Studies of the activation process over Pd perovskite-type oxides used for catalytic oxidation of toluene

Calcined and reduced catalysts Pd/LaBO₃ (B = Co, Fe, Mn, Ni) were used for the total oxidation of toluene. Easiness of toluene destruction was found to follow the sequence based on the T₅₀ values (temperature at which 50% of toluene is converted): Pd/LaFeO₃ > Pd/LaMnO_3+δ > Pd/LaCoO₃ > Pd/LaNiO₃. In order to investigate the activation process (calcination and reduction) in detail, the reducibility of the samples was evaluated by H₂-TPR on the calcined catalysts. Additionally, characterization of the Pd/LaBO₃ (B = Co, Fe) surface was carried out by X-ray photoelectron spectroscopy (XPS) at each stage of the global process, namely after calcination, reduction and under catalytic reaction at either 150 or 200 °C for Pd/LaFeO₃ and either 200 or 250 °C for LaCoO₃. The different results showed that palladium oxidized entities were totally reduced after pre-reduction at 200 °C for 2 h (2 L/h, 1 °C/min). As LaFeO₃ was unaffected by such a treatment, for the other perovskites, the cations B are partially reduced as B³⁺ (B = Mn) or B²⁺ even to B⁰ (B = Co, Ni). In the reactive stream (0.1% toluene in air), Pd⁰ reoxidized partially, more rapidly over Co than Fe based catalysts, to give a Pd²⁺/Pd⁴⁺ and Pd⁰/Pd²⁺/Pd⁴⁺ surface redox states, respectively. Noticeably, reduced cobalt species are progressively oxidized on stream into Co³⁺ in a distorted environment. By contrast, only the lines characteristic of the initial perovskite lattice were detected by XRD studies on the used catalysts. The higher activity performance of Pd/LaFeO₃ for the total oxidation of toluene was attributed here to a low temperature of calcination and to a remarkable high stability of the perovskite lattice whatever the nature of the stream which allowed to keep a same palladium dispersion at the different stages of the process and to resist to the oxidizing experimental conditions. On the contrary, phase transformations for the other perovskite lattices along the process were believed to increase the palladium particle size responsible of a lower activity.     

Microwave assisted N-propargylation of imidazole using alkaline promoted carbons

Two basic activated carbons (Na⁺ and Cs⁺-Norit) have been used as catalysts in the synthesis of N-propargyl imidazole. The effect of the microwave irradiation has been studied. Under the experimental conditions used higher yields and selectivities of N-propargyl imidazole than those obtained using other basic media were reached. The carbons were characterized by thermal analysis, nitrogen adsorption and X-ray photoelectron spectroscopy. Most of the basic sites in the promoted carbons have 13.3≤pK_a≤16.5. The order or basicity is Na⁺-Norit+-Norit. The basicity enhancement is directly connected with the size of the alkaline cation. The yield of the N-propargyl imidazole presents a maximum for 0.04 g of Cs⁺-Norit at 300 W in only 3 min of microwave irradiation.     

In situ FTIR characterization of the adsorption of CO and its reaction with NO on Pd-based FCC low NOx combustion promoters

The adsorption of CO and its reaction with NO in the 400–600 °C temperature range on Ceⁿ⁺/Na⁺/γ-Al₂O₃ and Pdⁿ⁺/Ceⁿ⁺/Na⁺/γ-Al₂O₃ type materials used commercially as FCC additives were monitored by FTIR spectroscopy. Exposure of both types of samples to CO leads to the formation of carboxylates and carbonates. The concentration of these species was higher in samples containing Pd, indicating that palladium catalyzes their formation. The Pdⁿ⁺ cations initially present in these samples undergo partial reduction to form metallic Pd in the presence of CO even at room temperature. More complete reduction of Pd, along with some aggregation, was observed after exposure to CO at elevated temperatures. Exposure of both types of samples to NO/CO mixtures in the 400–600 °C temperature range leads to the formation of surface isocyanate species. Both Na⁺ and Ceⁿ⁺ promote the formation of such NCO species. However, surface isocyanate species were formed with substantially higher rates in the presence of palladium. The formation of the isocyanate species strongly correlates with changes observed in the ν_OH region, indicating that hydroxyls actively participate in the surface chemistry involved and are capable of protonating the NCO species. The isocyanates are also reactive towards O₂ and NO yielding CO₂ and N₂. These results suggest that isocyanates are possibly involved as intermediates in the CO–NO reaction over the materials examined.     

Characterization of Pd-based FCC CO/NOx control additives by in situ FTIR and extended X-ray absorption fine structure spectroscopies

Pdⁿ⁺/Ceⁿ⁺/Na⁺/γ-Al₂O₃-type materials used as FCC additives for CO/NO_x control were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy and in situ FTIR. The EXAFS data indicate that in freshly prepared samples palladium is present in the form of highly dispersed PdO species. Reduction with H₂ at 500 °C leads to the formation of small Pd clusters incorporating on average approximately six to eight metal atoms at a Pd−Pd bond distance of 2.76 Å. All components of these materials can interact with NO and promote the formation of nitrate/nitrite species, essentially “trapping” NO_x species on the catalyst surface. However, the Na⁺ species dominate the surface chemistry and readily form sodium nitrates with a characteristic IR band at 1370–1385 cm⁻¹. Finally, hydroxyls from the support are also actively participating in the formation of HNO_x type compounds with characteristic stretching vibrations in the 3500–3572 cm⁻¹ region.     

NO reduction by CH4 in the presence of excess O2 over Pd/sulfated zirconia catalysts

The selective catalytic reduction (SCR) of NO by methane in the presence of excess oxygen has been studied on a series of Pd catalysts supported on sulfated zirconia (SZ). This support is not as sensitive to structural damage by steaming as the acidic zeolites, such as H-ZSM-5 and H-Mor. In previous studies, it was shown that this type of acidic zeolites are able to stabilize Pd²⁺ ions and promote high SCR activity and selectivity, which are typically not seen in Pd catalysts. In this contribution, it has been demonstrated that SZ is able to promote the NO reduction activity in a similar way to the acidic zeolites, by stabilizing Pd²⁺ ions that is selective for NO reduction. As in the case of acidic zeolites, the stabilization of Pd²⁺ ions can occur through a transfer of Pd species from particle to particle. One of the attractive features of Pd/SZ catalysts is that they are less sensitive to water and SO₂ poisoning than Pd/H-ZSM-5 catalyst and exhibit higher reversibility after removal of water or SO₂.     

An experimental study of electroreduction of CO2 to HCOOH on SnO2/C in presence of alkali metal cations (Li+, Na+, K+, Rb+ and Cs+) and anions (HCO3-, Cl-, Br- and I-)

It is well-known that the electrolytes can influence the electrochemical reduction of carbon dioxide (ERCO₂) in aqueous media. In this work, we explore the effects of alkali metal cations and anions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, HCO₃^-, Cl^-, Br^-, I^-) on the current density and product selectivity for the ERCO₂ into formic acid (HCOOH) on the SnO₂/carbon paper (SnO₂/C) electrode. Results of the ERCO₂ experiments show that for the cations, the promotion effects on current density and faradaic efficiencies (FEs) are in the order of Li⁺ < Na⁺ < K⁺ < Cs⁺ < Rb⁺. For the anions, the current density values are in the order of NaHCO₃ < NaCl < NaBr < NaI and KHCO₃ < KCl ≈ KI < KBr, respectively, and that on the FEs for the formation of the HCOOH (FE_HCOOH) is HCO₃^- < Cl^- < Br^- < I^-. Based on this result, the effects of alkali metal cations and anions on ERCO₂ are discussed.     

The effect of CeO2 structure on the activity of supported Pd catalysts used for methane steam reforming

Palladium (Pd) supported on CeO₂-promoted γ-Al₂O₃ with various CeO₂ (ceria) crystallinities, were used as catalysts in the methane steam reforming reaction. X-ray diffraction (XRD) analysis, FTIR spectroscopy of adsorbed CO, and X-ray photoelectron spectroscopy (XPS) were employed to characterize the samples in terms of Pd and CeO₂ structure and dispersion on the γ-Al₂O₃ support. These results were correlated with the observed catalytic activity and deactivation process. Arrhenius plots at steady-state conditions are presented as a function of CeO₂ structure. Pd is present on the oxidized CeO₂-promoted catalysts as Pd⁰, Pd⁺ and Pd²⁺, at ratios strongly dependent on CeO₂ structure. XRD measurements indicated that Pd is well dispersed (particles <2 nm) on crystalline CeO₂ and is agglomerated as large clusters (particles in 10–20 nm range) on amorphous CeO₂. FTIR spectra of adsorbed CO revealed that after pre-treatment under H₂ or in the presence of amorphous CeO₂, partial encapsulation of Pd particles occurs. CeO₂ structure influences the CH₄ steam reforming reaction rates. Crystalline CeO₂ and dispersed Pd favor high reaction rates (low activation energy). The presence of CeO₂ as a promoter conferred high catalytic activity to the alumina-supported Pd catalysts. The catalytic activity is significantly lower on Pd/γ-Al₂O₃ or on amorphous (reduced) CeO₂/Al₂O₃ catalysts. The reaction rates are two orders of magnitude higher on Pd/CeO₂/γ-Al₂O₃ than on Pd/γ-Al₂O₃, which is attributed to a catalytic synergism between Pd and CeO₂. The low rates on the reduced Pd/CeO₂/Al₂O₃ catalysts can be correlated with the loss of Pd sites through encapsulation or particle agglomeration, a process found mostly irreversible after catalyst regeneration.     

Identification of cationic and oxidic caesium species in basic Cs-overloaded BEA zeolites

A parent acidic H-BEA with crystallites very small in size and high external surface area was used to prepare a series of materials loaded with increasing Cs⁺ contents by firstly ion-exchange and then impregnation with CsOH solutions. The monitoring of the ion-exchange process by chemical analysis and by IR spectroscopy in presence of CO or NH₃ reveals that a relevant amount of Brønsted acid sites in dehydrated H-BEA is related to framework Al sites that, in aqueous solution, turn into partially extraframework Al species unable to act any longer as sites of cationic exchange. This limits the exchange capacity in solution and higher levels of ion-exchange are attained by subsequent impregnation and calcination. A possible explanation for such a behaviour is proposed. The formation of carbonates by adsorption of CO₂, monitored by IR, confirms that the basic character induced on framework oxygen atoms by exchange of H⁺ with Cs⁺ is significantly weaker than that reached upon Cs-overloading. For the latter, the strong basicity is related to the presence of Cs₂O-like nanoparticles (also detected by EXAFS), dispersed within the zeolite pores (as shown by pore volume and TEM/EDX measurements). IR spectroscopy of adsorbed CO shows that Cs⁺ as countercations or as surface sites of occluded Cs₂O-like species exhibit a similar Lewis acid strength. Noticeably, in Cs-overloaded BEA, pairs of Cs⁺ sites (formed by two countercations and/or one countercation and a Cs⁺ at the surface of Cs₂O-like particles) are present, where CO can be adsorbed in a head–tail form, producing a distinct ν_CO band at 2145 cm⁻¹.     

Cracking of n-heptane over Brønsted acid sites and Lewis acid Ga sites in ZSM-5 zeolite

A series of gallium-containing ZSM-5 zeolites prepared by wet impregnation, ion-exchange and chemical vapor deposition (CVD) methods are compared in the cracking of n-heptane. Impregnation results in the dispersion of some of the gallium oxide clusters into the zeolite pore network as charge-compensating Ga species after calcination. Reduction of impregnated Ga/HZSM-5 catalysts leads to complete transformation of the oxidic Ga precursors to charge-compensating Ga⁺ and GaH²⁺ species. A small amount of divalent GaH²⁺ species can be stabilized; however, with increasing Ga/Al ratio monovalent cations dominate. While a model Ga/HZSM-5 catalyst prepared by CVD of Ga(CH₃)₃ containing mainly charge-compensating Ga cations displays high selectivity to dehydrogenated products (olefins, toluene and coke), catalysts with a lower Ga/Al ratio display improved activity with a product mixture resulting from contributions of Ga sites (dehydrogenation, aromatization, olefin cracking) and of Brønsted acid sites (protolytic cracking, olefin cracking). The synergy between Ga dehydrogenation sites and Brønsted acid sites is proposed to improve the dehydrogenation rate: the high acidity of the zeolitic proton facilitates hydrogen recombination and concomitant removal of product olefin from the Ga active sites. Ion-exchanged Ga/HZSM-5 catalyst which combines a difficult to reduce gallium oxide phase and high Brønsted acidity has the highest activity with relatively weak coke formation.     

The alkylation of naphthalene over three-dimensional large pore zeolites: The influence of zeolite structure and alkylating agent on the selectivity for dialkylnaphthalenes

In order to elucidate how zeolite structure and alkylating agent play roles in the shape-selective catalysis, the alkylation, i.e., isopropylation, sec-butylation, and tert-butylation, of naphthalene (NP) was examined over three-dimensional twelve-membered (12-MR) zeolites, Y (FAU), Beta (BEA), and CIT-1 (CON), and compared to that of H-mordenite (MOR). The β,β-selectivities (for β,β-dialkylnapthalene (β,β-DAN)) and the 2,6-selctivities (for 2,6-dialkylnaphthalene (2,6-DAN)) among DAN isomers varied with the types of zeolites and alkylating agents. FAU, BEA, and CON gave only low selectivities for 2,6-diisopropylnaphthalene (2,6-DIPN) in the isopropylation, and predominant isomers were bulky and thermodynamically unstable ,β-DIPN (1,3-, 1,6-, and 1,7-DIPN) and ,-DIPN (1,4- and 1,5-DIPN) at lower temperatures, and the formation of the less bulky and thermodynamically stable β,β-DIPN (2,6- and 2,7-DIPN) increased with increasing the temperature: they have quite different features from the shape-selective catalysis over MOR. These results suggest that FAU, BEA, and CON are not shape-selective in the isopropylation, and that the isopropylation is principally controlled kinetically at lower temperatures, and thermodynamically at higher temperatures.

The β,β-selectivities over FAU, BEA, and CON increased with increasing the bulkiness of alkylating agents, and were almost 100% in the tert-butylation. On the other hand, the 2,6-selectivities over these zeolites were much lower than those over MOR at a typically moderate temperature, 250 °C. These results mean that FAU, BEA, and CON have the shape-selective nature to give the less bulky isomers, β,β-DAN, in the sec-butylation and tert-butylation by using bulkier alkylating agents, particularly 2-methyl-2-propene: they can differentiate β,β-DAN from their isomers at the transition states by the steric restriction of zeolite channels. However, the channels of these zeolites are too large for differentiating 2,6- and 2,7-DAN even with 2-methyl-2-propene.     

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.     

The role of lanthana loading on the catalytic properties of Pd/Al2O3-La2O3 in the NO reduction with H2

The role of La₂O₃ loading in Pd/Al₂O₃-La₂O₃ prepared by sol–gel on the catalytic properties in the NO reduction with H₂ was studied. The catalysts were characterized by N₂ physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO.

The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La₂O₃ inclusion. The selectivity depends on the NO/H₂ molar ratio (GHSV = 72,000 h⁻¹) and the extent of interaction between Pd and La₂O₃. At NO/H₂ = 0.5, the catalysts show high N₂ selectivity (60–75%) at temperatures lower than 250 °C. For NO/H₂ = 1, the N₂ selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H₂O vapor. The high N₂ selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdO_x phase interacting with La₂O₃. The formation of this phase is favored by the spreading of PdO promoted by La₂O₃. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al₂O₃ the O₂ uptake is consistent with the oxidation of PdO to PdO₂, and when La₂O₃ is present the O₂ uptake exceeds that amount (1.5 times). La₂O₃ in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N₂.     

A study on mechanism of charging/discharging at amorphous manganese oxide electrode in 0.1 M Na2SO4 solution

In the present work, the mechanism of charging/discharging at the amorphous manganese oxide electrode was investigated in 0.1 M Na₂SO₄ solution with respect to amount of hydrates and valence (oxidation) states of manganese using a.c.-impedance spectroscopy, anodic current transient technique and cyclic voltammetry. For this purpose, first the amorphous manganese oxide film was potentiostatically electrodeposited, followed by heat-treatment at 25–400 °C to prepare the electrode specimen with different amounts of hydrates and oxidation states of manganese. For as-electrodeposited electrode with the most hydrates, the anodic current transient clearly exhibited a linear relationship between the logarithm of current density and the logarithm of time, with a slope of −0.5, indicating that the charging/discharging is purely limited by Na⁺/H⁺ ion diffusion. From the analyses of the impedance spectra combined with anodic current transients measured on the hydrated electrode heat-treated at 25–150 °C, it was found that as the amount of hydrates decreases, the depth of cation diffusion in the electrode becomes shallower and the ratio of charge-transfer resistance to diffusion resistance also increases. This suggests that a transition occurs of pure diffusion control to a mixed diffusion and charge-transfer reaction control. For the dehydrated electrode heat-treated at 200–400 °C, the charging/discharging purely proceeds by the charge-transfer reaction. The reversibility of the redox reaction increases with increasing amount of hydrates and oxidation states of manganese, which provides us the higher power density. On the other hand, the pseudocapacitance decreases in value with increasing heat-treatment temperature, thus causing the lower energy density.     

Improvement of toluene catalytic combustion by addition of cesium in copper exchanged zeolites

HY and HMFI zeolites exchanged with copper and cesium have been studied for the catalytic combustion of toluene (800 ppm) with air. The catalysts activity has been analyzed by comparison of light-off curves and in both Cu zeolites, the addition of Cs leads to a decrease of the light-off temperature by 50 °C. Temperature-programmed reduction (H₂-TPR) and EPR studies have evidenced clear differences in the characteristics of the copper species both in the presence and absence of Cs co-cations. These differences account for the nature of the active centers in the Cu zeolites for the toluene oxidation. The position and geometry of the copper ions in the zeolite matrix are of great significance for the redox behavior and activity for toluene oxidation. In both MFI and FAU structures, the bulky Cs co-cations are located in the more accessible main zeolite pores, forcing the copper ions to occupy the most stable, but less accessible positions within each structure. In the case of the MFI zeolite, the EPR study revealed that the Cs exchange resulted in an increased abundance in the number of square pyramidal Cu²⁺ ions relative to the other Cu environments. Cs co-cations also lead to an increase in the reducibility of the copper ions mainly due the reduction of protons in Cu, Cs-containing samples.     

Hydrodechlorination of 3-chloropyridine and chlorobenzene in methanol solution over alkali-modified zirconia-supported palladium catalysts

The liquid-phase hydrodechlorination of 3-chloropyridine and chlorobenzene has been studied over alkali-modified zirconia-supported palladium catalysts. The modification of the ZrO₂ with alkali metal carbonates improves the catalytic activity of the final palladium catalyst. Therefore, the larger the ionic radii (Li⁺ < Na⁺ < K⁺), the greater the catalytic activity (TOF) of the palladium catalyst. For 3-chloropyridine, hydrodechlorination proceeds without catalyst deactivation. This is explained as the result of the interaction of reaction products (pyridine and HCl) forming pyridinium chloride, thus avoiding the detrimental effect of HCl on the palladium particles. Catalytic hydrodechlorination of chlorobenzene over Pd catalysts exhibits an initial catalytic activity (TOF) much lower than that of 3-chloropyridine and the Pd catalysts deactivate as the reaction proceeds. Finally, chlorobenzene hydrodehalogenation has also been carried out in the presence of an equimolecular amount of pyridine resulting in a decrease in the initial reaction rate on the one hand, but also in an increase in final conversion on the other.     

Formation of Pd nanoparticles in surfactant-mesoporous silica composites and surfactant solutions

Highly dispersed palladium nanoparticles containing mesoporous silicas MCM-41 and MCM-48 were prepared by one-pot synthesis. The method consists of the simultaneous formation of CTA⁺ surfactant templating MCM-41 mesophase and CTA⁺ micelle-capped PdO, which was reduced by hydrogen to Pd metal with particle size ≈ 2 nm and was observed to stay inside the mesochannels of MCM-41 (pore size ≈ 3.8 nm) by TEM, XAS, and PXRD. During hydrothermal synthesis of Pd/MCM-48, Pd nanoparticles of average size ≈ 6–7 nm were deposited on the MCM-48 of pore size = 4 nm. The deposition is probably derived from ethanol reduction of Pd(II) complex generated from PdCl₂ precursor by hydrolysis of TEOS and C₁₂H₂₅(OCH₂CH₂)₄OH surfactant. The formation of Pd(0) from Pd(II) species in solid mesoporous silicas by hydrogen reduction was monitored by in situ XAS, and compared with the formation of Pd(0) from [PdCl₄]²⁻, [PdCl₃(H₂O)], and Pd(OH)₂ by sodium dodecyl sulfate surfactant and alcohol reduction in aqueous solutions.     

A comparative study of TiO2 supported noble metal catalysts for the oxidation of formaldehyde at room temperature

The TiO₂ supported noble metal (Au, Rh, Pd and Pt) catalysts were prepared by impregnation method and characterized by means of X-ray diffraction (XRD) and BET. These catalysts were tested for the catalytic oxidation of formaldehyde (HCHO). It was found that the order of activity was Pt/TiO₂  Rh/TiO₂ > Pd/TiO₂ > Au/TiO₂  TiO₂. HCHO could be completely oxidized into CO₂ and H₂O over Pt/TiO₂ in a gas hourly space velocity (GHSV) of 50,000 h⁻¹ even at room temperature. In contrast, the other catalysts were much less effective for HCHO oxidation at the same reaction conditions. HCHO conversion to CO₂ was only 20% over the Rh/TiO₂ at 20 °C. The Pd/TiO₂ and Au/TiO₂ showed no activities for HCHO oxidation at 20 °C. The different activities of the noble metals for HCHO oxidation were studied with respect to the behavior of adsorbed species on the catalysts surface at room temperature using in situ DRIFTS. The results show that the activities of the TiO₂ supported Pt, Rh, Pd and Au catalysts for HCHO oxidation are closely related to their capacities for the formation of formate species and the formate decomposition into CO species. Based on in situ DRIFTS studies, a simplified reaction scheme of HCHO oxidation was also proposed.     

Oxidation behaviour and catalytic properties of Pd/Al2O3 catalysts in the total oxidation of methane

A series of Pd/Al₂O₃ catalysts with a wide range of mean Pd particle sizes (ca. 2–30 nm in diameter) was prepared by using various precursors (H₂PdCl₄, Pd(NO₃)₂ and Pd(AcAc)₂) and pre-treatments. The mean particle size of reduced samples was determined by H₂ chemisorption. The catalytic activity in methane oxidation under lean burn conditions was measured. The oxidation of reduced samples was studied at 300 °C. The extent of oxidation was found to decrease with increasing mean particle size. While small particles (<5 nm) oxidised very rapidly, the oxidation of large particles (ca. >15 nm) proceeded via a two-step process, being first fast and then slow. The decomposition of oxide species was studied by temperature-programmed experiments under vacuum. Two distinct oxidised species with different stability were evidenced depending on the particle size. Oxidised species in larger particles were found of lower stability than in smaller ones. A correlation between the existence of distinct types of oxide species and catalytic properties in methane oxidation was discussed.     

Evaluation of V2O5–WO3–TiO2 and alternative SCR catalysts in the abatement of VOCs

Two different commercial SCR catalysts belonging to the V₂O₅–WO₃–TiO₂ system, and different alternative catalysts based on Mn, Fe, Cr, Al and Ti oxides have been tested in the conversion of VOCs in excess oxygen in a temperature range typical of the SCR process (500–700 K). Propane, propene, isopropanol, acetone, 2-chloropropane and 1,2-dichlorobenzene have been fed with excess oxygen and helium. The industrial catalysts are poorly active in the conversion of propane, giving mainly rise to propene by oxy-dehydrogenation. The conversion of propene is higher with CO as the predominant product. In any case, the oxidation activity depends on the vanadium content of the catalyst. Isopropanol is mainly converted into acetone and propene, while acetone is burnt predominantly to CO. Mn- and Fe- containing systems are definitely more active in the conversion of hydrocarbons and oxygenates, giving rise almost exclusively to CO₂. 2-Chloropropane is selectively dehydrochlorinated to propene and HCl starting from 350 K, propene being later burnt to CO on the industrial V₂O₅–WO₃–TiO₂ catalysts, whose combustion activity is, apparently, not affected by chlorine. On the contrary, chlorine strongly affects the behavior of Mn-based catalysts, that are active in the dehydrochlorination of 2-chloropropane, but are simultaneously deactivated with respect to their combustion catalytic activity. The conversion of 1,2-dichlorobenzene gives rise to important amounts of heavy products in our experimental conditions with relatively high reactant concentration.     

Reactor and in situ FTIR studies of Pt/BaO/Al2O3 and Pd/BaO/Al2O3 NOx storage and reduction (NSR) catalysts

The reduction of NO under cyclic “lean”/“rich” conditions was examined over two model 1 wt.% Pt/20 wt.% BaO/Al₂O₃ and 1 wt.% Pd/20 wt.% BaO/Al₂O₃ NO_x storage reduction (NSR) catalysts. At temperatures between 250 and 350 °C, the Pd/BaO/Al₂O₃ catalyst exhibits higher overall NO_x reduction activity. Limited amounts of N₂O were formed over both catalysts. Identical cyclic studies conducted with non-BaO-containing 1 wt.% Pt/Al₂O₃ and Pd/Al₂O₃ catalysts demonstrate that under these conditions Pd exhibits a higher activity for the oxidation of both propylene and NO. Furthermore, in situ FTIR studies conducted under identical conditions suggest the formation of higher amounts of surface nitrite species on Pd/BaO/Al₂O₃. The IR results indicate that this species is substantially more active towards reaction with propylene. Moreover, its formation and reduction appear to represent the main pathway for the storage and reduction of NO under the conditions examined. Consequently, the higher activity of Pd can be attributed to its higher oxidation activity, leading both to a higher storage capacity (i.e., higher concentration of surface nitrites under “lean” conditions) and a higher reduction activity (i.e., higher concentration of partially oxidized active propylene species under “rich” conditions). The performance of Pt and Pd is nearly identical at temperatures above 375 °C.