Oscillatory CO Oxidation Over Pt/Al2O3 Catalysts Studied by In situ XAS and DRIFTS

Fresh and mildly aged Pt/Al₂O₃ model diesel oxidation catalysts with small and large noble metal particle size have been studied during CO oxidation under lean burn reaction conditions to gain more insight into the structure and oscillatory reaction behaviour. The catalytic performance, CO adsorption characteristics using in situ DRIFTS and oxidation state using in situ XAS were correlated. Stable and pronounced oscillations only occurred over the catalyst with smaller particle sizes. Characteristic for this catalyst are low-coordinated surface Pt sites (more corner and edge atoms) which seem to become oxidized at elevated temperature as evidenced by in situ DRIFTS and in situ XAS. In situ XAS further uncovered that the oxidation of the Pt surface starts from the end of the catalyst bed and the oxidation state oscillates like the catalytic activity.     

In situ Raman spectroscopy studies of catalysts

In situ Raman spectroscopy is rapidly becoming a very popular catalyst characterization method because Raman cells are being designed that can combine in situ molecular characterization studies with simultaneous fundamental quantitative kinetic studies. The dynamic nature of catalyst surfaces requires that both sets of information be obtained for a complete fundamental understanding of catalytic phenomena under practical reaction conditions. Several examples are chosen to highlight the capabilities of in situ Raman spectroscopy to problems in heterogeneous catalysis: the structural determination of the number of terminal M=O bonds in surface metal oxide species that are present in supported metal oxide catalysts; structural transformations of the MoO₃/SiO₂ and MoO₃/TiO₂ supported metal oxide catalysts under various environmental conditions, which contrast the markedly different oxide–oxide interactions in these two catalytic systems; the location and relative reactivity of the different surface M–OCH₃ intermediates present during CH₃OH oxidation over V₂O₅/SiO₂ catalysts; the different types of atomic oxygen species present in metallic silver catalysts and their role during CH₃OH oxidation to H₂CO and C₂H₄ epoxidation to C₂H₄O; and information about the oxidized and reduced surface metal oxide species, isolated as well as polymerized species, present in supported metal oxide catalysts during reaction conditions. In summary, in situ Raman spectroscopy is a very powerful catalyst characterization technique because it can provide fundamental molecular‐level information about catalyst surface structure and reactive surface intermediates under practical reaction conditions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Monodisperse Metal Nanoparticle Catalysts: Synthesis, Characterizations, and Molecular Studies Under Reaction Conditions

We aim to develop novel catalysts that exhibit high activity, selectivity and stability under real catalytic conditions. In the recent decades, the fast development of nanoscience and nanotechnology has allowed synthesis of nanoparticles with well-defined size, shape and composition using colloidal methods. Utilization of mesoporous oxide supports effectively prevents the nanoparticles from aggregating at high temperatures and high pressures. Nanoparticles of less than 2?nm sizes were found to show unique activity and selectivity during reactions, which was due to the special surface electronic structure and atomic arrangements that are present at small particle surfaces. While oxide support materials are employed to stabilize metal nanoparticles under working conditions, the supports are also known to strongly interact with the metals through encapsulation, adsorbate spillover, and charge transfer. These factors change the catalytic performance of the metal catalysts as well as the conductivity of oxides. The employment of new in situ techniques, mainly high-pressure scanning tunneling microscopy (HPSTM) and ambient-pressure X-ray photoelectron spectroscopy (APXPS) allows the determination of the surface structure and chemical states under reaction conditions. HPSTM has identified the importance of both adsorbate mobility to catalytic turnovers and the metal substrate reconstruction driven by gaseous reactants such as CO and O₂. APXPS is able to monitor both reacting species at catalyst surfaces and the oxidation state of the catalyst while it is being exposed to gases. The surface composition of bimetallic nanoparticles depends on whether the catalysts are under oxidizing or reducing conditions, which is further correlated with the catalysis by the bimetallic catalytic systems. The product selectivity in multipath reactions correlates with the size and shape of monodisperse metal nanoparticle catalysts in structure sensitive reactions.     

Laser Raman spectroscopy – a powerful tool for in situ studies of catalytic materials

Advantages and limitations of laser Raman spectroscopy (LRS) as an in situ vibrational spectroscopy for the study of catalytic materials and surfaces under working conditions are discussed. Measurements can be carried out at temperatures as high as 1200 K in controlled atmospheres. Modern instrumentation permits time resolutions in the sub‐second regime for materials with high Raman cross sections. Transient studies are thus possible. Several examples are presented of in situ LRS studies including the phase analysis of bismuth molybdate and VPO oxidation catalysts, synergy effects and oxygen exchange in Sb₂O₃/MoO₃ oxide mixtures, intermediates in oxidative coupling of methane, NO decomposition on Ba/MgO catalysts, and transient SERS studies of partial oxidation of methanol on Ag single crystal surfaces and of the reduction of oxide overlayers on electrodeposited Rh layers. This revised version was published online in August 2006 with corrections to the Cover Date.     

Simulating the Complexities of Heterogeneous Catalysis with Model Systems: Case studies of SiO2 Supported Pt-Group Metals

Model catalyst surfaces, consisting of vapor-deposited metal nanoparticles supported on a planar oxide support, can help to link reactivity studies on well-defined single crystal surfaces with those conducted on high-surface area supported catalysts. When coupled with near atmospheric pressure kinetic and spectroscopic techniques, these well-defined model catalyst surfaces represent a useful approach to combine the power of surface analytical techniques with reactivity studies under relevant reaction conditions. Here, we review recent results of our investigations characterizing the physical and catalytic properties of Pt/SiO₂ and Rh/SiO₂ model catalyst surfaces. As will be discussed, the model catalyst approach can help simulate the complexities of catalytic reactions on supported catalysts, helping to provide insights into the role of particle size, particle morphology, and surface adsorbates in dictating the observed structure-sensitivity (activity and selectivity) during reactions at near atmospheric pressures.     

In situ combustion synthesis of structured Cu-Ce-O and Cu-Mn-O catalysts for the production and purification of hydrogen

The combustion method was employed for the in situ synthesis of nanocrystalline Cu-Ce-O and Cu-Mn-O catalyst layers on Al metal foam, without the need of binder or additional calcination steps. Copper-manganese spinel oxides have been proposed as a catalytic system for hydrogen production via methanol steam reforming, while CuO-CeO₂ catalysts have been successfully examined for CO removal from reformed fuels via selective oxidation. In this work, the performance of these catalysts supported on Al metal foam has been investigated in the reactions of methanol reforming and selective CO oxidation. The Cu-Ce-O foam catalyst exhibited similar catalytic performance to the one of the powder catalyst in the selective oxidation of CO. The performance of the Cu-Mn-O foam catalyst in the steam reforming of methanol was inferior to the one of the powder catalyst at intermediate conversion levels, but almost complete conversion of methanol was obtained at the same temperature with both foam and powder catalysts.     

Looking at Heterogeneous Catalysis at Atmospheric Pressure Using Tunnel Vision

This paper addresses the “pressure gap” between traditional surface science experiments and catalysis under practical conditions. We review high-pressure, microflow experiments at elevated temperatures during the catalytic oxidation of CO. Using a specially constructed “Reactor-STM” we simultaneously determine the surface structure of a model catalyst by scanning tunneling microscopy and the reaction kinetics by online mass spectrometry. For both Pt(110) and Pd(100) we find that under O₂-rich conditions surface oxides are formed on the otherwise metallic surfaces. The presence of the oxide is correlated with a superior catalytic activity. Whereas the reaction on the metal surfaces shows traditional Langmuir–Hinshelwood kinetics, the reaction on the oxides follows the Mars-Van Krevelen oxidation–reduction mechanism, as we conclude from the reaction kinetics and the reaction-induced roughening of the surface. We emphasize that in addition to a pressure gap there can also be a temperature gap, requiring experiments to be performed not only at high pressures but also at sufficiently high temperatures.     

Structure, reactivity, and mobility of carbonaceous overlayers during olefin hydrogenation on platinum and rhodium single crystal surfaces

The hydrogenation of olefins (ethylene, propylene, and isobutene) and a cyclic olefin (cyclohexene) has been characterized on platinum and rhodium single crystal surfaces under conditions ranging from ultrahigh vacuum (UHV) to elevated pressures. A carbonaceous overlayer, formed by C–H bond activation, exists on the metal surface during catalytic hydrogenation, and the structure of this overlayer has been characterized using sum frequency generation (SFG) vibrational spectroscopy. The dehydrogenated carbonaceous species are unreactive even in the presence of excess hydrogen, while the intermediates that turnover are weakly bonded to the metal surface. The formation of this carbonaceous overlayer is accompanied by a restructuring of the metal surface. The overlayer is mobile on the surface during hydrogenation, as shown by high pressure scanning tunneling microscopy (HP-STM) results. Coadsorbed CO induces ordered surface structures, and as a consequence poisons the reaction.     

In situ IR,Raman, and UV-Vis DRS spectroscopy of supported vanadium oxide catalysts during methanol oxidation

The application of in situ Raman, IR, and UV-Vis DRS spectroscopies during steady-state methanol oxidation has demonstrated that the molecular structures of surface vanadium oxide species supported on metal oxides are very sensitive to the coordination and H-bonding effects of adsorbed methoxy surface species. Specifically, a decrease in the intensity of spectral bands associated with the fully oxidized surface (V⁵⁺) vanadia active phase occurred in all three studied spectroscopies during methanol oxidation. The terminal V = O (∼1030 cm⁻¹) and bridging V–O–V (∼900–940 cm⁻¹) vibrational bands also shifted toward lower frequency, while the in situ UV-Vis DRS spectra exhibited shifts in the surface V⁵⁺ LMCT band (>25,000 cm⁻¹) to higher edge energies. The magnitude of these distortions correlates with the concentration of adsorbed methoxy intermediates and is most severe at lower temperatures and higher methanol partial pressures, where the surface methoxy concentrations are greatest. Conversely, spectral changes caused by actual reductions in surface vanadia (V⁵⁺) species to reduced phases (V³⁺/V⁴⁺) would have been more severe at higher temperatures. Moreover, the catalyst (vanadia/silica) exhibiting the greatest shift in UV-Vis DRS edge energy did not exhibit any bands from reduced V³⁺/V⁴⁺ phases in the d–d transition region (10,000–30,000 cm⁻¹), even though d–d transitions were detected in vanadia/alumina and vanadia/zirconia catalysts. Therefore, V⁵⁺ spectral signals are generally not representative of the percent vanadia reduction during the methanol oxidation redox cycle, although estimates made from the high temperature, low methoxy surface coverage IR spectra suggest that the catalyst surfaces remain mostly oxidized during steady-state methanol oxidation (15–25% vanadia reduction). Finally, adsorbed surface methoxy intermediate species were easily detected with in situ IR spectroscopy during methanol oxidation in the C–H stretching region (2800–3000 cm⁻¹) for all studied catalysts, the vibrations occurring at different frequencies depending on the specific metal oxide upon which they chemisorb. However, methoxy bands were only found in a few cases using in situ Raman spectroscopy due to the sensitivity of the Raman scattering cross-sections to the specific substrate onto which the surface methoxy species are adsorbed. This revised version was published online in August 2006 with corrections to the Cover Date.     

The kinetics of methanol oxidation on a supported Pd model catalyst: molecular beam and TR-IRAS experiments

Combining a multi-molecular-beam approach and in situ time-resolved IR reflection absorption spectroscopy (TR-IRAS), we investigate the kinetics of methanol oxidation on a well-defined supported Pd model catalyst. The model catalyst is prepared under ultra-high-vacuum (UHV) conditions by Pd deposition onto a well-ordered Al₂O₃ film grown on NiAl (110). In previous studies, this system has been characterized in detail with respect to its geometric and electronic structure and its adsorption properties. Crossing molecular beams of methanol and oxygen on the sample surface, we systematically probe the rate of total methanol oxidation to CO₂ as a function of surface temperature and reactant fluxes. The results are compared with equivalent experiments for the related CO oxidation reaction. Pronounced differences are observed in the kinetics of the two processes, both under steady state and under transient conditions. The dissimilarities can be related to the dehydrogenation step of methanol, which is found to be strongly inhibited at high oxygen coverage. At low oxygen fluxes, CO is formed as the main product of methanol decomposition. Via a three-beam isotope-exchange experiment combined with TR-IRAS, the kinetics of CO formation is investigated as a function of reactant fluxes and surface temperature. Mean-field simulations of the kinetics are performed in a two-step procedure. First, the kinetics of CO oxidation is described, both under steady state and transient conditions. In a second step the microkinetic model is extended to include the formation of CO formed by methanol dehydrogenation. A comparison with the experimental data indicates that the transient kinetics cannot be fully described by a mean-field approach.     

Characterisation of active phases of a copper catalyst for methanol oxidation under reaction conditions: an in situ X-ray absorption spectroscopy study in the soft energy range

The oxidation of methanol over copper is investigated by X-ray absorption spectroscopy in the soft X-ray range under reaction conditions. This in situ method allows the surface electronic structure of the catalyst to be correlated with its performance. The correlation reveals information about the catalytic function of various oxygen species on the surface. Oxide and metastable suboxide species affect in distinctly different ways the multiple action of copper as selective or unselective heterogeneous catalyst.     

Carbon incorporation and deactivation of MgO(0 0 1) supported Pd nanoparticles during CO oxidation

We have investigated the structure and composition of the model catalyst system Pd/MgO(0 0 1) during oxidation, CO reduction and CO oxidation at near atmospheric pressures by a combination of in situ X-ray diffraction and ex situ transmission electron microscopy and spectroscopy techniques. From the in situ X-ray experiments, we find: (a) the Pd nanoparticles with 9 nm in diameter transform into epitaxial PdO above 10⁻¹ mbar O₂ pressure at 570 K, (b) the oxidation process can be reverted by CO exposure, recovering Pd nanoparticles in their initial orientation, and (c) during CO oxidation in a mixture of 50 mbar O₂ and 50 mbar CO a new phase is evolving with lattice constant close to the MgO substrate value, which we assign to expanded Pd nanoparticles forming upon carbon incorporation. Ex situ transmission electron microscopy and different spectroscopy techniques uncover the CO₂ induced growth of a disordered overlayer containing C, Mg and O, which forms during CO oxidation and leads to an overgrowth of Pd nanoparticles thereby deactivating the catalyst.     

Facile Preparation of an Excellent Pt/RuO2‐MnO2/CNTs Nanocatalyst for Anodes of Direct Methanol Fuel Cells

RuO₂‐MnO₂ complex supported by multi‐wall carbon nanotubes (CNTs) was firstly synthesised by the oxidation–reduction precipitation of RuCl₃ and KMnO₄ in one step. Then Pt was loaded onto the obtained RuO₂‐MnO₂/CNTs to fabricate a novel anodic catalyst Pt/RuO₂‐MnO₂/CNTs for direct methanol fuel cells (DMFCs). The catalyst was characterised by transmission electron microscopy (TEM), X‐ray diffraction (XRD), temperature programmed reduction (TPR), X‐ray photoelectron spectroscopy (XPS) and BET specific surface areas (BET). Pt nanoparticles were found uniformly dispersed on the surface of CNTs, with the average diameter of about 2.0 nm. The activities of methanol and CO electrocatalytic oxidation were analysed, and the reaction mechanism of methanol electro‐oxidation on Pt/RuO₂‐MnO₂/CNTs catalyst was discussed. The MnO₂ in the catalysts improves the proton conductivity and electrochemical active surface area (EAS) for the catalysts. RuO₂ improves the CO oxidation activity and Pt dispersion. CNTs provide effectively electron channels. Thus, the Pt/RuO₂‐MnO₂/CNTs catalyst has high utilisation of the noble metal Pt, high CO oxidation ability and excellent methanol electro‐oxidation activity, being an outstanding anode catalyst for DMFC.     

Infrared studies of the reactive adsorption of organic molecules over metal oxides and of the mechanisms of their heterogeneously-catalyzed oxidation

The use of IR spectroscopic techniques to provide information on the mechanisms of catalytic oxidation over metal oxide catalysts is briefly discussed. The data published on studies of the catalytic oxidation of methanol, of linear C₄ hydrocarbons and of methylaromatics over different metal oxide surfaces are reviewed and discussed. Lattice oxygen appears to act as the active oxygen species in both selective and total oxidation. Generalized mechanisms of these complex oxidation reactions are proposed and the catalyst features affecting selectivities in these reactions are discussed. The reaction network is apparently essentially governed by the organic chemistry of the reacting molecule (thus being substantially the same over the different oxide catalysts). However, the catalyst surface governs the rate of the different steps, favoring some paths over others. Thus, selectivity is determined by the catalyst chemical behavior and by the reaction variables (contact time, temperature, gas-phase composition, presence of steam, etc.). IR studies, if performed under conditions where some intermediates are actually detectable and jointly with other techniques, can give valuable information on the catalysis mechanisms. On the other hand, it has been concluded that in situ studies frequently do not give reliable information on reaction mechanisms, because under reaction conditions spectators rather than intermediates are detected.     

Molecular surface studies of adsorption and catalytic reaction on crystal (Pt,Rh) surfaces under high pressure conditions (atmospheres) using sum frequency generation (SFG) – surface vibrational spectroscopy and scanning tunneling microscopy (STM)

Sum frequency generation (SFG) – surface vibrational spectroscopy and the scanning tunneling microscope (STM) have been used to study adsorption and catalyzed surface reactions at high pressures and temperatures using (111) crystal surfaces of platinum and rhodium. The two techniques and the reaction chambers that were constructed to make these studies possible are described. STM and SFG studies of CO at high pressures reveal the high mobility of metal atoms, metal surface reconstruction, ordering in the adsorbed molecular layer, and new binding states for the molecule. CO oxidation occurs at high turnover rates on Pt(111). Different adsorbed species are observed above and below the ignition temperature. Some inhibit the reaction, and others are reaction intermediates since their surface concentration is proportional to the reaction rate. The dehydrogenation of cyclohexene on Pt(100) and Pt(111) proceeds through a 1,3‐cyclohexadiene surface intermediate. The higher dehydrogenation rate is related to the higher surface concentration of these molecules on the (100) crystal face. This revised version was published online in August 2006 with corrections to the Cover Date.     

Raman and infrared spectroscopies as in situ probes of catalytic adsorbate chemistry at electrochemical and related metal–gas interfaces: some perspectives and prospects

Some recent progress in the utilization of infrared and especially Raman spectroscopies for the in situ vibrational characterization of adsorbates at electrochemical interfaces having relevance to catalytic chemistry is briefly outlined, and illustrated by means of examples culled chiefly from our laboratory. The primary factors responsible for the differences as well as similarities in the experimental strategies pursued for metal–solution interfaces as compared with metal surfaces in gas‐phase and ultrahigh vacuum (UHV) environments are discussed, and the distinct virtues of surface‐enhanced Raman scattering (SERS) and infrared reflection‐absorption spectroscopy (IRAS) for scrutinizing the first interfacial type are assessed. The detailed influences of the electrochemical double layer on chemisorbate vibrational properties at ordered metal–solution interfaces as gleaned by in situ IRAS data in comparison with spectra for analogous “model electrochemical” interfaces in UHV are described, and briefly illustrated for carbon monoxide on Pt(111) and Ir(111). The significance of the surface potential φ in controlling chemisorbate properties on metal surfaces in gaseous and UHV as well as electrochemical environments is pointed out. Evidence for the occurrence of “redox pinning” of φ by gaseous species in ambient‐pressure systems is outlined, along with possible catalytic implications. The burgeoning prospects for utilizing SERS as a versatile as well as uniquely sensitive vibrational probe of catalytically significant, especially transition‐metal, interfaces in both electrochemical and gas‐phase environments are delineated. Emphasis is placed on the typically richer vibrational spectra attainable for SERS compared to IRAS, arising from differing surface selection rules along with the greater sensitivity and wider wavenumber ranges accessible to the former method, and exemplified by benzene adsorption on rhodium and palladium electrodes. The anticipated power of SERS for assessing the reactivity as well as identity of adsorbed intermediates in ambient catalytic systems by means of transient in situ spectral measurements is noted, and illustrated briefly for ambient‐pressure methanol oxidation on rhodium. This revised version was published online in August 2006 with corrections to the Cover Date.     

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.     

Molecular mechanisms in partial oxidation of methane on Ir/α-Al2O3: reactivity dependence on catalyst properties and transport phenomena limitations

An in situ DRIFT and mass spectrometric study of catalytic partial oxidation of methane with Ir/-Al₂O₃ has enlightened relationships between the formation of surface metal carbonyl clusters and residence time and temperature conditions. Some cluster species produced during catalytic partial oxidation were also originated during CO₂ hydrogenation and CO₂ reforming experiments described in previous literature. An EXAFS analysis of the catalyst precursor, prepared through a solid-liquid reaction between Ir₄(CO)₁₂ clusters and the reactive surface sites of-Al₂O₃, is also included to discuss clusters structure produced at the surfaces.     

Catalytic Oxidation of Thiol Compounds by Novel Fuel Cell-inspired Co-Porphyrin and Co-Imidazole Catalysts

The catalytic performance of pyrolyzed carbon-supported cobalt-nitrogen donor (CoN₄) catalysts for the oxidation of thiol compounds by dioxygen in aqueous solution was studied. This paper continues our previous line of research, which was inspired by the electrocatalytic reduction of oxygen on pyrolyzed carbon-supported cobalt-porphyrins and related tetra-coordinated nitrogen donor-transition metal complexes (MeN₄, where Me stands for a transition metal atom). Both pyrolyzed carbon-supported Co-imidazole and Co-porphyrin exhibited fast catalytic oxidation of the different thiols. The rate of oxidation of different thiols on the pyrolyzed CoN₄ catalysts was compared to the homogeneous rate of oxidation using 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin Co(II) tetrasodium salt as catalyst. Based on the cobalt content, the heterogeneous catalysts always outperformed the homogeneous one, and at times even exhibited 4,100-fold better catalysis. The dependence of the catalytic rate of oxidation on the preparation temperature was investigated, showing an optimal catalysis at ˜650 °C for the cobalt-imidazole catalyst. The decrease in catalytic performance after heat treatment at elevated temperature was attributed to the formation of cobalt metal acting as a generator of carbon nanotubes.     

A high performance bimetallic catalyst for photo-Fenton oxidation of Orange II over a wide pH range

A bimetallic catalyst supported on MCM-41 was synthesized by chemical vapour deposition and evaluated in the photo-Fenton degradation of Orange II. An in situ oxidation method recently developed in our group was applied to stabilize the metal catalyst supported on MCM-41, achieving an extremely low metal leaching level. This FeCu/MCM-41 shows TOC removals of 93%, 83%, and 78% at pHs of 3, 5.5, and 7, respectively, and maintains its high catalytic activity after 10 consecutive runs. This catalyst successfully overcomes the two problems faced by the heterogeneous photo-Fenton process – metal leaching and narrow working pH range.