NO reduction by C3H6 in excess oxygen over fresh and sulfated Pt‐ and Rh‐based catalysts

The selective catalytic reduction (SCR) of NO with C₃H₆ was studied over three noble‐metal‐based catalysts: 2% Pt/γ‐Al₂O₃, 2% Rh/γ‐Al₂O₃ and 1.5% Rh/TiO₂(4% WO₃). The SO₂ effect on the catalyst activity was examined using sulfated samples of the above catalysts and SO₂‐containing feeds. Temperature‐programmed desorption and oxidation studies were carried out to examine the adsorption characteristics of NO and C₃H₆, respectively, in the absence or the presence of SO₂. The adsorption data were linked to variations in the NO reduction rates over fresh and sulfated samples. Modification of the support surface as a result of the SO₂ presence affects the NO and propene sorption characteristics, the NO oxidation and the propene consumption rates. This revised version was published online in August 2006 with corrections to the Cover Date.     

n-heptane reforming over Pt supported on beta zeolite exchanged with Cs and Li cations

Raman spectra of SO_x adsorbed on γ-alumina and Pt/γ-alumina model catalysts have been obtained with a 244 nm Raman spectrometer. Strong peaks in the 980–1380 cm^-1 region characteristic of adsorbed sulfates are clearly portrayed in the spectra, which contrast with fluorescence-dominated scans obtained using visible excitation. Broad bands are also observed in the 3500–3700 cm^-1 O–H stretch region on the γ-alumina, which belong to weakly-bound physisorbed water and more strongly-bound surface hydroxyls. These features are monitored as the samples are heated up to 600°C in the presence of nitrogen. The sulfate peaks vary in position depending on whether or not the γ-alumina is loaded with platinum, hydrated, or dehydrated. Platinum appears to inhibit the physisorption of water and the formation of hydroxyls on the γ-alumina surface, as evidenced by the absence of O–H stretch vibrations on the Pt-loaded sample. Our spectral data demonstrate that UV Raman spectroscopy is a useful technique for analytical studies of adsorbed SO_x on γ-alumina, and holds promise for future in situ investigations of other adsorbed species on catalytic substrates of automotive interest. This revised version was published online in July 2006 with corrections to the Cover Date.     

The effect of Pd/Al2O3 pretreatment on catalytic activity in cyclopentane/deuterium exchange

Big variations in overall activity and product selectivity in the cyclopentane/deuterium exchange reaction were found in effect of various pretreatments of two chlorine‐free Pd/γ‐Al₂O₃ catalysts. The most important changes are observed when severely prereduced (at 600 °C) Pd/Al₂O₃ catalysts have been reoxidised and mildly rereduced: the multiple type of exchange, typical of mildly pretreated Pd catalysts, is replaced by a stepwise mode, and a big increase in catalytic activity occurs. At this state, the Pd/γ‐Al₂O₃ catalysts retain some water (as surface hydroxyls) generated by reoxidation and mild reduction. Deuterium spillover from Pd onto alumina and changes in acidity of alumina are invoked to rationalize the kinetic results. Changes in the state of Pd after various pretreatments, as probed by temperature‐programmed hydride decomposition, can hardly be correlated with changes in the catalytic behaviour in the exchange reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation and photocatalytic properties of a novel kind of loaded photocatalyst of TiO2/SiO2/γ‐Fe2O3

A novel kind of loaded photocatalyst of TiO₂/SiO₂/γ‐Fe₂O₃ (TSF) that can photodegrade effectively organic pollutants in the dispersion system and can be recycled easily by a magnetic field is reported in this paper. The γ‐Fe₂O₃ cores in TiO₂/γ‐Fe₂O₃ are found to reduce the activity of the TiO₂ photocatalyst in the photodegradation of dyes under either UV or visible light irradiation. Addition of a SiO₂ membrane between the γ‐Fe₂O₃ core and the TiO₂ shell weakens efficiently the influence of the γ‐Fe₂O₃ cores on the TiO₂ photocatalytic activity and leads to a highly active and magnetically separable photocatalyst on TSF. Comparison of the photodegradation processes of dyes under UV and visible irradiation is also carried out. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic synthesis of thiophene from the reaction of n-butanol and carbon disulfide over K<Subscript>2</Subscript>CO<Subscript>3</Subscript>-promoted Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>/<Emphasis Type="Italic">γ</Emphasis>-alumina catalyst

The synthesis of thiophene from the reaction of n-Butanol and carbon disulfide was performed in a fixed-bed reactor in the presence of promoted chromia on γ-alumina. A high selectivity to thiophene (87%) and a long lifetime of the catalyst (55 hour) was obtained at 450 °C with a 1: 6 n-Butanol to carbon disulfide molar ratio and LHSV 1 h⁻¹ over γ-Al₂O₃ promoted by 7% K₂CO₃ with 15% Cr₂O₃ loaded. The catalytic behavior of these catalysts can be attributed to their dual-functional acidity and dehydrogenating and cyclized properties.     

Modification of the alumina‐supported Mo‐based hydrodesulfurization catalysts by tungsten

The incorporation effect of tungsten as an activity‐promotional modifier into the Ni‐promoted Mo/γ‐Al₂O₃ catalyst was studied. Series of W‐incorporated catalysts with different content of tungsten were prepared by changing the impregnation order of nickel and tungsten onto a base Mo/γ‐Al₂O₃. Catalytic activities were measured from the atmospheric reactions of thiophene hydrodesulfurization (HDS) and ethylene hydrogenation (HYD). The HDS and HYD activities of the WMo/γ‐Al₂O₃ catalysts (WM series) initially increased and subsequently decreased with increasing content of tungsten as compared with those of their base Mo/γ‐Al₂O₃. The maximal activity promotion occurred at the W/(W + Mo) atomic ratio 0.025. For the Ni‐promoted Mo/γ‐Al₂O₃ catalysts, the effect of W incorporation was greatly dependent on the impregnation order of tungsten. The catalysts prepared by impregnating Ni onto the WMo/γ‐Al₂O₃ catalysts showed the same trend of activity promotion as for the WM series, while those by impregnating W onto a NiMo/γ‐Al₂O₃ catalyst resulted in lower activities than their base NiMo/γ‐Al₂O₃ catalyst. To characterize the catalysts, temperature‐programmed reduction and low‐temperature oxygen chemisorption were conducted. The effects of W incorporation on the NiMo‐based catalysts were discussed in reference to those on the CoMo‐based catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Gas‐phase pinacol conversion on AlPO4, γ‐Al2O3 and SiO2 catalysts

Pinacol (2,3‐dimethyl‐2,3‐butanediol) conversion over AlPO₄ (Al/P = 1) and γ‐Al₂O₃ catalysts proceeded in two parallel reaction pathways with formation of 2,3‐dimethyl‐1,3‐butadiene (by 1,2‐elimination) and 3,3‐dimethyl‐2‐butanone (by rearrangement), the latter being the main reaction product. The activity was in accordance with the surface acidity data as measured versus cyclohexene skeletal isomerization reaction. Thus, AlPO₄ showed the highest activity (almost total conversion at 523 K). The 1,2‐elimination/rearrangement ratio depended on the type of catalyst used and diene formation increased with reaction temperature. Moreover, pinacolone was a reaction intermediate for diene production. This revised version was published online in July 2006 with corrections to the Cover Date.     

Deactivation and coke formation on palladium and platinum catalysts in vegetable oil hydrogenation

Deactivation of palladium and platinum catalysts due to coke formation was studied during hydrogenation of methyl esters of sunflower oil. The supported metal catalysts were prepared by impregnating γ-alumina with either palladium or platinum salts, and by impregnating α-alumina with palladium salt. The catalysts were reused for several batch experiments. The Pd/γ-Al₂O₃ catalyst lost more than 50% of its initial activity after four batch experiments, while the other catalysts did not deactivate. Samples of used catalysts were cleaned from remaining oil by repeated extractions with methanol, and the amount of coke formed on the catalysts was studied by temperature-programmed oxidation. The deactivation of the catalyst is a function of both the metal and the support. The amount of coke increased on the Pd/γ-Al₂O₃ catalyst with repeated use, but the amount of coke remained approximately constant for the Pt/γ-Al₂O₃ catalyst. Virtually no coke was detected on the Pd/α-Al₂O₃ catalyst. The formation of coke on Pd/α-Al₂O₃ may be slower than on the Pd/γ-Al₂O₃ owing to the carrier’s smaller surface area and less acidic character. The absence of deactivation for the Pt/γ-Al₂O₃ catalyst may be explained by slower formation of coke precursors on platinum compared to palladium.     

Nonoxidative dehydrogenation and aromatization of methane over W/HZSM‐5‐based catalysts

Highly active and heat‐resisting W/HZSM‐5‐based catalysts for nonoxidative dehydro‐aromatization of methane (DHAM) have been developed and studied. It was found from the experiments that the W−H₂SO₄/HZSM−5 catalyst prepared from a H₂SO₄‐acidified solution of ammonium tungstate (with a pH value at 2–3) displayed rather high DHAM activity at 973–1023 K, whereas the W/HZSM‐5 catalyst prepared from an alkaline or neutral solution of (NH₄)₂WO₄ showed very little DHAM activity at the same temperatures. Laser Raman spectra provided evidence for existence of (WO₆)^n- groups constructing polytungstate ions in the acidified solution of ammonium tungstate. The H₂‐TPR results showed that the reduction of precursor of the 3% W–H₂SO₄/HZSM‐5 catalyst may occur at temperatures below 900 K, producing W species with mixed valence states, W⁵⁺ and W⁴⁺, whereas the reduction of the 3% W/HZSM‐5 occurred mainly at temperatures above 1023 K, producing only one type of dominant W species, W⁵⁺. The results seem to imply that the observed high DHAM activity on the W–H₂SO₄/HZSM‐5 catalyst was closely correlated with (WO₆)^n- groups with octahedral coordination as the precursor of catalytically active species. Incorporation of Zn (or La) into the W–H₂SO₄/HZSM‐5 catalyst has been found to pronouncedly improve the activity and stability of the catalyst for DHAM reaction. Over a 2.5% W–1.5% Zn–H₂SO₄/HZSM‐5 catalyst and under reaction conditions of 1123 K, 0.1 MPa, and GHSV=1500 ml/(h g−cat.), methane conversion (XCH₄) reached 23% with the selectivity to benzene at ∼96% and an amount of coke for 3 h of operation at 0.02% of the catalyst weight used. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of homogeneous decane oxidation on the catalytic performance of lean NO x catalysts

Extensive homogeneous gasphase reactions were observed when decane was used as the hydrocarbon reductant for the selective reduction of NO _x . The catalytic performance of a SnO₂/CoO _x /Al₂O₃ catalyst was found to be strongly dependent on the extent of the homogeneous reaction in the precatalytic volume. The effect of the homogeneous reaction on the catalytic performance also depended on whether SO₂ was present in the feed. By filling the precatalytic volume with 25–35 mesh irregularly shaped quartz chips, gasphase reaction was suppressed significantly. This methodology was used to evaluate the inherent catalytic performance of SnO₂/CoO _x /Al₂O₃ and SnO₂/Al₂O₃ catalysts with decane as a reductant. It was found that in the absence of SO₂, SnO₂/Al₂O₃ was a better catalyst than SnO₂/CoO _x /Al₂O₃, but in the presence of 30 ppm of SO₂ the latter was a far better catalyst.     

Role of cobalt on γ-Al2O3 based NO x storage catalyst

Co/Pt/Ba/γ-Al₂O₃, Co/Ba/γ-Al₂O₃, Pt/Ba/γ-Al₂O₃, Co/Pt/γ-Al₂O₃, Ba/γ-Al₂O₃, Pt/γ-Al₂O₃, and Co/γ-Al₂O₃ type catalysts were prepared by a conventional impregnation method, and their NO _x storage capacities were evaluated by colorimetric assay. Co-containing catalysts had a higher NO _x storage capacity than that of Co-free counterparts. The role of each component, especially Co, for the catalysts prepared was investigated by using in-situ FTIR. The high NO _x storage for Co-containing catalysts including Co/Ba/γ-Al₂O₃ and Co/Pt/Ba/γ-Al₂O₃ is mainly due to the formation of Co₃O₄ on the catalyst surface identified by XAFS.     

n‐octane reforming over alumina‐supported Pt, Pt–Sn and Pt–W catalysts

Pt, Pt–Sn and Pt–W supported on γ‐Al₂O₃ were prepared and characterized by H₂ chemisorption, TEM, TPR, test reactions of n‐C₈ reforming (500°C), cyclohexane dehydrogenation (315°C) and n‐C₅ isomerization (500°C), and TPO of the used catalysts. Pt is completely reduced to Pt⁰, but only a small fraction of Sn and of W oxides are reduced to metal. The second element decreases the metallic properties of Pt (H₂ chemisorption and dehydrogenation activity) but increases dehydrocyclization and stability. In spite of the large decrease in dehydrogenation activity of Pt in the bimetallics, the metallic function is not the controlling function of the bifunctional mechanisms of dehydrocyclization. Pt–Sn/Al₂O₃ is the best catalyst with the highest acid to metallic functions ratio (due to its lower metallic activity) presenting a xylenes distribution different from the other catalysts. The acid function of Pt–Sn/Al₂O₃ is tuned in order to increase isomerization and cyclization and to decrease cracking, as compared to Pt and Pt–W. This revised version was published online in July 2006 with corrections to the Cover Date.     

Interaction of SO2 with CeO2 and Cu/CeO2 catalysts: photoemission, XANES and TPD studies

CeO₂ and Cu/CeO₂ are effective catalysts/sorbents for the removal or destruction of SO₂. Synchrotron‐based high‐resolution photoemission, X‐ray absorption near‐edge spectroscopy (XANES), and temperature‐programmed desorption (TPD) have been employed to study the reaction of SO₂ with pure and reduced CeO₂ powders, ceria films (CeO₂, CeO_2−x, Ce₂O_3+x) and model Cu/CeO₂ catalysts. The results of XANES and photoemission provide evidence that SO₄ was formed upon the adsorption of SO₂ on pure powders or films of CeO₂ at 300 K. The sulfate decomposed in the 390–670 K temperature range with mainly SO₂ and some SO₃ evolving into gas phase. At 670 K, there was still a significant amount of SO₄ present on the CeO₂ substrates. The introduction of O vacancies in the CeO₂ powders or films favored the formation of SO₃ instead of SO₄. Ceria was able to fully dissociate SO₂ to atomic S only if Ce atoms with a low oxidation state were available in the system. When Cu atoms were added to CeO₂ new active sites for the destruction of SO₂ were created improving the catalytic activity of the system. The surface chemistry of SO₂ on the Cu‐promoted CeO₂ was much richer than on pure CeO₂. The behavior of ceria in several catalytic processes (oxidation of SO₂ by O₂, reduction of SO₂ by CO, automobile exhaust converters) is discussed in light of these results. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic Reduction of Nitric Oxide by Hydrogen Sulfide Over γ-alumina

The ability of H₂S to reduce NO in a fixed bed reactor using a γ-alumina catalyst was studied with the objective of generating new methods for conversion of NO to N₂. Compared to the homogenous reaction of NO with H₂S, the catalyzed reaction showed improved conversions of NO to N₂. Using a gas space velocity of 1000 h⁻¹ and a feed of 1% NO and 1% H₂S in argon, it was found that the conversion of NO to N₂ was complete at 800 °C. This result compared to a 38% conversion of NO to N₂ for the homogeneous gas phase reaction at 800 °C. At temperatures below 800 °C, a short fall in the nitrogen balance was discovered when the γ-alumina was employed as a catalyst. This discrepancy was explained by conversion of NO to NH₃ and subsequent reaction of the NH₃ with any SO₂ in the system to form ammonium sulfur oxy-anion salts. This suggestion is supported by the finding that when larger amounts of H₂S were used relative to NO, more NH₃ was formed together in tandem with lower N₂ mass balances. Several reaction pathways have been proposed for the catalytic reduction of NO by H₂S.     

Low temperature selective catalytic reduction of NO by NH3 over V2O5 supported on TiO2–SiO2–MoO3

The V₂O₅ catalysts supported on TiO₂–SiO₂–MoO₃ (TSM) prepared by the coprecipitation method were investigated for the selective catalytic reduction (SCR) of NO by NH₃ at low temperatures. The V₂O₅/TSM catalyst with 7–13 wt% SiO₂ was found to exhibit a superior SCR activity and a good sulfur tolerance at low temperatures (<250 °C). The presence of highly active polymeric vanadates formed by the incorporation of MoO₃ to TiO₂–SiO₂ and superior redox properties seems to enhance SCR activity, and furthermore the very lower SO₂ oxidation activity due to the higher acidity leads to the remarkable improvement of sulfur tolerance.     

Hydrothermal synthesis of crystalline α-/β-MnO2 nanorods via γ-MnOOH nanorod precursors

The crystalline α-MnO₂ and β-MnO₂ nanorods have been successfully prepared via a facile hydrothermal method from γ-MnOOH nanorods precursor, respectively. The samples were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), field emission scanning electron microscope (FESEM) and Fourier transformed infrared spectra (FTIR). The morphology and structure of γ-MnOOH nanorods precursors have a great influence on the crystal structure of the obtained products. The α-MnO₂ nanorods are prepared from the 100°C γ-MnOOH precursor, while the β-MnO₂ nanorods are obtained from the 150°C γ-MnOOH precursor, respectively. Besides, the catalytic activity of the prepared α-MnO₂ and β-MnO₂ nanorods for the H₂O₂ decomposition has been investigated comparatively, and the latter shows better catalytic activity.     

Cyclohexene dehydrogenation and hydrogenation on Pt(111) monitored by SFG surface vibrational spectroscopy: different reaction mechanisms at high pressures and in vacuum

The hydrogenation and dehydrogenation reactions of cyclohexene on Pt(111) crystal surfaces were investigated by surface vibrational spectroscopy via sum frequency generation (SFG) both under vacuum and high pressure conditions with 10 Torr cyclohexene and various hydrogen pressures from 30 up to ~600 Torr. At high pressures, the gas composition and turnover rate (TOR) were measured by gas chromatography. In vacuum, cyclohexene on Pt(111) undergoes a change from π/σ‐bonded, σ‐bonded cyclohexene and c‐C₆H₉ surface species to adsorbed benzene when the surface was heated from 130 to 330 K. A site‐blocking effect was observed at saturation coverage of cyclohexene that caused dehydrogenation to shift to somewhat higher surface temperature. At high pressures, however, none of the species observed in vacuum conditions were detectable. 1,4‐cyclohexadiene (1,4‐CHD) was found to be the major species on the surface at 295 K, even with the presence of nearly 600 Torr of hydrogen. Hydrogenation was the only detectable reaction at the temperature range between 300 and 400 K with 1,3‐cyclohexadiene (1,3‐CHD) on the surface, as revealed by SFG. Further increasing the surface temperature results in a decrease in hydrogenation reaction rate and an increase in dehydrogenation reaction rate and both 1,3‐CHD and 1,4‐CHD were present on the surface simultaneously. The simultaneous observation of the reaction kinetic data and the chemical nature of surface species allows us to postulate a reaction mechanism at high pressures: cyclohexene hydrogenates to cyclohexane via a 1,3‐CHD intermediate and dehydrogenates to benzene through both 1,4‐CHD and 1,3‐CHD intermediates. Isomerisation of the 1,4‐CHD and 1,3‐CHD surface species is negligible. This revised version was published online in July 2006 with corrections to the Cover Date.     

Vapour‐phase synthesis of n‐butanethiol from n‐butanol and carbon disulfide over alkali‐promoted chromia on γ‐alumina catalysts

The vapour‐phase reaction of n‐butanol and carbon disulfide was performed in a fixed‐bed flow reactor in the presence of a potassium‐carbonate‐promoted chromia on γ‐alumina catalyst, namely G41P from Girdler. A high selectivity to n‐butanethiol (85%) was obtained at 250°C with a 1 : 1 n‐butanol : carbon disulfide molar ratio, a contact time of 6 s and a flow rate of 0.03 ml/min. Under these conditions no isomeric mercaptans were obtained. The amount of secondary products, di‐n‐butyl sulfide and di‐n‐butyl disulfide, is relatively low and decreases with decrease of n‐butanol conversion. However, the catalyst was shown to deactivate relatively rapidly. This revised version was published online in July 2006 with corrections to the Cover Date.     

Simultaneous removal of N2O and CH4 as the strong greenhouse‐effect gases over Fe‐BEA zeolite in the presence of excess O2

Simultaneous catalytic removal of N₂O and CH₄ as the strong greenhouse‐effect gases was found to be possible over an Fe‐ion‐exchanged BEA zeolite (Fe‐BEA) by the selective catalytic reduction (SCR) of N₂O with CH₄. The direct decomposition of N₂O (2N₂O → 2N₂ + O₂) and the oxidation of CH₄ (CH₄ + 2O₂ → CO₂ + 2H₂O) over Fe‐BEA zeolite required high temperature above 400 and 450 °C, respectively. Nevertheless, the catalytic reduction of N₂O by adding CH₄ over Fe‐BEA zeolite readily occurred at much lower temperatures (ca. 250–350 °C) whether in the presence of O₂ or not. No oxidation of CH₄ by O₂ took place at these temperatures. On the basis of these results and the kinetic studies, it was concluded that CH₄ reacted selectively with N₂O to produce N₂, CO₂ and H₂O over Fe‐BEA zeolite even in the presence of excess O₂. Overall stoichiometry of the SCR of N₂O with CH₄ was determined as follows: 4N₂O + CH₄ → 4N₂ + CO₂ + 2H₂O. This revised version was published online in August 2006 with corrections to the Cover Date.     

Simulation of SCR equipped vehicles using iron-zeolite catalysts

Iron-catalysts, based on ZSM-5 (FeZSM5) and Cuban natural Mordenite (FeMORD) zeolites have been prepared by a conventional ion-exchange method and their catalytic activity in the selective catalytic reduction (SCR) of NO with ammonia was studied in the presence of H₂O and SO₂. A commercial SCR catalyst (CATCO) based on V₂O₅–WO₃–TiO₂, was also studied as a reference. This paper presents the experimental results of using these catalysts without toxic vanadium and also exploits a neural network-based approach to predict NO_x conversion efficiency of three SCR catalysts. The mathematical functions derived have been integrated into a numerical model to simulate diesel road vehicles equipped with SCR catalysts such as those studied here. The main results indicate that despite toxic vanadium and N₂O formation, CATCO shows better NO_x conversion efficiencies. However, FeMORD does not produce N₂O and performs better than the FeZSM5. The simulation results on real cycles show lower level of NO_x for heavy-duty and light-duty diesel vehicles compared with homologation load cycles.