CO oxidation on a model Cu/Rh(100) catalyst

The reaction between carbon monoxide and molecular oxygen on a model Cu/Rh(100) bimetallic catalyst was studied at 455 K using a CO/O₂ = 2 reactant gas mixture at a total pressure of 10.0 Torr. A maximum in the initial activity was observed at a Cu coverage of 1.3 monolayers. However, the Cu overlayers were found to be unstable at the reaction conditions employed in that the Cu films interact strongly with surface oxygen to form three-dimensional CuO_x clusters. The morphological modifications were found to influence markedly the catalytic properties of the surface. However, the initial catalytic activity and surface morphology of the Cu films could be restored by flashing the sample to > 750 K.     

Periodic Control for Improved Low-Temperature Catalytic Activity

The influence of transient changes in the gas composition on the low-temperature activity of a commercial three-way catalyst and a Pt/Al₂O₃ model catalyst has been studied. By introducing well-controlled periodic O₂ pulses to simple gas mixtures of CO or C₃H₆ (in N₂), a substantial improvement of the low temperature oxidation activity was observed for both catalysts. The reason for low activity at low temperatures is normally attributed to self-poisoning by CO or hydrocarbons. The improved catalytic performance observed here is suggested to origin from the transients causing a surface reactant composition that is favourable for the reaction rate.     

Carbon Monoxide Oxidation over Au/Ce1−x Zr x O2 Catalysts: Effects of Moisture Content in the Reactant Gas and Catalyst Pretreatment

The Au/Ce_1?x Zr _x O₂ (x = 0, 0.25, 1) catalysts were synthesized, characterized by BET, XRD, TPR-H₂, HRTEM, AAS and tested in CO oxidation. The effect of moisture in the reactant gas on CO conversion has been studied in a wide range of concentrations (~0.7–6000 ppm). Moisture generates a positive effect on catalytic activity and wet conditions gave higher CO conversions. The optimum concentration of moisture for CO oxidation over Au/CeO₂ and Au/Ce_0.75Zr_0.25O₂ is 200–1000 ppm, while further increase in the moisture content suppresses CO conversion. The activity of the studied Au catalysts depends on the amount of moisture adsorbed on the catalyst rather than on its content in the feed stream, which suggests that the reaction involves water-derived species on the catalysts surface. The effect of the catalysts pretreatment in air, dry He, H₂ stream as well as H₂ + H₂O gas mixture on their catalytic performance in CO oxidation has been also investigated. The model of the active sites for CO oxidation over the studied catalysts was proposed.     

Formation and catalytic activity of partially oxidized Pd nanoparticles

Combining multi molecular beam (MB) experiments and in-situ time-resolved infrared reflection absorption spectroscopy (TR-IRAS), we have studied the formation and catalytic activity of Pd oxide species on a well-defined Fe₃O₄ supported Pd model catalyst. It was found that for oxidation temperatures up to 450 K oxygen predominantly chemisorbs on metallic Pd whereas at 500 K and above (~10⁻⁶ mbar effective oxygen pressure) large amounts of Pd oxide are formed. These Pd oxide species preferentially form a thin layer at the particle/support interface. Their formation and reduction is fully reversible. As a consequence, the Pd interface oxide layer acts as an oxygen reservoir providing oxygen for catalytic surface reactions. In addition to the Pd interface oxide, the formation of surface oxides was also observed for temperatures above 500 K. The extent of surface oxide formation critically depends on the oxidation temperature resulting in partially oxidized Pd particles between 500 and 600 K. It is shown that the catalytic activity of the model catalyst for CO oxidation decreases significantly with increasing surface oxide coverage independent of the composition of the reactants. We address this deactivation of the catalyst to the weak CO adsorption on Pd surface oxides, leading to a very low reaction probability.     

Methanol oxidation over model cobalt catalysts: Influence of the cobalt oxidation state on the reactivity

X-ray photoelectron and absorption spectroscopies (XPS and XAS) combined with on-line mass spectrometry were applied under working catalytic conditions to investigate methanol oxidation on cobalt. Two cobalt oxidation states (Co₃O₄ and CoO) were prepared and investigated as regards their influence on the catalytic activity and selectivity. In addition adsorbed species were monitored in the transition of the catalyst from a non-active state, to an active one. It is shown that the surface oxidation state of cobalt is readily adapted to the oxygen chemical potential in the CH₃OH/O₂ reaction mixture. In particular, even in oxygen-rich mixtures the Co₃O₄ surface is partially reduced, with the extent of surface reduction following the methanol concentration. The reaction selectivity depends on the cobalt oxidation state, with the more reduced samples favouring the partial oxidation of methanol to formaldehyde. In the absence of oxygen, methanol effectively reduces cobalt to the metallic state, also promoting H₂ and CO production. Direct evidence of methoxy and formate species adsorbed on the surface upon reaction was found by analysing the O 1s and C 1s photoelectron spectra. However, the surface coverage of those species was not proportional to the catalytic activity, indicating that they might also act as reaction inhibitors.     

The transient response of ZrO2 oxygen sensors to step changes in gas composition

The transient voltage response of ZrO₂ oxygen sensors was examined following step changes in gas composition. The experiments were performed on a laboratory flow reactor at 600° C. Composition changes between (a) 100% and (b) 1% O₂ in N₂ produced response curves whose symmetry varied between composition steps (a) from low-to-high oxygen and (b) from high-to-low oxygen. This difference is due to the logarithmic dependence of sensor voltage on oxygen partial pressure. Corresponding oxygen partial pressure-time curves, derived from experimental voltage via the Nernst equation, are symmetric with respect to the direction of composition changes. Abrupt transitions are found in voltage-time curves at 600° C following step changes of reactive gases; e.g. from O₂/N₂ mixtures to CO/N₂, H₂/N₂ or D₂/N₂ mixtures. These voltage-steps represent transitions in stoichiometry of the surface boundary layer on the ZrO₂ sensor. Delay times before the transition also reflect reaction stoichiometry. Response times with O₂/CO, O₂/H₂ and O₂/D₂ follow trends predicted by the kinetic theory of gases. A limited number of experiments were performed to examine the relationships between sensor response and sensor catalytic activity. Poorer oxidation catalytic activity parallels slower response characteristics.     

Virtual Control for High Conversion of Methane Over Supported Pt

A transient model for oxidation of methane over Pt/Al₂O₃ monolith catalysts has been developed by rigorous consideration of mass- and heat transport and mean-field treatment of the reaction kinetics. By coupling a virtual regulator using the reactant slip, methane or oxygen partial pressures, or oxygen surface coverage as feedback variable(s) as such or in combinations for control of feed composition, the influence of gas composition changes on the methane conversion has been investigated.     

La0.6Sr0.4Co0.8Ga0.2O3‐δ (LSCG) hollow fiber membrane reactor: Partial oxidation of methane at medium temperature

In this study, La_0.6Sr_0.4Co_0.8Ga_0.2O_3‐δ (LSCG) hollow fiber membrane reactor was integrated with Ni/LaAlO₃‐Al₂O₃ catalyst for the catalytic partial oxidation of methane (POM) reaction. The process was successfully carried out in the medium temperature range (600–800°C) for reaction of blank POM with bare membrane, catalytic POM reaction and swept with H₂:CO gas mixture. For the catalytic POM reaction, enhancement in selectivity to H₂ and CO is obtained between 650–750°C when O₂:CH₄ <1. High CH₄ conversion of 97% is achieved at 750°C with corresponding H₂ and CO selectivity of about 74 and 91%. The oxygen flux of the membranes also increased with the increase in oxygen partial pressure gradient across the membrane. The postreacted membranes were tested via XRD and FESEM‐EDX for their crystallinity and surface morphology. XPS analysis was further used to investigate the O1s, Co 2p and Sr 3d binding energies of the segregated elements from the reducing reaction environment. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3874–3885, 2013     

Kinetic modeling of CO oxidation on Pt/CeO2 in a gradientless reactor

Cerium oxide is a major additive in three-way catalysts used in emission control of automobile exhaust. Pt/CeO₂ was studied in order to better understand the role of ceria in promoting CO oxidation reaction. The kinetics of carbon monoxide oxidation on Pt/cerium oxide catalyst, was studied over the temperature range 100–170°C. Steady state kinetic measurements of CO oxidation were obtained in a computer controlled micro-CSTR reactor. Activation energies were reported to vary between 39·5 and 51·2 kJ mol⁻¹. At low concentrations of either reactant (CO, O₂) and total conversion, the catalyst exhibited multiple steady states, similar to the multiplicity behavior of Pt/Al₂O₃. The total conversion was reached at 120°C. In comparison, the total conversion at low reactant concentrations was reached at a temperature of 148°C for the alumina-supported catalyst. Langmuir–Hinshelwood mechanisms gave a good fit to the data. However, no single rate expression could effectively describe the CO oxidation data over the whole concentration in the product of the CSTR reactor. The facts gathered indicate that oxygen adsorbed on interfacial Pt/Ce sites and ceria lattice oxygen provides oxygen for CO oxidation. Cerium oxide has been found to lower CO oxidation activation energy, enhance reaction activity and tends to suppress the usual CO inhibition effect.     

The Effect of Oxygen Concentration on the Reaction of NOx with Soot Over BaAl2O4

The effect of oxygen concentration on the catalytic reaction of NO_x with soot over BaAl₂O₄ has been studied by Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS). The introduction of O₂ into the NO flow can result in a reactant mixture of NO/NO₂/O₂. Increasing the O₂ concentration from 2 % to 5 % in the NO‐containing flow promotes the formation of NO₂ from the gas phase oxidation of NO. The reactant mixture with high O₂/NO flow, allows for the formation of greater amounts of nitrate species than that with low O₂/NO flow, which further promotes the reaction of soot with NO_x and leads to a high conversion efficiency of NO_x into N₂ and N₂O. In the absence of O₂, N₂O is not observed since the N₂O produced at high temperatures has reacted with soot before it can be detected.     

Performance of an oxygen-permeable membrane reactor for partial oxidation of methane in coke oven gas to syngas

Perovskite-type oxygen-permeable membrane reactors of BaCo_0.7Fe_0.2Nb_0.1O_3−δ packed with Ni-based catalyst had high oxygen permeability and could be used for syngas production by partial oxidation of methane in coke oven gas (COG). The BCFNO membrane itself had a poor catalytic activity to partial oxidation of CH₄ in COG. After the catalyst was packed on the membrane surface, 92% of methane conversion, 90% of H₂ selectivity, 104% of CO selectivity and as high as 15 ml/cm²/min of oxygen permeation flux were obtained at 1148 K. During continuously operating for 550 h at 1148 K, no degradation of performance of the BCFNO membrane reactor was observed under the condition of hydrogen-rich COG. The possible reaction pathways were proposed to be an oxidation-reforming process. The oxidation of H₂ in COG with the surface oxygen on the permeation side improves the oxygen flux through the membrane, and H₂O reacts with CH₄ by reforming reactions to form H₂ and CO.     

CO Oxidation Activity of Ag/TiO2 Catalysts Prepared via Oxalate Co-precipitation

Ag/TiO₂ catalysts with different Ag loadings (2, 4, 7 and 10% (w/w)) have been prepared by means of co-precipitation of Ag- and TiO-oxalates followed by temperature programmed oxidation (TPO). The catalysts were subjected to CO oxidation in a flow reactor at atmospheric pressure and temperatures up to 573 K. Best conversion performance was obtained in a CO/O₂ = 1:1 mixture over 10% Ag/TiO₂ for which the temperature of 50% CO conversion was T ₅₀ = 333 K. The initial reaction rates were determined in a circulation reactor at low conversions and apparent activation energies between 13 and 25 kJ/mol were found for all catalysts. Transmission electron microscopy shows a broad range of nano-sized Ag particles on TiO₂ (nearly pure anatase).     

The kinetics of CO oxidation by adsorbed oxygen on well‐defined gold particles on TiO2(110)

Very tiny Au particles on TiO₂ show excellent activity and selectivity in a number of oxidation reactions. We have studied the vapor deposition of Au onto a TiO₂(110) surface using XPS, LEIS, LEED and TPD and found that we can prepare Au islands with controlled thicknesses from one to several monolayers. In order to understand at the atomic level the unusual catalytic activity in oxidation reactions of this system, we have studied oxygen adsorption on Au/TiO₂(110) as a function of Au island thickness, and have measured the titration of this adsorbed oxygen with CO gas to yield CO₂, as function of Au island thickness, CO pressure and temperature. A hot filament was used to dose gaseous oxygen atoms. TPD results show higher O₂ desorption temperatures (741 K) from ultrathin gold particles on TiO₂(110) than from thicker particles (545 K). This implies that O_a bonds much more strongly to ultrathin islands of Au. Thus from Brønsted relations, ultrathin gold particles should be able to dissociatively adsorb O₂ more readily than thick gold particles. Our studies of the titration reaction of oxygen adatoms with CO (to produce CO₂) show that this reaction is extremely rapid at room temperature, but its rate is slightly slower for the thinnest Au islands. Thus the association reaction (CO_g + O_a → CO_2,g) gets faster as the oxygen adsorption strength decreases, again as expected from Brønsted relations. For islands of about two atomic layers thickness, the rate increases slowly with temperature, with an apparent activation energy of 11.4 ± 2.8 kJ/mol, and shows a first‐order rate in CO pressure and oxygen coverage, similar to bulk Au(110).     

Determination of Mechanism for Soot Oxidation with NO on Potassium Supported Mg‐Al Hydrotalcite Mixed Oxides

Soot oxidation with NO (in the absence of gas phase O₂) on potassium‐supported Mg‐Al hydrotalcite mixed oxides (K/MgAlO) was studied using a temperature‐programmed reaction and in situ FTIR techniques. Nitrite and the ketene group were identified as the reaction intermediates and thus a nitrite‐ketene mechanism was proposed in which surface active oxygen on K sites of K/MgAlO is transferred to soot by NO through nitrites. In the absence of gas phase O₂, soot oxidation with NO at lower temperatures (below 450 °C) is limited by the amount of active oxygen on the K sites. This kind of active oxygen is not reusable but can be replenished in the presence of gas phase O₂.     

Hydrogen production by partial oxidation of methanol over bimetallic Au–Ru/Fe2O3 catalysts

Hydrogen production by partial oxidation of methanol (POM) was investigated over Au–Ru/Fe₂O₃ catalyst, prepared by deposition–precipitation. The activity of Au–Ru/Fe₂O₃ catalyst was compared with bulk Fe₂O₃, Au/Fe₂O₃ and Ru/Fe₂O₃ catalysts. The reaction parameters, such as O₂/CH₃OH molar ratio, calcination temperature and reaction temperature were optimized. The catalysts were characterized by ICP, XRD, TEM and TPR analyses. The catalytic activity towards hydrogen formation is found to be higher over the bimetallic Au–Ru/Fe₂O₃ catalyst compared to the monometallic Au/Fe₂O₃ and Ru/Fe₂O₃ catalysts. Bulk Fe₂O₃ showed negligible activity towards hydrogen formation. The enhanced activity and stability of the bimetallic Au–Ru/Fe₂O₃ catalyst has been explained in terms of strong metal–metal and metal–support interactions. The catalytic activity was found to depend on the partial pressure of oxygen, which also plays an important role in determining the product distribution. The catalytic behavior at various calcination temperatures suggests that chemical state of the support and particle size of Au and Ru plays an important role. The optimum calcination temperature for hydrogen selectivity is 673 K. The catalytic performance at various reaction temperatures, between 433 and 553 K shows that complete consumption of oxygen is observed at 493 K. Methanol conversion increases with rise in temperature and attains 100% at 523 K; hydrogen selectivity also increases with rise in temperature and reaches 92% at 553 K. The overall reactions involved are suggested as consecutive methanol combustion, partial oxidation, steam reforming and decomposition. CO produced by methanol decomposition is subsequently transformed into CO₂ by the water gas shift and CO oxidation reactions.     

Oxidation of methane on a Au + SrFeO3−δ//YSZ electrode characterised by mass spectroscopy and 18O2 pulses

A solid state electrochemical reactor is described in which reactants can be oxidised at high temperatures over an anode/catalyst using co-fed oxygen gas as well as electrochemically supplied oxygen. The setup permits injection of isotopic pulses in the reactant streams. The composition and isotopic distribution in the products are recorded with a quadrupole mass spectrometer. The use of the system is exemplified by oxidation of methane over a Au + SrFeO_3?δ//YSZ anode at 800–850°C. Pulses of ¹⁸O₂ in the stream of co-fed O₂ were used to study the reactivity and products of gaseous oxygen as distinguished from the electrochemically supplied oxygen. The results indicate that the anode used supports oxygen pumping, but is only moderately active for methane oxidation. The products are mainly CO and CO₂. The content of ¹⁸O in the products is low, indicating that methane oxidation takes place by ¹⁶O-rich lattice oxygen. In comparison, a reference Au//YSZ electrode was found to be a slower anode for oxygen pumping, but a better catalyst for the reaction between CH₄ and gaseous O₂, seemingly involving adsorbed oxygen.     

Low-Temperature CO Oxidation over a Pt/Al2O3 Monolith Catalyst Investigated by Step-Response Experiments and Simulations

The ignition–extinction processes for CO oxidation over a Pt/Al₂O₃ monolith catalyst have been studied by flow-reactor experiments and simulations. The study was performed by stepwise changes of the inlet O₂ concentration ranging 0–20 vol% while the CO concentration and the inlet gas temperature were kept constant at 1.0 vol% and 423 K, respectively. Several features observed experimentally are qualitatively simulated with our model: (i) the ignition of the CO oxidation demands 8.0vol% O₂ (ii) corresponding to a catalyst ignition temperature of 433 K (due to the exothermicity of the reaction) and (iii) occurs in the rear part of the monolith where (iv) a local reaction zone is formed which (v) moves towards the reactor inlet as a function of time on stream. Additionally, the simulations show first order kinetic phase transitions, i.e. rapid adsorbate concentration changes, where the catalyst surface is predominantly CO covered in the low reactive state and almost completely oxygen covered in the high reactive state. For the ignition process the kinetic phase transition occurs after the actual catalytic ignition. However, the extinction process is more difficult to simulate dynamically without changing the model parameters for O₂ adsorption in the low and high reactive state, respectively. The influence of diffusion limitations and the role of formation of a less reactive Pt state under oxidising conditions is discussed.     

Catalytic oxidation of hydrogen over Au/TiO2 catalysts

Selective catalytic oxidation of hydrogen in the presence of hydrocarbons was studied in a fixed bed quartz reactor, over 3 wt%Au/TiO₂ and 5 wt%Au/TiO₂ catalysts. This reaction can be utilised in the production of light alkenes via catalytic dehydrogenation, providing in situ heat to the endothermic dehydrogenation reaction and simultaneously removing a fraction of the produced hydrogen. It is important to avoid the non-selective combustion of the hydrocarbons in the mixture. Both 3 wt%Au/TiO₂ and 5 wt%Au/TiO₂ are active for the combustion of hydrogen, but in a gas mixture with propane and oxygen the selectivity is dependent upon the feed ratio of hydrogen and oxygen. At 550 °C, with propane present, no carbon oxides are formed when the H₂:O₂ ratio is four, but at lower ratios some CO₂ and some CO is formed.     

Synthesis gas production in methane conversion using the P|yttria-stabilized zirconia|Ag electrochemical membrane system

The electrochemical membrane reactor of YSZ (yttria-stabilized zirconia) solid electrolyte coated with Pd and Ag as anode and cathode, respectively, has been applied to the partial oxidation of methane to synthesis gas (CO + H₂). The Pd|YSZ|Ag catalytic system has shown a remarkable activity for CO production at 773 K, and the selectivity to CO was quite high (96.3%) under oxygen pumping condition at 5 mA. The H₂ production strongly depended on the oxidation state of the Pd anode surface. Namely, the H₂ treatment of the Pd anode at 773 K for 1 h drastically reduced the rate of H₂ production, while air treatment enhanced the H₂ production rate. From the results of the partial oxidation of CH₄ with molecular oxygen, it is considered that the reaction site of the electrochemical oxidation of CH₄ to synthesis gas was the Pd–YSZ–gas-phase boundary (triple-phase boundary). In addition, it is found that the oxygen species pumped electrochemically over the Pd surface demonstrated similar activity to adsorbed oxygen over Pd, PdO_ad, for the selective oxidation of CH₄ to CO, when the Pd supported on YSZ was used as a fixed-bed catalyst for CH₄ oxidation with the adsorbed oxygen. The difference with respect to the H₂ formation between the electrochemical membrane system and the fixed-bed catalyst reactor results from differences in the average particle size of Pd and the way of the oxygen supply to the Pd surface. This revised version was published online in July 2006 with corrections to the Cover Date.     

The catalytic removal of CO and NO over Co-Pt(Pd, Rh)/γ-Al2O3 catalysts and their structural characterizations

A series of Co-Pt(Pd, Rh)/γ- Al₂O₃ catalysts were prepared by successive wetness impregnation. The catalytic activities for CO oxidation, NO decomposition and NO selective catalytic reduction (SCR) by C₂H₄ over the samples calcined at 500°C and reduced at 450°C were determined. The activities of the samples calcined at 750°C and reduced at 450°C for NO selective catalytic reduction (SCR) by C₂H₄ were also determined. All the samples were characterized by XRD, XPS, XANES, EXAFS, TPR, TPO and TPD techniques. The results of activity measurements show that the presence of noble metals greatly enhances the activity of Co/γ-Al₂O₃ for CO or C₂H₄ oxidation. For NO decomposition, the H₂-reduced Co-Pt(Pd, Rh)/γ- Al₂O₃ catalysts exhibit very high activities during the initial period of catalytic reaction, but with the increase of reaction time, the activities decrease obviously because of the oxidation of surface cobalt phase. For NO selective reduction by C₂H₄, the reduced samples are oxidized more quickly by the excess oxygen in reaction gas. The oxidized samples possess very low activities for NO selective reduction. The results of XRD, XPS and EXAFS indicate that all the cobalt in Co-Pt(Pd, Rh)/γ-Al₂O₃ has been reduced to zero valence during reduction by H₂ at 450°C, but in Co/γ-Al₂O₃ only a part of the cobalt has been reduced to zero valence, the rest exists as CoAl₂O₄-like spinel which is difficult to reduce. For the samples calcined at 750°C, the cobalt exists as CoAl₂O₄ which cannot be reduced by H₂ at 450°C and possesses better activities for NO selective reduction. The results of XANES spectra show that the cobalt in Co/γ- Al₂O₃ has lower coordination symmetry than that in Co-Pt(Pd, Rh)/γ-Al₂O₃. This difference mainly results from the distorting tetrahedrally- coordinated Co²⁺ ions which have lower coordination symmetry than Co⁰ in the catalysts. The coordination number for the Co-Co shell from EXAFS has shown that the cobalt phase is highly dispersed on Co-Pt(Pd, Rh)/γ- Al₂O₃ catalysts. The TPR results indicate that the addition of noble metals to Co/γ- Al₂O₃ makes the TPR peaks shift to lower temperatures, which implies the spillover of hydrogen species from noble metals to cobalt oxides. The oxygen spillover from noble metals to cobalt is also inferred from the shift of TPO peaks to lower temperatures and the increased amount of desorbed oxygen from TPD. For CO oxidation, the Co⁰ is the main active phase. For NO decomposition and selective reduction, Co⁰ is also catalytically active, but it can be oxidized into Co₃O₄ by oxygen at high reaction temperature. This revised version was published online in July 2006 with corrections to the Cover Date.