Comparison of the reactivity of bulk and surface oxides on Pd(100)

The reactivity of bulk PdO clusters produced by plasma oxidation of Pd(100) towards propene oxidation was characterized using temperature programmed desorption (TPD) and isothermal oxygen titration. The TPD results were dominated by simultaneous CO₂ and water desorption in a peak at 490 K. The only other product observed was a small amount of CO near saturation propene coverages that also desorbed at 490 K. The propene coverage saturated at exposures between 0.5–1 l, indicating a sticking coefficient close to one. In the titration experiments, CO₂ production peaked almost immediately upon exposure to propene, indicating that the propene oxidation rate fell as the surface was reduced. Above 450 K, virtually all of the propene was completely oxidized to CO₂ and water, while at lower temperatures small amounts of CO were observed and unreacted propene fragments accumulated on the surface. In comparison, previous results for a well-ordered surface oxide on Pd(100) were similar in that CO₂ and water also desorbed simultaneously indicating a similar mechanism, but different in that the sticking coefficient on the surface oxide was a factor of 20 lower, and the desorption peaked 60 K lower. These differences cause the bulk oxide to be far more active at higher temperatures than the surface oxide, but the surface oxide displays some activity down to lower temperatures where propene simply accumulates on the bulk oxide surface.     

A molecular mechanics study of the adsorption of ethane and propane on V2O5(001) surfaces with oxygen vacancies

Adsorption geometries and energies of ethane and propane physisorbed on the (001) surface of vanadium pentoxide with oxygen vacancies were determined by a molecular mechanics simulation. Three types of oxygen vacancies, built up by removal of vanadyl oxygen, two-fold and three-fold coordinated oxygen, respectively, have been modeled as defects. The energetically most favorable adsorption site is on top of a vacancy of two-fold coordinated oxygen for ethane and propane, respectively. The next favorable site for both alkanes is on top of a vacancy of vanadyl oxygen. Due to the generation of a “van der Waals cage” which traps the hydrocarbon the adsorption on the defect site is favored in comparison with the ideal surface for these two defect types. A vacancy of three-fold coordinated oxygen does not lead to an enhancement of adsorption and pushes the reactant towards the unperturbed surface areas due to the fact, that no energy minimum can be obtained in the vicinity of the defect. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ordered Mesoporous Silica (OMS) Supported Vanadium Nitride and Carbide Catalysts

Nanostructured vanadium nitride and carbide catalysts were prepared by the nitridation and carburization of vanadium oxide supported on M41S materials (MCM-41 and SBA-15) and activated carbon. The oxide precursors, V₂O₅/M41S, were obtained in three different synthesis strategies using “in situ” and “ex situ” incorporation of vanadia precursors (V(acac)₃) into the mesoporous host. For the oxide precursors specific surface areas exceeding 1,200 m² g⁻¹ were achieved. After nitridation a slight decrease of surface area was observed. All VN catalysts show a high activity in propane dehydrogenation with a selectivity exceeding 80% towards propene. Impregnation and nitridation conditions have profound influence upon the catalytic activity. The highest activity was observed for VN supported on NORIT A.     

Mechanistic aspects of the oxidative dehydrogenation of propane over an alumina-supported VCrMnWOx mixed oxide catalyst

Mechanistic and kinetic aspects of the catalytic oxidative dehydrogenation of propane (ODP) were studied within a wide range of temperatures (673–773 K), partial pressures of oxygen (0–20 kPa), propane (0–40 kPa) and propene (0–4 kPa) under both steady-state ambient-pressure and transient, vacuum conditions in the temporal analysis of products (TAP) reactor. A Mn_0.18V_0.3Cr_0.23W_0.26O_x–Al₂O₃ catalyst was identified as a selective catalyst for ODP by high-throughput experiments. For comprehensive catalyst characterization, XRD, BET, and in situ UV–visible techniques were applied. The results from transient experiments in combination with UV–visible tests reveal that selective and non-selective propane oxidation occurs on the same active surface sites, i.e., lattice oxygen. CO_x formation takes place almost exclusively via consecutive propene oxidation, which involves both lattice and adsorbed oxygen species, with the latter being active in CO formation. However, the adsorbed species play a minor role. CO₂ formation was found to increase in the presence of propene in the reaction feed. Optimized operating conditions for selective propane oxidation were derived and discussed based on the experimental observations with respect to the influence of temperature and partial pressures of O₂, C₃H₆ and C₃H₈ on the reaction. In co-feed mode with a propane to oxygen ratio of 2, optimal catalytic performance is achieved at low partial pressures of oxygen and high temperature. Propene selectivity can be also improved by carrying out the ODP reaction in a periodic mode; that is an alternate feed of propane and air.     

Oxidation state of platinum clusters during the reduction of NOx with propene and propane

The oxidation state of platinum supported on mesoporous SiO₂ and Al₂O₃ with MCM-41 type structure during the reduction of NO_x with propene or propane was investigated using in situ X-ray absorption spectroscopy. Platinum supported on MCM-41 (SiO₂) was reduced at low and oxidized at high reaction temperatures when propene was used as reducing agent, while it was found to be always oxidized in Pt/MCM-41 (Al₂O₃). When propane was used as reducing agent significant NO conversion was not observed over Pt/MCM-41 (SiO₂) and on both supports platinum was in an oxidized state. At the successive adsorption of the reactants, the prereduced catalysts were oxidized after NO adsorption and reduced after addition of the hydrocarbons. Addition of oxygen re-oxidized the catalysts, while the presence of water vapor did not influence the oxidation state.     

Adsorption and reaction of CO on CuO–CeO2 catalysts prepared by the combustion method

Temperature-programmed techniques were employed to investigate the interaction of CO with CuO–CeO₂ prepared by the urea-nitrates combustion method. These catalysts exhibited high and stable CO oxidation activity at relatively low reaction temperatures (< 150 °C). The CO adsorption capacity and catalytic activity of the catalysts was analogous to the concentration of easily-reduced copper oxide surface species. TPD and TPSR results can be explained by a dual scheme of CO adsorption: (i) on oxidized sites, which get reduced with simultaneous formation of surface CO₂ and (ii) on reduced sites created by the former interaction. 10–20% of adsorbed CO desorbs molecularly in the absence of gas-phase O₂, but reacts totally towards CO₂ in the presence of gas-phase O₂. Inhibition by CO₂ observed under steady-state CO oxidation conditions is due to CO₂ adsorption as found by CO₂-TPD.     

Surface composition and possible rearrangement of disperse Pt and Rh catalysts: does the presence of carbon and oxygen contribute to different catalytic properties?

The surface composition of Rh and Pt blacks (as determined by XPS) shows carbon and oxygen impurities in the untreated state. Oxygen on Pt is present as adsorbed O as well as OH/H₂O groups and oxidized carbon. Rh was partly oxidized to Rh₂O₃, in agreement with UPS showing hardly any Fermi‐edge intensity in untreated Rh as opposed to untreated Pt. High Fermi‐edge intensities indicated a predominant metallic surface after an in situ treatment with H₂ at 483 K, increasing the purity (XPS) to ∼90%. This treatment reduced Rh to metal and removed its C impurity. Pt, in turn, retained much carbon after H₂ treatment, present mainly as graphitic carbon. A minor amount of CO was also detected, some of the O 1s peak belonging to it. The two metals were tested in methylcyclopentane reactions. Considering the necessity of carbon for nondegradative reactions and oxygen enhancing fragmentation, a correlation is suggested between the typical impurities of Pt and Rh and their respective catalytic propensities: the high fragmentation activity of Rh and the predominant nondegradative reactions to C₆ “ring opening products” on Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

Methanol Adsorption on V2O3(0001)

Well ordered V₂O₃(0001) layers may be grown on Au(111) surfaces. These films are terminated by a layer of vanadyl groups which may be removed by irradiation with electrons, leading to a surface terminated by vanadium atoms. We present a study of methanol adsorption on vanadyl terminated and vanadium terminated surfaces as well as on weakly reduced surfaces with a limited density of vanadyl oxygen vacancies produced by electron irradiation. Different experimental methods and density functional theory are employed. For vanadyl terminated V₂O₃(0001) only molecular methanol adsorption was found to occur whereas methanol reacts to form formaldehyde, methane, and water on vanadium terminated and on weakly reduced V₂O₃(0001). In both cases a methoxy intermediate was detected on the surface. For weakly reduced surfaces it could be shown that the density of methoxy groups formed after methanol adsorption at low temperature is twice as high as the density of electron induced vanadyl oxygen vacancies on the surface which we attribute to the formation of additional vacancies via the reaction of hydroxy groups to form water which desorbs below room temperature. Density functional theory confirms this picture and identifies a methanol mediated hydrogen transfer path as being responsible for the formation of surface hydroxy groups and water. At higher temperature the methoxy groups react to form methane, formaldehyde, and some more water. The methane formation reaction consumes hydrogen atoms split off from methoxy groups in the course of the formaldehyde production process as well as hydrogen atoms still being on the surface after being produced at low temperature in the course of the methanol ?? methoxy + H reaction.     

Study of surface and lattice oxygen atoms over magnesium vanadate phases by isotopic exchange with C18O2

Different magnesium vanadate phases, V-Mg-O phases (α- Mg₂V₂O₇, Mg₃V₂O₈ and β- MgV₂O₆), MgO and V₂O₅ oxides have been compared with respect to their surface properties and their oxygen exchange capacities with C¹⁸O₂ in the gas phase. By temperature- programmed desorption of carbon dioxide, the absence of any basic impurities (i.e., MgO or residual oxidised K impurities resulting from the preparation) has been evidenced on the surface of magnesium vanadate phases. This demonstrates that the catalytic properties of the magnesium vanadate phases for oxidative dehydrogenation of propane as previously studied cannot be explained by synergetic effects due to the presence of any basic component impurities since they are absent in this case. While on MgO an important surface exchange process occurs with C¹⁸O₂ of the gas phase, this exchange is very low on V₂O₅ and pure V-Mg-O phases. A comparison of the different magnesium vanadate phases in the same experimental conditions indicates that the α-Mg₂V₂O₇ phase (which exhibited the highest selectivity for oxidative dehydrogenation of propane to propene) shows the lowest lattice oxygen exchange with C¹⁸O₂ of the gas phase. This is another specificity of this phase. This revised version was published online in July 2006 with corrections to the Cover Date.     

Propane Ammoxidation Over the Mo�CV�CTe�CNb�CO M1 Phase: Reactivity of Surface Cations in Hydrogen Abstraction Steps

Density functional theory calculations (GGA-PBE) have been performed to investigate the adsorption of C₃ (propane, isopropyl, propene, and allyl) and H species on the proposed active center present in the surface ab planes of the bulk Mo?CV?CTe?CNb?CO M1 phase in order to better understand the roles of the different surface cations in propane ammoxidation. Modified cluster models were employed to isolate the closely spaced V=O and Te=O from each other and to vary the oxidation state of the V cation. While propane and propene adsorb with nearly zero adsorption energy, the isopropyl and allyl radicals bind strongly to V=O and Te=O with adsorption energies, ??E, being ???1.75 eV, but appreciably more weakly on other sites, such as Mo=O, bridging oxygen (Mo?CO?CV and Mo?CO?CMo), and empty metal apical sites (??E > ?1 eV). Atomic H binds more strongly to Te=O (??E ?? ?3 eV) than to all the other sites, including V=O (??E = ?2.59 eV). The reduction of surface oxo groups by dissociated H and their removal as water are thermodynamically favorable except when both H atoms are bonded to the same Te=O. Consistent with the strong binding of H, Te=O is markedly more active at abstracting the methylene H from propane (E _a  ?? 1.01 eV) than V=O (E _a  = 1.70 eV on V⁵⁺=O and 2.13 eV on V⁴⁺=O). The higher-than-observed activity and the loose binding of Te=O moieties to the mixed metal oxide lattice of M1 raise the question of whether active Te=O groups are in fact present in the surface ab planes of the M1 phase under propane ammoxidation conditions.     

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 Au in V2O5/SiO2 and MoO3/SiO2 catalysts on physicochemical and catalytic properties in oxidation of C3 hydrocarbons and of CO

Silica supported vanadia and molybdena catalysts with, and without Au, were prepared, characterized with XRD, TEM, XPS, H₂-TPR and probe reaction of isopropanol decomposition, and tested in the oxidation of propene, propane and CO. The presence of Au: (a) does not affect markedly structural and textural properties, such as specific surface area, size of V₂O₅ or MoO₃ crystallites, or the electronic state of V and Mo ions, (b) increases the reducibility of vanadia and molybdena phase, (c) enhances the dehydrogenation properties in isopropanol decomposition, and (d) modifies catalytic activity in oxidation reactions. The Au particles increase the total activity in CO oxidation. For propane oxidation at high temperatures the increase in total activity is observed, with the decrease in the selectivity to oxidative dehydrogenation product (propene) and increase in the selectivity to CO₂. The catalytic performance in propene oxidation at 200–300 °C depends on the Au presence and the composition of the reaction mixture. The gold-containing catalysts favour allylic oxidation of propene to acrolein and oxyhydration to acetone, and suppress the C₂ products (ethanal, acetic acid) of partial degradation of a propene molecule. In the presence of hydrogen in the reaction mixture, higher selectivities of acetone (product of oxyhydration) were observed for all the catalysts.     

Propane and oxygen action on NOx adspecies on low-exchanged Cu-ZSM-5

A surface intermediate with a C/N ratio close to 3 has been shown by TPD to form at co-adsorption of NO and propane as well as NO, propane and O₂ on low-exchanged Cu-ZSM-5. The adsorption of NO, propane and oxygen has been studied to evaluate their effect on the formation of this complex. Its formation is accompanied by a decrease in the concentration of surface nitrite–nitrate. The kinetics of nitrite–nitrate adspecies formation as a function of the reagents concentration and temperature has been investigated. Some NO adspecies have been found to decompose yielding N₂O. This revised version was published online in July 2006 with corrections to the Cover Date.     

The structure of vanadium oxide species on γ-alumina; an in situ X-ray absorption study during catalytic oxidation

The mechanism of catalytic oxidation reactions was studied using in situ X-ray absorption spectroscopy (XAFS) over a 17.5 wt% V₂O⁵/Al₂O₃ catalyst, i.e., at reaction temperatures and in the presence of reactants. It was found that X-ray absorption near-edge structure (XANES) is a powerful tool to study changes in the local environment and the oxidation state of the vanadium centres during catalytic oxidation. At 623 K, the catalyst follows the associative mechanism in CO oxidation. XAFS revealed that the Mars–van Krevelen mechanism is operative at 723 K for CO oxidation. The extended X-ray absorption fine structure (EXAFS) results showed that the structure of the supported V₂O⁵ phase consists of monomeric tetrahedral (Al–O)₃–V=O units after dehydration in air at 623 K. However, the residuals of the EXAFS analysis indicate that an extra contribution has to be accounted for. This contribution probably consists of polymeric vanadate species. The structure remains unchanged during steady-state CO oxidation at 623 and 723 K. Furthermore, when oxygen was removed from the feed at 623 K, no changes in the spectra occurred. However, when oxygen is removed from the feed at 723 K, reduction of the vanadium species was observed, i.e., the vanadyl oxygen atom is removed. The V³⁺ ion subsequently migrates into the γ-Al₂O₃ lattice, where it is positioned at an Al³⁺ octahedral position. This migration process appears to be reversible; so the (Al–O)₃–V=O units are thus restored by re-oxidation. This revised version was published online in June 2006 with corrections to the Cover Date.     

Influence of carbon precursor on porosity,surface composition and catalytic behaviour of CMK-3 in oxidative dehydrogenation of propane to propene

Ordered mesoporous CMK-3 carbon replicas were synthesized by infiltration of mesopores present in a SBA-15 silica template with two different carbon precursors, i.e. sucrose and poly(furfuryl alcohol). The obtained composites were carbonized under an inert gas atmosphere at 550, 650, 750 and 850?°C, and the template was etched with a HF solution. The final carbon replicas were analyzed by various physicochemical techniques, including low-temperature N₂ adsorption, X-ray diffraction, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy, and tested as catalysts in the oxidative dehydrogenation of propane (ODP) at 450?°C. Both series of materials differed strongly with respect to their porosity, but showed very similar surface composition determined by XPS. Higher porosity of CMK-3 prepared using the sucrose precursor influenced propane conversion and selectivity to propene. Furthermore, oxygen containing groups (e.g. carbonyl-type) were found to be less sensitive to the type of carbon precursor than to the ODP reaction conditions.     

Propene Adsorption on Gold Particles on TiO2(110)

The adsorption of propene on rutile TiO₂(110) and on gold islands dispersed on TiO₂(110) [Au/TiO₂(110)], both at 120 K, has been studied using temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and He⁺ low energy ion scattering spectroscopy (LEIS). Propene adsorbs on both TiO₂(110) and Au/TiO₂(110), with desorption peak temperatures at low coverage of 190 and 240 K, respectively. When only 16% of the TiO₂(110) surface is covered by gold islands [16% Au/TiO₂(110)], moderate propene doses populate both the 240 and 190 K TPD peaks, in that order. The 190 K peak, seen also without Au, is due to propene bound to bare Ti sites. The 240 K peak is attributed to propene adsorbed to Ti sites at the edges of gold islands. Tiny doses of propene to the 16% Au/TiO₂(110) surface give this a 240 K TPD peak but no 190 K feature, showing that the propene is mobile on TiO₂(110). A TPD feature at 150 K, which is more prominent at higher Au coverages and higher propene doses, is due to propene bound only to metallic Au islands. Propene desorption shows additional intensity at 265-310 K when the gold islands are only one atom thick, due to propene adsorbed on 2D Au islands or at Ti sites near their edges.     

Mechanism of di(methyl)ether (DME) electrooxidation at platinum electrodes in acid medium

The electrooxidation of DME was studied at a bulk platinum electrode. It was shown that the DME adsorption was a slow step in the overall oxidation reaction. The DME adsorption is potential dependent in the hydrogen region of platinum and independent in the double layer region. From low potential scan rate voltammetry and DME stripping experiments, it was shown that the DME oxidation mechanism occurred via several reaction paths. At low potentials, DME oxidation leads to the existence of a positive current plateau. “In situ” Infrared Reflectance Spectroscopy experiments were carried out to identify the intermediate and reaction products of DME adsorption and oxidation at different potentials. CO_L (linearly bonded CO), CO_B (bridge bonded CO), adsorbed COOH species and CO₂ were detected. From these electrochemical and spectro-electrochemical results, it was proposed that some adsorbed DME was hydrolysed and directly oxidized to CO₂ or HCOOH species and some partially blocked platinum sites at the surface forming Pt–CHO and/or Pt–CO. Then, as soon as platinum becomes able to activate water, a bifunctionnal mechanism occurs to form either HCOOH or CO₂ again following two different reaction paths.     

Support effects in the dissociation of CO on Rh/CeO2(111)

The adsorption and reaction of CO on Rh particles supported on stoichiometric and partially reduced CeO₂(111) surfaces was studied using a combination of HREELS and TPD. A fraction of the CO adsorbed on the supported Rh particles was found to undergo dissociation to produce adsorbed C and O atoms. TPD results for isotopically labeled CO demonstrated that O atoms produced by CO dissociation rapidly exchange with the oxygen in the ceria lattice. The fraction of adsorbed CO which dissociated was found to increase significantly with the extent of reduction of the CeO₂(111) surface, suggesting that oxygen vacancies on the surface of the support play a direct role in the CO dissociation reaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic dense membranes of doped Bi4V2O11 (BIMEVOX) for selective partial oxidation: chemistry of defects versus catalysis

A catalytic dense membrane reactor (CDMR) is used to physically separate the reaction step from the reoxidation of the catalyst. By decoupling the redox mechanism prevailing in mild oxidation of hydrocarbons, the operating conditions may be optimized resulting in an increase of selectivity. The membranes are made up of BIMEVOX oxides, obtained by partial substitution of V in γ-Bi₄V₂O₁₁ by ME (Co, Cu, Ta). Experiments performed on BIMEVOX dense membranes using propene and propane are described in terms of, (i) active sites on polished or unpolished surfaces, (ii) operating conditions (T, pO₂ in the high oxygen partial pressure compartment), which determine the selectivity, either to mild oxidation products (acrolein, hexadiene, CO), or to partial oxidation products (CO, H₂), and, (iii) nature of ME cations and relative properties. The discussion deals with the respective role of electronic versus oxide ion conductivities which depend on defects in the structure as well as on the redox properties of cations.