Effect of iron on Cu/SiO2 catalysts for the dehydrogenation of cyclohexanol to cyclohexanone

At the temperature range of 250–390°C, the addition of iron to Cu/SiO₂ catalyst increased the conversion and the selectivity of cyclohexanone. The iron incorporation into Cu/SiO₂ catalyst enhanced the reduction temperature of copper oxide, increased the dispersion of copper metal and decreased the selectivity of cyclohexene. Copper was enriched on the surface of the used metal catalyst compared to that in freshly calcined or reduced catalyst. Unlike Cu dispersed on bulk iron oxide, the Cu-Fe dispersed on silica showed negligible amount of phenol formation, thus keeping the selectivity of cyclohexanone very high even at high reaction temperatures. The Fe³⁺ ion in the reduced Cu/Fe/SiO₂ catalyst resulted in a significant resistance of the Cu particle to sintering and a decrease in the selectivity of phenol arisen from the magnetite.     

Dehydrogenation of cyclohexanol to cyclohexanone over Cu/SiO2 catalysts : Dispersion and catalytic activity

Copper catalysts supported on silica (Cu/SiO₂) were prepared by three different methods; incipient wetness, precipitation, and ion exchange. Catalytic properties in the dehydrogenation of cyclohexanol over these catalysts were examined. Copper surface area increased in the order of incipient wetness precipitation ion-exchange method for the catalysis with the same loading of copper. Conversion was mainly dependent on the copper surface area regardless of preparation methods, and selectivity to cyclohexanone was very high for all Cu/SiO₂ catalysts.     

Dehydrogenation of cyclohexanol on Cu–ZnO/SiO2 catalysts: The role of copper species

For the dehydrogenation of cyclohexanol a series of Cu–ZnO/SiO₂ catalysts with various Cu to ZnO molar ratios was prepared using the impregnation method, with the loading of copper fixed at 9.5 at.%. The catalysts were characterized by XPS, H₂–N₂O titration, BET, H₂-TPR, NH₃-TPD and XRD techniques. The results indicate that the addition of ZnO can improve the dispersion of copper species on reduced Cu–ZnO/SiO₂ (CZS) catalysts. Cu⁰ and Cu⁺ species were found on the reduced CZS catalysts surface, and the amount of Cu⁺ increased with the content of ZnO increasing. The addition of ZnO increased the acidity of the CZS catalysts. However, only Cu⁰ species can be found on the reduced Cu/SiO₂ (CS) catalyst surface. According to the reaction results, we found that the selectivity to phenol was related to the amount of Cu⁺ species, the Cu⁺ species should be the active sites for the production of phenol, the Cu⁰ is responsible for cyclohexanol dehydrogenation to cyclohexanone.     

Highly active and selective Cu/SiO2 catalysts prepared by the urea hydrolysis method in dimethyl oxalate hydrogenation

Cu/SiO₂ catalysts have been successfully prepared via urea hydrolysis method. The catalysts have been systematically characterized by X-ray diffraction, high-resolution transmission electron microscopy, N₂-physisorption and H₂ temperature-programmed reduction. The results demonstrated the presence of copper nanoparticles and their high dispersion on the SiO₂ support. Catalysts with different copper loadings were prepared, and their performances in the hydrogenation of dimethyl oxalate to ethylene glycol were studied. A 100% conversion of dimethyl oxalate and maximum 98% selectivity of ethylene glycol were reached with 15.6 wt.% copper loading at 200 °C and 2 MPa. Furthermore, under the same reaction conditions, the catalyst can maintain the selectivity of 90% when the reduction temperature reduced from 350 °C to 200 °C. The high activity and selectivity over the catalyst may be ascribed to the homogenously distribution of copper nanoparticles on the large surface.     

Catalytic combustion of benzene over supported metal oxides catalysts

Catalytic combustion of benzene over supported metal oxides has been investigated. The catalysts have been prepared by incipient wetness method and characterized by XRD, FT-Raman, ESR and TPR. Among supported metal oxides, CuO_x, supported on TiO₂ is found to have the highest activity for benzene oxidation. In addition, among the catalysts of copper oxide supported on TiO₂, A1₂O₃ and SiO₂, titania-supported catalyst (CuO_x/TiO₂) gives the highest catalytic activity. CuO_x/TiO₂ (Cu loading 5.5 wt%) shows the total oxidation of benzene at about 250 °C. From the ESR and FT-Raman results, the CuO dispersed on the TiO₂ surface acts as an active site of CuO_x/TiO₂ catalysts on the oxidative decomposition of benzene. The catalytic activity gradually increases with an increase of Cu loading on TiO₂. When Cu loading reaches 5.5 wt%, the total conversion temperature is lowered to 300 °C. However, the catalytic activity considerably decreases at 7 wt% Cu loading. The catalytic activity increased with an increase of oxygen concentration but the concentration of benzene showed no difference in the benzene conversion. This result suggests that the rate determining step is the adsorption of oxygen.     

Ambient temperature oxidation of carbon monoxide using a Cu2Ag2O3 catalyst

The mixed copper–silver oxide, Cu₂Ag₂O₃, has been prepared by co-precipitation and tested for ambient temperature carbon monoxide oxidation. The catalyst demonstrated appreciable low temperature oxidation activity and the catalyst aged for 4 h was the most active. Carbon monoxide conversion increased with time-on-stream, reaching steady state after ca. 1000 min. Acomparison of the catalytic activity has been made with a representative sample of a high activity hopcalite, mixed copper/manganese oxide catalyst. On the basis of CO oxidation rate data corrected for the effect of catalyst surface area the Cu₂Ag₂O₃, aged for 4 h was at least as active as the hopcalite.     

Gas phase hydrogenation of maleic anhydride to tetrahydrofuran by Cu/ZnO/TiO2 catalysts in the presence of n-butanol

Cu/ZnO/TiO₂ catalysts were prepared via the coprecipitation method. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectrometry, temperature programmed reduction, and N₂ adsorption. The catalytic activity of Cu/ZnO/TiO₂ catalyst in gas phase hydrogenation of maleic anhydride in the presence of n-butanol was studied at 235–280 °C and 1 MPa. The conversion of maleic anhydride was more than 95.7% and the selectivity of tetrahydrofuran was up to 92.7%. At the same time, n-butanol was converted to butyraldehyde and butyl butyrate via reactions, namely, dehydrogenation, disproportionation, and esterification. There were two kinds of CuO species present in the calcined Cu/ZnO/TiO₂ catalysts. At a lower copper content, the CuO species strongly interacted with ZnO and TiO₂; at a higher copper content, both the surface-anchored and bulk CuO species were present. The metallic copper (CuO) produced by the reduction of the surface-anchored CuO species favored the deep hydrogenation of maleic anhydride to tetrahydrofuran. The deep hydrogenation activity of Cu/ZnO/TiO₂ catalyst increased with the decrease of crystallite sizes of CuO and the increase of microstrain values. Compensations of reaction heat and H₂ in the coupling reaction of maleic anhydride hydrogenation and n-butanol dehydrogenation were distinct.     

Effect of support modification by carbon coverage in the dehydrogenation activity of Cu/Al2O3 catalyst

Gamma alumina and carbon covered gamma alumina supported Cu catalysts were prepared and characterized by adsorptive decomposition of N₂O, NH₃ chemisorption and temperature-programmed reduction. The decrease in interaction of copper species with alumina of carbon covered alumina has influence on the conversion and selectivity of the reaction of cyclohexanol to cyclohexanone.     

An effective heterogeneous WO3/TiO2–SiO2 catalyst for selective oxidation of cyclopentene to glutaraldehyde by H2O2

TiO₂–SiO₂ mixed oxide with large pore size was synthesized by the xerogel method and it was then used to prepare the WO₃/TiO₂–SiO₂ catalyst by an incipient wetness method. The as‐prepared WO₃/TiO₂–SiO₂ sample was employed as the first heterogeneous catalyst in the liquid‐phase cyclopentene oxidation by aqueous H₂O₂, which exhibited higher selectivity (about 75%) to glutaraldehyde (GA) and, in turn, higher GA yield than the WO₃/SiO₂ heterogeneous catalyst and even the tungstic acid homogeneous catalyst under the same reaction conditions. The amorphous WO₃ phase was identified as the active sites and the loss of the active sites was proved to be not important. The lifetime of the catalyst was determined and its regeneration method was proposed. The effects of various factors on the catalytic behaviors, such as the WO₃ loading, the calcination temperature, the surface acidity and the reaction media, were investigated and discussed based on various characterizations including BET, XRD, XPS, FTIR, EXAFS and Raman spectra etc. This revised version was published online in July 2006 with corrections to the Cover Date.     

CO hydrogenation over a RhVO4/SiO2 catalyst after H2 reduction

The hydrogenation of CO over a RhVO₄/SiO₂ catalyst has been investigated after H₂ reduction at 773 K. A strong metal–oxide interaction (SMOI) induced by the decomposition of RhVO₄ in H₂ enhanced not only the selectivity to C₂ oxygenates but also the CO conversion drastically, compared with an unpromoted Rh/SiO₂ catalyst. The selectivity of the RhVO₄/SiO₂ catalyst was similar to those of conventional V₂O₅‐promoted Rh/SiO₂ catalysts (V₂O₅–Rh/SiO₂), but the CO dissociation activity (and TOF) was much higher than for V₂O₅–Rh/SiO₂, and hence the yield of C₂ oxygenates was increased. This revised version was published online in July 2006 with corrections to the Cover Date.     

Direct epoxidation of propylene to propylene oxide on various catalytic systems: A combinatorial micro-reactor study

A combinatorial approach is used to investigate several bimetallic catalytic systems and the promoter effect on these catalysts to develop highly active and selective catalysts for direct epoxidation of propylene to propylene oxide (PO) using molecular oxygen. 2%Cu/5%Ru/c-SiO₂ catalyst yielded the highest performance with high propylene conversion and PO selectivity among the bimetallic catalytic systems including silver, ruthenium, manganese and copper metals. On the other hand, the most effective catalyst and promoter in the epoxidation reaction was determined to be sodium chloride promoted Cu–Ru catalyst supported over SiO₂ with 36% selectivity & 9.6% conversion (3.46% yield) at 300 °C and 0.5 feed gas ratio (propylene/oxygen).     

Study on the Mechanism of CO Formation in Reverse Water Gas Shift Reaction Over Cu/SiO2 Catalyst by Pulse Reaction, TPD and TPR

The mechanism of reverse water gas shift reaction over Cu catalyst was studied by pulse reaction with QMS monitoring, temperature programmed desorption (TPD) and temperature programmed reduction (TPR) of Cu/SiO₂ catalyst. The reduced and/or oxidized copper offered low catalytic activity for the dissociation of CO₂ to CO in the pulse reaction study with 1 ml volume of He/CO₂, but the rate of CO formation was significantly enhanced with H₂ participating in the reaction. The TPD spectra of CO₂ obtained by feeding H₂/CO₂ over copper at 773 K provided strong evidence of the formation of formate at high temperature. The formate derived from the association of H₂ and CO₂ is proposed to be the key intermediate for CO production. The formate dissociation mechanism is the major reaction route for CO production.     

Immobilization of manganese tetraphenylporphyrin on Au/SiO2 as new catalyst for cyclohexane oxidation with air

Manganese tetraphenylporphyrin was successfully immobilized on Au/SiO₂, by using mercaptopyridine with sulfhydryl and pyridyl groups as bridging agent. The synthesized catalyst with novel structure was characterized by FTIR spectroscopic technique, XPS measurement, TG–DTA analysis and so on. During aerobic oxidation of cyclohexane in the presence of this material, the conversion of cyclohexane and total selectivity to cyclohexanone and cyclohexanol were up to 5.39% and 88.74%, respectively.     

Spinel CuFe2O4: a precursor for copper catalyst with high thermal stability and activity

Spinel CuFe₂O₄ has been studied as a precursor for copper catalyst. The spinel CuFe₂O₄ was effectively formed on the SiO₂ by calcination in air at 800 °C with the atomic ratio of Fe/Cu = 2. The spinel CuFe₂O₄ on the SiO₂ was reduced to fine dispersion of Cu and Fe₃O₄ particles by the H₂ reduction at 240 °C. After H₂ reduction at 600 °C, sintering of Cu particles over the CuFe₂O₄/SiO₂ (Fe/Cu = 2) was inhibited significantly, while fatal sintering of Cu particles over the Cu/SiO₂ (Fe/Cu = 0) occurred. The CuFe₂O₄/SiO₂ catalyst exhibited much higher activity and thermal stability for steam reforming of methanol (SRM), compared with the Cu/SiO₂ catalyst. The spinel CuFe₂O₄ on the SiO₂ can be regenerated after an intentional sintering treatment by calcination in air at 800 °C where the activity is also restored completely. Based on these findings, we propose that spinel CuFe₂O₄ is an effective precursor for a high performance copper catalyst in which the immiscible interaction between Cu and Fe (or Fe oxide) plays an important role in the stabilization of Cu particles.     

Steam reforming of methanol using Cu-ZnO catalysts supported on nanoparticle alumina

Methanol steam reforming was studied over several catalysts made by deposition of copper and zinc precursors onto nanoparticle alumina. The results were compared to those of a commercially available copper, zinc oxide and alumina catalyst. Temperature programmed reduction, BET surface area measurements, and N₂O decomposition were used to characterize the catalyst surfaces. XRD was used to study the bulk structure of the catalysts, and XPS was used to determine the chemical states of the surface species. The nanoparticle-supported catalysts achieved similar conversions as the commercial reference catalyst but at slightly higher temperatures. However, the nanoparticle-supported catalysts also exhibited a significantly lower CO selectivity at a given temperature and space time than the reference catalyst. Furthermore, the turnover frequencies of the nanoparticle-supported catalysts were higher than that of the commercial catalyst, which means that the activity of the surface copper is higher. It was determined that high alumina concentrations ultimately decrease catalytic activity as well as promote undesirable CH₂O formation. The lower catalytic activity may be due to strong Cu-Al₂O₃ interactions, which result in Cu species which are not easily reduced. Furthermore, the acidity of the alumina support appears to promote CH₂O formation, which at low Cu concentrations is not reformed to CO₂ and H₂. The CO levels present in this study are above what can be explained by the reverse water-gas-shift (WGS) reaction. While coking is not a significant deactivation pathway, migration of ZnO to the surface of the catalyst (or of Cu to the bulk of the catalyst) does explain the permanent loss of catalytic activity. Cu₂O is present on the spent nanoparticle catalysts and it is likely that the Cu⁺/Cu⁰ ratio is of importance both for the catalytic activity and the CO selectivity.     

Low-Temperature SCR of NO with NH3 over USY-Supported Manganese Oxide-Based Catalysts

A series of catalysts of manganese oxide, manganese–cerium and iron–manganese oxide supported on USY (ultra-stable Y zeolite) were studied for the low-temperature selective catalytic reduction (SCR) of NO with ammonia in the presence of excess oxygen. It was found that MnO_x/USY have high activity and high selectivity to N₂ in the temperature range 80-180 °C. The addition of iron and cerium oxide increased NO conversion significantly although the single-component Fe/USY and Ce/USY catalysts had low activities. Among the catalysts studied in this work, the 14% Ce-6% Mn/USY showed the highest activity. The results showed that this catalyst yielded nearly 100% NO conversion at 180 °C at a space velocity of 30 000 cm³ g^-1 h^-1. The only product is N₂ (with no N₂O) below 150 °C. The effects of the concentration of oxygen, NO and NH₃ were studied and the steady-state kinetics were also investigated. The reaction order is 1 with respect to NO and zero with respect to NH₃ on the 14% Ce-6% Mn/USY catalyst at 150 °C.     

Spectroscopic evidence for adsorption sites located at Cu/ZnO interfaces

FTIR spectra are reported of CO and formic acid adsorption on a series of Cu/ZnO/SiO₂ catalysts. Peaks due to linear CO adsorbed on copper diminished in intensity as the loading of ZnO was increased. This behaviour was explained in terms of ZnO island growth on the copper surface. Similarly, reduction of the copper concentration while maintaining a constant ZnO loading also resulted in further attenuation in bands ascribed to CO chemisorbed on copper. Formic acid exposure to a Cu/SiO₂ sample produced a formate species displaying a _as(COO) mode at 1585 cm^–1. Addition of a small quantity of ZnO to the catalyst resulted in substantial promotion of formate growth, which was accompanied by a shift (and broadening) of the _as(COO) vibration to 1660–1600 cm^–1. Since further ZnO incorporation poisoned formate creation it was concluded that formate species bonded to Cu and Zn sites located at interfacial positions had been formed. The role of such species in methanol synthesis is discussed.     

Influence of preparation method on performance of Cu(Zn)(Zr)-alumina catalysts for the hydrogen production via steam reforming of methanol

The selective production of hydrogen via steam reforming of methanol (SRM) was performed using prepared catalysts at atmospheric pressure over a temperature range 200–260^∘C. Reverse water gas shift reaction and methanol decomposition reactions also take place simultaneously with the steam reforming reaction producing carbon monoxide which is highly poisonous to the platinum anode of PEM fuel cell, therefore the detailed study of effect of catalyst preparation method and of different promoters on SRM has been carried out for the minimization of carbon monoxide formation and maximization of hydrogen production. Wet impregnation and co-precipitation methods have been comparatively examined for the preparation of precursors to Cu(Zn)(Al₂O₃) and Cu(Zn)(Zr)(Al₂O₃). The catalyst preparation method affected the methanol conversion, hydrogen yield and carbon monoxide formation significantly. Incorporation of zirconia in Cu(Zn)(Al₂O₃) catalyst enhanced the catalytic activity, hydrogen selectivity and also lower the CO formation. Catalyst Cu(Zn)(Zr)(Al₂O₃) with composition Cu/Zn/Zr/Al:12/4/4/80 prepared by co-precipitation method was the most active catalyst giving methanol conversion up to 97% and CO concentration up to 400 ppm. Catalysts were characterized by atomic absorption spectroscopy (AAS), Brunauer-Emett-Teller (BET) surface area, pore volume, pore size and X-ray powder diffraction (XRPD). The XRPD patterns revealed that the addition of zirconia improves the dispersion of copper which resulted in the better catalytic performance of Cu(Zn)(Zr)(Al₂O₃). The time-on-stream (TOS) catalysts stability test was also conducted for which the Cu(Zn)(Zr)(Al₂O₃) catalyst gave the consistent performance for a long time compared to other catalysts.     

Ti-containing MCM-41 catalysts for liquid phase oxidation of cyclohexene with aqueous H2O2 and tert-butyl hydroperoxide

Framework Ti-substituted and Ti-grafted MCM-41 mesoporous material has been prepared by direct hydrothermal synthesis and a post-synthesis grafting method. The materials have been tested as catalysts for cyclohexene oxidation with aqueous H₂O₂ and tert-butyl hydroperoxide (TBHP). With aqueous H₂O₂ in methanol, the major products were cyclohexene diol and its methyl ethers. No cyclohexene oxide was produced. Titanium leaching was a serious problem, and the catalyst lost its activity irreversibly after only one cycle of reaction. With TBHP, the selectivity for cyclohexene oxide was near 100%, titanium leaching was negligible, and the catalyst could be repeatedly used after regeneration without suffering significant activity loss. However, the reaction rate was lower than when H₂O₂ was used. Framework substituted material and catalysts prepared by Ti-grafting onto a MCM-41 support behaved similar, but the Ti-grafted MCM-41 is somewhat more active. The turnover frequency (TOF) per mole of Ti decreases with an increase of Ti content in the catalyst. This is caused by a reduced Ti dispersion within the silica matrix. This revised version was published online in July 2006 with corrections to the Cover Date.     

Characterization and catalytic properties of the CuO/SiO2 catalysts prepared by precipitation-gel method in the hydrogenolysis of glycerol to 1,2-propanediol: Effect of residual sodium

The effect of residual sodium on the CuO/SiO₂ catalysts prepared by precipitation-gel (PG) method has been investigated in correlation with the detailed characteristics of active component performance and catalytic performance in glycerol hydrogenolysis. Characterization of the catalysts showed that the residual sodium had a negative effect on the chemical–physical properties of the catalysts, such as the BET surface area, the dispersion of copper, and the reducibility of Cu²⁺ species as well as the adsorbility of reactant molecules. As a consequence, the conversion and selectivity of the catalysts in glycerol reactions generally decreased with increasing sodium content. The leaching of sodium from catalyst surface as a base could, however, on the one hand, weakly promote the activity of the catalyst, and on the other hand, could help retard the leaching of the active copper component and reduce the deactivation rate of the catalyst. The glycerol hydrogenolysis reaction is supposed to be a structure-sensitive reaction, in which copper particle sizes lower than a critical limit or those that did not fulfill a certain ensemble requirement were not active for glycerol reaction. Such details explained the lower TOFs of the catalysts with much smaller sizes. A certain amount of sodium is deduced to be needed for CuO/SiO₂ catalyst to exhibit both high catalytic activity and good stability. In addition, a reaction mechanism based on the effect of sodium on the activity and selectivity in glycerol hydrogenolysis has been proposed.