phase segregation was higher (50%). The addition of zirconium was proven to decrease the oxygen vacancy concentration on the catalyst surface and change the intensity of (111) crystal of cerium oxide in the catalysts. Among the prepared catalysts, the Ce_0.90Zr_0.10O_x catalyst with the maximum strength of the (111) crystal plane of cerium oxide exhibited the better catalytic oxidation performance for the dehydrogenation of propane to propylene. Compared with ZrO₂ in the blank experiment, the average propane conversion and propylene selectivity of the Ce_0.90Zr_0.10O_x catalyst were increased by 10.78% and 17.95%, respectively.     

An Efficient and Ecofriendly WOx–ZrO2 Solid Acid Catalyst for Classical Mannich Reaction

An ecofriendly WO_x–ZrO₂ solid acid catalyst has been employed for the synthesis of β-amino ketones by a three-component Mannich reaction in the liquid phase under solvent-free conditions at ambient temperature. To make the WO_x–ZrO₂ catalyst, WO_x from ammonium metatungstate was incorporated into the hydrous zirconia and calcined at 923 K. The incorporated promoter showed a strong influence on the surface and bulk properties of the zirconia. Surface and bulk properties of the catalyst were investigated by means of X-ray powder diffraction, temperature programmed desorption of ammonia, Raman spectroscopy, scanning electron microscopy, and BET surface area methods. Characterization studies reveal that the WO_x–ZrO₂ catalyst exhibits strong solid acidity. The catalytic activity results suggest that the methodology adopted offers significant improvements for the synthesis of β-amino ketones with regard to yield of products, simplicity in the operation, and green aspects by avoiding toxic conventional catalysts and solvents.