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Hydroxyl adsorbates generally appear as transient species during water formation from adsorbed oxygen and hydrogen atoms on a metal surface, a reaction that is part of the catalytic cycle in various important surface-catalyzed reactions such as Fischer-Tropsch synthesis. In the present work, temperature-programmed desorption and in situ synchrotron XPS were used to study water adsorption and OH reactivity on a flat and a stepped cobalt single crystal surface. Water adsorbs intact on the flat Co(0001) surface and desorbs around 160K. Electrons induce dissociation of water and produce OH species at low temperature. Hydroxyl species can also be formed by the reaction between Oad and H2O, but only for high initial oxygen coverage while low coverage Oad appears largely unreactive. Reactive hydrogen species (H atoms) produced by a hot tungsten filament hydrogenate adsorbed oxygen atoms at low temperature already and both OHad and H2O are formed. In all cases, hydroxyl adsorbates react around 190K to form water via 2 OHad -> H2O (g) + Oad associated with an activation barrier of 40-50 kJ mol-1. Water readily dissociates on the step sites exposed by vicinal Co(10-19). A part of the OHad species recombine to form water and oxygen between 200 and 300K, while decomposition of OHad into Oad and Had dominates above 370K. For catalysis, the high reactivity of step sites for water dissociation and the high stability of OHad at these sites implies that O removal from these sites may be difficult and may limit the overall rate of Fischer-Tropsch synthesis on cobalt catalysts.

Photocatalytic conversion of polyols to value-added products is of great interest for the utilization of biomass as a chemical feedstock. Current research focuses on boosting the reaction rate and ...

A novel setup to study the effect of fast, high temperature pulses on catalytic reactions has been developed. The system is based on a microreactor and a generic catalyst support, with an integrated heater that allows for temperature changes up to 230 °C within 20–30 µs and temperature measurements with µs time resolution. Standard microfabrication techniques were used to prepare the catalyst support and the heater element, a 100 nm thick Pt film on a SiO2 terminated Si wafer. Atomic layer deposition (ALD) was used to cover the Pt film with a uniform Al2O3 nanolayer, making sure it solely works as a heater. The Al2O3 terminated wafers could thus be used as a generic platform for the study of supported catalysts under conditions where extremely fast temperature changes occur. ALD was then further used to deposit Pt nanoparticles of various sizes on the Al2O3 surface, serving as model catalysts. CO oxidation was chosen as the test reaction to investigate the concept of temperature pulsed operation and the results show that reaction rates can be accurately controlled and increased significantly by the application of fast, well-controlled temperature pulses, while the power input required to drive the reaction is lower than for steady state operation. Simulations of the reaction kinetics show that reactants desorb from the surface during the fast, high temperature pulses and that the reaction rate enhancement takes place mainly during the relatively slow re-population of the catalyst surface after the temperature pulse.

Cobalt catalysts are used on a commercial scale to produce synthetic fuels via the Fischer-Tropsch synthesis process. As adsorbed hydrogen atoms are involved in many of the elementary reaction steps that occur on the catalyst surface during the reaction it is of interest to study how the structure of the catalyst surface affects the reactivity with di-hydrogen as well as with adsorbed hydrogen atoms. In the present study we use a combination of experimental and theoretical methods to gain insight into how the structure of a cobalt surface affects the H 2 dissociation reaction and the adsorption bond strength of the hydrogen atoms produced in this step. A comparison of the open Co(11–20) and (10–12) surfaces with the flat, close packed Co(0001) surface confirms that undercoordinated Co atoms strongly enhance the rate of H 2 dissociation. At the same time, the lower desorption temperatures found on the more open surfaces indicate that the bond strength of adsorbed hydrogen decreases, in the following order: Co(0001)>Co(10–12)>Co(11–20). DFT calculations confirm this trend, showing that hydrogen adsorbs weaker on the more open surfaces for both low and high coverages. In the context of the Fischer-Tropsch synthesis reaction we propose that step and kink sites are important for efficient H 2 dissociation. After dissociation, the higher hydrogen adsorption strength on terrace sites would promote diffusion away from the dissociation site to flat terraces where they can participate in hydrogenation reactions.

Photocatalytic removal of single volatile organic compounds (VOCs) has been widely investigated; however, photodecomposition of VOC mixtures has been rarely addressed, which may bring safety doubts in indoor air purification due to possible formation of harmful compounds. Here we show that in photocatalytic oxidation of formaldehyde–toluene and formaldehyde–xylene mixtures, the introduction of Pd cocatalyst on TiO2 photocatalyst successfully inhibits the formation of toxic methylphenols, thus promoting the complete mineralization of VOC mixtures into CO2 via the harmless benzaldehyde intermediates. Mechanistic analysis reveals that the loading of Pd cocatalyst effectively removes the inherent surface −OH groups of TiO2, which significantly promotes the activation of O2 into radical dotOH radicals. The Pd cocatalyst also directs the radical dotOH radicals to attack the methyl group instead of the aromatic ring for the formation of benzaldehyde and its further oxidation to CO2, thus yielding a better overall photocatalytic performance.

With the purpose of investigating the reactivity of Fe carbide as an active phase in Fischer-Tropsch catalysis, we studied the formation of a well-defined Fe carbide surface structure resulting from carbon exposure of an Fe film on Au(111). Using two different sources of carbon (C), namely atomic carbon and ethylene gas, we used synchrotron X-ray photoelectron spectroscopy (XPS) to show that a 6 ML Fe film readily converts into a well-defined and thermodynamically stable carbide phase. Scanning tunneling microscopy (STM) showed that the surface of the Fe carbide film is crystalline and is dominated by Fe(110)-like facets perturbed into a (2 × 2) periodic structure due to insertion of C in the interstitial sites. The reactivity of the carbide film toward CO, H 2 , and O 2 was furthermore probed by XPS under vacuum conditions. While the pristine Fe carbide surface was unreactive toward hydrogen gas at 500 K, we interestingly found that CO dissociation from a preadsorbed monolayer of CO takes place already at low temperature. This observation points to an intrinsic activity of the Fe carbide phase where additional carbon originating from CO can be placed in the Fe carbide surface. The catalytic significance of the model catalyst surface presented here is that it can be seen as a stable Fe carbide phase with intrinsically vacant sites for additional C insertion at elevated pressure, and we propose that such additional C may act as active species in C-C coupling reactions during FTS. The studies pave the way for a better understanding of FTS processes on Fe-based catalysts on the basis of a well-defined model surface.

The intercalation process of iron atoms in the interface between graphene and Ru(0001) was systematically investigated both experimentally and computationally. Scanning tunneling microscopy and low-energy electron diffraction indicate that Fe intercalates at 700 K in the graphene/Ru(0001) system, where the graphene monolayer covers the whole substrate. An atomic-level understanding of the process is achieved using dispersion-corrected density functional theory (DFT) calculation. The results indicate that single-Fe atom intercalation causes only minor energy changes in the system. In contrast, the intercalation of a Fe dimer leads to a considerable drop in the total energy, more than twice the energy change in the case of the single-atom intercalation. In a sequential process, intercalation of the second Fe releases more energy, indicating that once the initial intercalation occurs, the subsequent process is thermodynamically more favored than the first. Combining the experimental observations with theoretical insights from the DFT calculations, we provide a clear picture of Fe intercalation into graphene/Ru(0001), which we believe is of interest to the field of interface and materials science and catalysis.

Photocatalytic polyol conversion provides a green approach for the synthesis of value-added products. However, efficient and selective photocatalysts that can prevent unwanted full oxidation are still missing, mostly due to a lack of mechanistic understanding. Here we use ethylene glycol (EG) as model compound to study the reaction pathways in photocatalytic polyol dissociation under aerated conditions using in-situ vibrational spectroscopy coupled with mass spectrometry. On pristine TiO2, the presence of oxygen leads to the formation of formaldehyde via photocatalytic C C bond cleavage, where the removal of photo-generated surface adsorbed proton (Hads+) in the form of water is the rate determining step (RDS). The photo-generated formaldehyde molecules subsequently convert into CO2 via complete oxidation by oxygen, or into paraformaldehyde by polymerization with water. A promotion effect is observed when noble metal (Au, Pt, Ag) nanoparticles (NPs) are used as cocatalysts. While Ag and Au selectively promote the formation of paraformaldehyde, the addition of Pt facilitates the complete oxidation of EG into CO2. By performing the reaction under a low oxygen partial pressure, we rationalize that Ag and Au NPs accelerate the polymerization of formaldehyde by providing water rapidly through direct oxidation of Hads oxidation, whereas Pt NPs supply water indirectly, in a pathway via H2 or formaldehyde oxidation.

Model catalysts consisting of iron particles with similar size deposited on thin-film silica (Fe/SiO2) and on silicon (Fe/Si) were used to study iron carbidization in a CO atmosphere using in situ near-ambient-pressure X-ray photoelectron spectroscopy. Significant differences were observed for CO adsorption, CO dissociation, and iron carbidization when the support was changed from thin-film silica to silicon. Stronger adsorption of CO on Fe/Si than that on Fe/SiO2 was evident from the higher CO equilibrium coverage found at a given temperature in the presence of 1 mbar of CO gas. On thin-film silica, iron starts to carbidize at 150 °C, while the onset of carbidization is at 100 °C on the silicon support. The main reason for the different onset temperature for carbidization is the efficiency of removal of oxygen species after CO dissociation. On thin-film silica, oxygen species formed by CO dissociation block the iron surface until ∼150 °C, when CO2 formation removes surface oxygen. Instead, on the silicon...

The organic linkers of Zeolitic Imidazole Framework-8 (ZIF-8) nanoparticles influence its adsorption of CO2 gases. Solvent Assisted Ligand Exchange (SALE) was successfully used to exchange ∼ 13% of the 2-methylimidazolate linkers of ZIF-8 nanoparticles with 2-mercaptobenzimidazole, 2-aminobenzimidazole or 2-phenylimidazole. With 2-nitroimidiazole ∼67% exchange was achieved, since no bulky benzyl groups were present. During SALE treatment the SOD (sodalite zeolitic framework type) topology of ZIF-8 was maintained, but after the higher exchange percentage of 2-nitroimidazole an frl topology was observed. Up to a two-fold increase in CO2 adsorption was recorded after SALE of ZIF-8 with imidazole derivatives containing NO2 and SH electron withdrawing functional groups. In the case of 2-aminobenzimidazole only a moderate increase in CO2 adsorption was observed.

The influence of different iron carbides on the activity and selectivity of iron-based Fischer–Tropsch catalysts has been studied. Different iron carbide phases are obtained by the pretreatment of a binary Fe/SiO2 model catalyst (prepared by coprecipitation method) to different gas atmospheres (syngas, CO, or H2). The phase structures, compositions, and particle sizes of the catalysts are characterized systematically by XRD, XAFS, MES, and TEM. It is found that in the syngas-treated catalyst only χ-Fe5C2 carbide is formed. In the CO-treated catalyst, Fe7C3 and χ-Fe5C2 with a bimodal particle size distribution are formed, while the H2-treated catalyst exhibits the bimodal size distributed e-Fe2C and χ-Fe5C2 after a Fischer–Tropsch synthesis (FTS) reaction. The intrinsic FTS activity is calculated and assigned to each corresponding iron carbide based on the phase composition and the particle size. It is identified that Fe7C3 has the highest intrinsic activity (TOF = 4.59 × 10–2 s–1) among the three candidat...

The study of magnetic perovskite oxides has led to novel and very active compounds for O2 generation and other energy applications. Focusing on three different case studies, we summarise the bulk electronic and magnetic properties that initially serve to classify active perovskite catalysts for the oxygen evolution reaction (OER). Ab-initio calculations centred on the orbital physics of the electrons in the d-shell provide a unique insight into the complex interplay between spin dependent interactions versus selectivity and OER reactivity that occurs in these transition-metal oxides. We analyse how the spin, orbital and lattice degrees of freedom establish rational design principles for OER. We observe that itinerant magnetism serves as an indicator for highly active oxygen electro-catalysts. Optimum active sites individually have a net magnetic moment, giving rise to exchange interactions which are collectively ferromagnetic, indicative of spin dependent transport. In particular, optimum active sites for OER need to possess sufficient empty orthogonal orbitals, oriented towards the ligands, to preserve an incoming spin aligned electron flow. Calculations from first principles open up the possibility of anticipating materials with improved electro-catalytic properties, based on orbital engineering.

Preferential oxidation of CO in H2 was studied by in situ ultraviolet–visible (UV–Vis) and mass spectrometry on flat model Cu and Cu/CeOx catalysts. The experimental findings were interpreted and compared with the results from density functional theory (DFT) calculations of the adsorption and activation energies for the essential reaction steps on Cu(1 1 1). It was found that oxidation of CO preferentially takes place on Cu(0) and that no significant H2 oxidation took place under any of the investigated conditions. The presence of CeOx accelerates Cu(0)-oxidation which leads to catalyst deactivation. In contrast, CeOx promotes the CO oxidation rate on catalysts that were already oxidized to CuOx. The coexistence of CO and H2 is important to sustain the stability of metallic Cu and thereby a high rate of CO2 formation. In pure CO/O2 gas, the metallic phase can only be maintained as long as full O2 conversion is reached. In pure H2/O2, Cu is always partly but never fully oxidized, suggesting that a passivating surface layer is formed. This is also the case for H2 rich gas mixtures with small amounts of CO and O2. The most active surface termination, Cu(0), can therefore not be maintained under the industrially most interesting reaction condition where full conversion of trace amounts of CO in H2 is required. DFT calculations predict that the dissociative H2 adsorption is a key limiting step for hydrogen oxidation on the Cu(1 1 1) surface, especially when the low sticking coefficient is taken into account.

The present article aims to show how work function measurements (WF) can be applied in the study of elementary surface reaction steps on metallic single crystal surfaces. The work function itself can in many cases not be interpreted directly, as it lacks direct information on structural and chemical nature of the surface and adsorbates, but it can be a powerful tool when used together with other surface science techniques which provide information on the chemical nature of the adsorbed species. We here, illustrate the usefulness of work function measurements using Rh(100) as our model catalyst. The examples presented include work function measurements during adsorption, surface reaction, and desorption of a variety of molecules relevant for heterogeneous catalysis. Surface coverage of adsorbates, isosteric heat of adsorption, and kinetic parameters for desorption, desorption/decomposition temperatures of surface species, different reaction regimes were determined by WF with the aid of other surface science techniques.

We report on the structure and reactivity of the Co-Si polycrystalline surfaces that form at room temperature (RT). Scanning tunneling microscopy (STM) was used to examine the surface morphology while X-ray photoelectron spectroscopy (XPS) was used to detect the chemical states of cobalt and silicon as a function of cobalt coverage. Moreover, XPS measurements after exposing the Co-Si(1 1 1) samples to CO gas provide information about CO adsorption and dissociation. When 5 ML, an indication that Co-rich silicides and metallic Co present. The CO adsorption capacity increases with cobalt dose up to 30 ML after which it levels off, an indication that metallic cobalt sites are dominantly exposed on the surface. Furthermore, a closed metal film is formed for 200 ML dose. Some dissociation of CO was observed during heating of the CO-covered samples for Co doses ≥30 ML.

Polyol conversion to value-added products is of great interest for the bio-diesel industry. Photocatalytic oxidation processes may offer a green approach for polyol conversion; however the lack of comprehensive mechanistic understanding from an interdisciplinary perspective limits or even misleads the design of highly selective and efficient photocatalysts for such process. Here we have studied the photocatalytic polyol conversion on pristine TiO 2 and metal (Au, Pd, and Pt) nanoparticles (NPs) decorated TiO 2 using ethylene glycol (EG) as the model compound. We have developed a mechanistic picture at molecular level by coupling in-situ surface science study on rutile (110) surface with in-situ vibrational-mass spectrometry study on TiO 2 nanopowders. The C C bond cleavage was found to be the only pathway in EG photo-conversion under deaerated conditions, leading to the formation of formaldehyde and hydrogen. We rationalized that the desorption of the surface adsorbed H (H ads ) to be the rate determining step (RDS), making pristine TiO 2 a poor photocatalyst that only catalyze the EG conversion at very low surface coverages. The addition of metal NPs on TiO 2 surface promotes the desorption of H ads significantly, thus leading to an enhanced C C bond cleavage performance at higher surface coverages that is more applicable.

Manganese oxides with a half-metallic ground state are particularly active for oxygen reduction reactions (ORR). La0.67Sr0.33MnO3 (LSMO) perovskite is the archetypal example for compositions with a Curie temperature (TC) above room temperature, and with a high intrinsic activity for the partial reduction of triplet state O2. The ferromagnetic (FM) character of the superexchange interactions in LSMO facilitates both the charge and spin transport below 370 K. Other than the enhanced electronic conductivity, the reduced spin entropy seems to be of relevance in oxygen catalysis, as the magnetic ordering extends to the surface. The sign of the exchange interactions determines the adsorption of the triplet oxygen molecule with its spin antiparallel to the FM catalysts. On the basis of transition state theory, we report that on LSMO the hindrance due to the magnetic entropy for the initial reduction of O2 by two antiparallel electrons to diamagnetic intermediates (like H2O2) is minimum. On the other hand, the additional reduction of H2O2 to H2O, diamagnetic steps, prefers paramagnetic catalysts, with higher magnetic entropy like La0.4Sr0.6MnO3, to avoid spin accumulation.

Structural evolution of iron nanoparticles involving the formation and growth of iron carbide nuclei in the iron nanoparticle was directly visualized at the atomic level, using environmental transmission electron microscopy (TEM) under reactive conditions mimicking Fischer-Tropsch synthesis. Formation of the iron carbide nuclei and surface reconstruction of the iron nanoparticle play an essential role in carburization of the iron nanoparticle and consequent formation of Fe5C2. Identification of carbide and oxide intermediates evidenced by high-resolution TEM images, electron diffraction patterns and electron energy-loss spectra provides a detailed picture from initial activation to final degradation of iron under synthesis gas. (Chemical Equation Presented).

Monomeric forms of carbon play a central role in the synthesis of long chain hydrocarbons via the Fischer–Tropsch synthesis (FTS). We explored the chemistry of C1Hxad species on the close-packed surface of cobalt. Our findings on this simple model catalyst highlight the important role of surface hydrogen and vacant sites for product selectivity. We furthermore find that COad affects hydrogen in multiple ways. It limits the adsorption capacity for Had, lowers its adsorption energy and inhibits dissociative H2 adsorption. We discuss how these findings, extrapolated to pressures and temperatures used in applied FTS, can provide insights into the correlation between partial pressure of reactants and product selectivity. By combining the C1Hx stability differences found in the present work with literature reports of the reactivity of C1Hx species measured by steady state isotope transient kinetic analysis, we aim to shed light on the nature of the atomic carbon reservoir found in these studies.

A series of new ferrocene- and ruthenocene-containing iridium(III) heteroleptic complexes of the type [(ppy)2Ir(RCOCHCOR&prime, )], with ppy = 2-pyridylphenyl, R = Fc = FeII(&eta, 5-C5H4)(&eta, 5-C5H5) and R&prime, = CH3 (1) or Fc (2), as well as R = Rc = RuII(&eta, = CH3 (3), Rc (4) or Fc (5) was synthesized via the reaction of appropriate metallocene-containing &beta, diketonato ligands with [(ppy)2(-Cl)Ir]2. The single crystal structure of 3 (monoclinic, P21/n, Z = 4) is described. Complexes 1&ndash, 5 absorb light strongly in the region 280&minus, 480 nm the metallocenyl -diketonato substituents quench phosphorescence in 1&ndash, 5. Cyclic and square wave voltammetric studies in CH2Cl2/[N(nBu)4][B(C6F5)4] allowed observation of a reversible IrIII/IV redox couple as well as well-resolved ferrocenyl (Fc) and ruthenocenyl (Rc) one-electron transfer steps in 1&minus, 5. The sequence of redox events is in the order Fc oxidation, then IrIII oxidation and finally ruthenocene oxidation, all in one-electron transfer steps. Generation of IrIV quenched phosphorescence in 6, [(ppy)2Ir(H3CCOCHCOCH3)]. This study made it possible to predict the IrIII/IV formal reduction potential from Gordy scale group electronegativities, &chi, R and/or &Sigma, &chi, R&prime, of -diketonato pendent side groups as well as from DFT-calculated energies of the highest occupied molecular orbital of the species involved in the IrIII/IV oxidation at a 98 % accuracy level.

Cobalt is an important catalyst for Fischer–Tropsch synthesis, and it can form cobalt carbide under syngas (CO + H2) reaction conditions, especially in CO-rich mixtures. As cobalt carbide has been credited as a promoter which brings about significant selectivity changes in CO hydrogenation, we are interested in studying it using a surface science approach, to understand its interaction with important reaction intermediates. In the present study, we use a NiAl(110) surface to produce a flat alumina film and prepare cobalt and cobalt carbide thereon. We find that cobalt is thermally stable up to 800 K on alumina/NiAl(110). Different preparation temperatures result in different morphologies of the surface. Cobalt carbide is obtained by evaporating cobalt in an C2H4 environment, as proved by the appearance of a C 1s peak at 283.3 eV of carbidic carbon and at 286.2 eV of chemisorbed CO on cobalt carbide in the XPS spectra. Large cobalt carbide crystals with a typical size of 100 nm × 50 nm are revealed by STM. The results show that cobalt and cobalt carbide on alumina/NiAl(110) can serve as suitable model systems for studying structures, adsorption and catalytic properties.

Water electrolysis is the most promising method for efficient production of high purity hydrogen (and oxygen), while the required power input for the electrolysis process can be provided by renewable sources (e.g. solar or wind). The thus produced hydrogen can be used either directly as a fuel or as a reducing agent in chemical processes, such as in Fischer–Tropsch synthesis. Water splitting can be realized both at low temperatures (typically below 100 °C) and at high temperatures (steam water electrolysis at 500–1000 °C), while different ionic agents can be electrochemically transferred during the electrolysis process (OH−, H+, O2−). Singular requirements apply in each of the electrolysis technologies (alkaline, polymer electrolyte membrane and solid oxide electrolysis) for ensuring high electrocatalytic activity and long-term stability. The aim of the present article is to provide a brief overview on the effect of the nature and structure of the catalyst–electrode materials on the electrolyzer's performance. Past findings and recent progress in the development of efficient anode and cathode materials appropriate for large-scale water electrolysis are presented. The current trends, limitations and perspectives for future developments are summarized for the diverse electrolysis technologies of water splitting, while the case of CO2/H2O co-electrolysis (for synthesis gas production) is also discussed.

The present article summarizes experimental findings of the interaction of CO with single crystal surfaces of cobalt. We first provide a quantitative study of non-dissociative CO adsorption on Co(0001) and establish a quantitative correlation between θCO and adsorption site occupation. In light of these findings we revisit the structure of previously reported ordered CO/Co(0001) adsorbate layers. Measurements of the CO coverage at equilibrium conditions are used to derive a phase diagram for CO on Co(0001). For low temperature Fischer-Tropsch synthesis conditions the CO coverage is predicted to be ≈0.5 ML, a value that hardly changes with pCO. The CO desorption temperature found in temperature programmed desorption is practically structure-independent, despite structure-dependent heats of adsorption reported in the literature. This mismatch is attributed to a structure-dependent pre-exponential factor for desorption. IR spectra reported throughout this study provide a reference point for IR studies on cobalt catalysts. Results for CO adsorbed on flat and defect-rich Co surfaces as well as particular, CO adsorbed on top sites, and in addition affect the distribution of COad over the various possible adsorption sites.

The current paper presents a mechanistic view on important steps in the Fischer-Tropsch synthesis on cobalt catalysts, inspired by surface science studies. By revisiting the relation between activity and selectivity that results from the ASF assumption we highlight that knowledge about the number of growing chains as well as their residence time (∼growth rate) is of crucial importance to sketch a physically realistic scenario for FTS. This motivates further investigations into the microscopic scenario for FTS chain growth on fcc cobalt nanoparticles, by looking into the reaction mechanism in relation to surface structure and by determining the activation energies for key elementary steps. Such studies indicate that the modest activity of Co FTS catalysts might very well be attributable to the difficulty to remove chemisorbed oxygen from the metallic surface, rather than to dissociation of CO, which was found to proceed readily at step edge sites. Chain growth is envisaged to take place on the close-packed surfaces, with chain initiation via CH + CH to form acetylene, followed by hydrogenation to form ethylidyne, C CH3, a reaction that is shown to be promoted by co-adsorbed CO. Ethylidyne then couples with CH to form propyne, HC C CH3, etc. We propose that a fairly large number of surface sites is involved in the growth of a single chain. In such a “growth ensemble” multiple active step sites produce CHx monomer species that spill over onto the same close-packed coupling terrace, where one or only a few chains grow at the same time. In such a scenario diffusion of hydrocarbonaceous surface species is an essential step in the overall reaction sequence. We explore which factors need to be taken into account when considering of CxHy species under realistic reaction conditions. In addition, we note that the coupling reaction itself, via CH + C CnH2n+1, is a source of growing chain mobility.

We have performed an in-depth ab initio study of the magnetic structure within the most active perovskites for the oxygen evolution reaction. In all cases, the ground state exhibits an extended antiferromagnetic coupling in the unit cell. Layered antiparallel alignment of the magnetic moments appears to be related to their electrocatalytic activity. All the perovskites calculated within this paper show space-separated charge-transport channels depending on the spin orientation. Comparing the electronic structures with the reported activities, we find a direct correlation between the magnetic accumulation on the spin channels in the bulk material and the catalytic activity. We discuss the possible implications of such observations in terms of magnetic interactions. During oxygen evolution in water electrolysis, reactants and products do not preserve spin. For triplet state oxygen to evolve, the catalyst at the anode can speed up the reaction if it is able to balance the magnetism of the oxygen molecule by extracting electrons with an opposite magnetic moment, conserving the overall spin.

Dissociation of CO on a Co(0001) surface is explored in the context of Fischer-Tropsch synthesis on cobalt catalysts. Experiments show that CO dissociation can occur on defect sites around 330 K, with an estimated barrier between 90 and 104 kJ mol- 1. Despite the ease of CO dissociation on defect sites, extensive carbon deposition onto the cobalt surface up to 0.33 ML requires a combination of high surface temperature and a relatively high CO pressure. Experimental data on the CO oxidation reaction indicate a high reaction barrier for the CO + O reaction, and it is argued that, due to the rather strong Co-O bond, (i) oxygen removal is the rate-limiting step during surface carbidization and (ii) in the context of Fischer-Tropsch synthesis, removal of surface oxygen rather than CO bond scission might be limiting the overall reaction rate.

Although Fischer-Tropsch synthesis (FTS) was discovered more than 90 years ago, it remains a fascinating topic, having relevance from both an industrial and academic perspective. FTS based on cobalt and iron catalysts was studied in depth during an extensive 15-year collaboration between Eindhoven University of Technology, The Netherlands, and Sasol, South Africa. The primary objective of the collaboration was to obtain fundamental information that could assist in understanding practical issues in FTS over iron and cobalt catalysts. For iron-based catalysts, industrial slurry reactor work was combined with SSITKA and DFT modeling, resulting in improved clarity, with respect to the kinetics and mechanisms of FTS. This knowledge is important, with respect to designing large-scale industrial processes. In the case of cobalt-based FTS research, the combination of commercially relevant supported cobalt catalysts with sophisticated characterization tools, as well as the application of flat model catalyst systems, has led to significantly improved knowledge of deactivation mechanisms. This improved knowledge has assisted in the understanding of new catalysts systems and regeneration processes. Finally, the success of the collaboration has been due to many factors. It has been beneficial to both parties to have had a long-term collaboration, in which important fundamental catalysis topics were investigated that often took a substantial period of time. The access to high-quality modeling and characterization tools and fundamental understanding, as well as industrially relevant supported catalysts operated under realistic conditions, has proved vital in our contribution toward the advancement of the science and technology of FTS.

Alcohol electrolysis using polymeric membrane electrolytes is a promising route for storing excess renewable energy in hydrogen, alternative to the thermodynamically limited water electrolysis. By properly choosing the ionic agent (i.e. H+ or OH−) and the catalyst support, and by tuning the catalyst structure, we developed membrane-electrode-assemblies which are suitable for cost-effective and efficient alcohol electrolysis. Novel porous electrodes were prepared by Atomic Layer Deposition (ALD) of Pt on a TiO2-Ti web of microfibers and were interfaced to polymeric membranes with either H+ or OH− conductivity. Our results suggest that alcohol electrolysis is more efficient using OH− conducting membranes under appropriate operation conditions (high pH in anolyte solution). ALD enables better catalyst utilization while it appears that the TiO2-Ti substrate is an ideal alternative to the conventional carbon-based diffusion layers, due to its open structure. Overall, by using our developmental anodes instead of commercial porous electrodes, the performance of the alcohol electrolyser (normalized per mass of Pt) can be increased up to ∼30 times.

In order to better understand intramolecular communication between molecular fragments, a series of ferrocene-functionalized β-diketonato manganese(III) complexes, [Mn(FcCOCHCOR)3] with R = CF3, 1, CH3, 2, Ph = C6H5, 3, and Fc = FeII(η5-C5H4)(η5-C5H5), 4, the mixed ligand β-diketonato complex [Mn(FcCOCHCOFc)2(FcCOCHCOCH3)], 5, as well as the acac complex [Mn(CH3COCHCOCH3)3], 6, were subjected to an electrochemical and X-ray photoelectron spectroscopy (XPS) study. The ferrocenyl (FeII) and MnIII redox potentials, E°′, and photoelectron lines were sufficiently resolved in each complex to demonstrate a linear correlation between E°′ and group electronegativities of ligand R groups, R, or ςR, as well as with binding energies of both the Fe 2p3/2 and Mn 2p3/2 photoelectron lines. These relationships are consistent with effective communication between molecular fragments of 1-5. From these relationships, prediction of Mn and Fe core electron binding energies in [Mn(R1COCHCOR2)3] complexes from known manganese and/or ferrocenyl redox potentials are, therefore, now possible. Ligand infrared carbonyl stretching frequencies were successfully related to binding energy as a measure of the energy required for inner-sphere reorganization. In particular it became possible to explain why, upon electrochemical oxidation or photoionization, the ferrocenyl FeII inner-shell of 1-5 needs more energy in complexes with ligands bearing electron-withdrawing (CF3) groups than in ligands bearing electron-donating groups such as ferrocenyl. The XPS determined entity Iratio (the ratio between the intensities of the satellite and main metal 2p3/2 photoelectron lines) is an indication not only of the amount of charge transferred, but also of the degree of inner-sphere reorganization. Just as for binding energy, the quantity Iratio was also found to be related to the energy requirements for the inner-sphere reorganization depicted by the vibrational frequency, vco.

Oxygen adsorption and removal on flat and defective Co(0001) surfaces have been investigated experimentally using scanning tunneling microscopy, temperature-programmed and isothermal reduction, synchrotron X-ray photoemission spectroscopy, and work function measurements under ultrahigh vacuum conditions and H2/CO pressures in the 10-5 mbar regime. Exposure of the Co(0001) to O2(g) at 250 K leads to the formation of p(2 × 2) islands with a local coverage of 0.25 ML. Oxygen adsorption continues beyond 0.25 ML, reaching a saturation point of ∼0.39 ML Oad, without forming cobalt oxide. Chemisorbed oxygen adlayers can be reduced on both flat and defective Co(0001) surfaces by heating in the presence of ∼2.3 × 10-5 mbar H2(g). The onset of the oxygen removal as water during temperature-programmed reduction experiments (1 K s-1) is at around 450 K on flat Co(0001) and 550 K on defective Co(0001). By evaluation of isothermal reduction experiments using a kinetic model, the activation energy for water formation is found to be ∼129 ± 7 kJ/mol for the flat Co(0001) and ∼136 ± 7 kJ/mol for the defective Co(0001). Adsorbed oxygen cannot be reduced by CO(g) on flat and defective Co(0001) using CO pressures up to 1 × 10-5 mbar and temperatures up to 630 K.

The adsorption and decomposition of ethanol on Rh(100) was studied as a model reaction to understand the role of C-OH functionalities in the surface chemistry of biomass-derived molecules. A combination of experimental surface science and computational techniques was used: (i) temperature programmed reaction spectroscopy (TPRS), reflection absorption infrared spectroscopy (RAIRS), work function measurements (Kelvin Probe-KP), and density functional theory (DFT). Ethanol produces ethoxy (CH3CH2O) species via O-H bond breaking upon adsorption at 100 K. Ethoxy decomposition proceeds differently depending on the surface coverage. At low coverage, the decomposition of ethoxy species occurs via β-C-H cleavage, which leads to an oxometallacycle (OMC) intermediate. Decomposition of the OMC scissions (at 180-320 K) ultimately produces CO, H2 and surface carbon. At high coverage, along with the pathway observed in the low coverage case, a second pathway occurs around 140-200 K, which produces an acetaldehyde intermediate via α-C-H cleavage. Further decomposition of acetaldehyde produces CH4, CO, H2 and surface carbon. However, even at high coverage this is a minor pathway, and methane selectivity is 10% at saturation coverage. The results suggests that biomass-derived oxygenates, which contain an alkyl group, react on the Rh(100) surface to produce synthesis gas (CO and H2), surface carbon and small hydrocarbons due to the high dehydrogenation and C-C bond scission activity of Rh(100).

Oxygenated compounds have previously been detected on spent Co/Al2O3FTS catalyst and have also been proposed to be precursors for carbon formation. Build-up of polymeric carbon on the catalyst during Fischer-Tropsch synthesis (FTS) can negatively influence activity over an extended reaction time. Adsorbed oxygenates detected on spent Co/γ-Al2O3FTS catalyst are deduced to be located on the γ-Al2O3support using attenuated total reflectance infrared spectroscopy (ATR-IR). The formation of a metal-carboxylate compound is not detected (ATR-IR) and deduced to be unlikely since acetic acid decomposes at low temperature on a Co metal surface (single crystal Co(0 0 0 1) experiments under ultra-high vacuum conditions). Acetic acid undergoes dissociative adsorption on the γ-Al2O3(1 1 0) and (1 0 0) surfaces (DFT), forming an acetate species. Acetic acid vapor, contacted with reduced Co/Pt/Al2O3catalyst at model FTS conditions (i.e. 1 bar(a)H2/CO:2/1 at 230 °C), results in predominantly atomic carbon deposition on the catalyst. Co-feeding of excess acetic acid during FTS does not enhance Co/Pt/Al2O3catalyst deactivation nor does it significantly impact methane selectivity. Therefore, carboxylic acids can cause atomic carbon formation on Co/γ-Al2O3catalyst during FTS and result in strongly adsorbed carboxylates on γ-Al2O3support, but these factors do not significantly impact catalyst deactivation.

This study investigated the operation of gold as a potential substitute for the platinum promoter in the Co/Al2O3Fischer–Tropsch catalyst. Au–Co/Al2O3was tested in conjunction with a model Hybrid Au–Co sample (comprised of a mechanical mixture of Au/Al2O3 + Co/Al2O3) to investigate hydrogen spillover which has been demonstrated to play a vital role in the reduction promotion mechanism. TPR, TGA and in situ XRD provided evidence to support the improved reducibility of supported cobalt oxide crystallites in Au–Co/Al2O3. However, no improvement in the reducibility of the Hybrid Au–Co catalyst was observed, in contrast to previous studies on noble metal reduction promoters. It was hypothesized that even though gold-to-cobalt spillover occurred during reduction in Au–Co/Al2O3, the great separation between the gold and cobalt crystallites, combined with gold's much lower affinity for hydrogen activation adversely affected the efficiency of the spillover process in the hybrid sample. Nevertheless, Au–Co/Al2O3had an improved mass-based activity, and a turnover frequency comparable to a platinum promoted sample, which highlighted the potential of gold as a reduction promoter for Co/Al2O3catalysts.

Catalyst deactivation is an important topic for industrial catalyst development. Sintering of small cobalt crystallites is one of the deactivation mechanisms of cobalt-based Fischer–Tropsch synthesis (FTS) catalysts. This study investigates the mechanism of cobalt sintering at low-conversion FTS conditions. A Co/SiO2/Si(1 0 0) model catalyst is exposed to 20 bar dry synthesis gas (H2/CO: 2/1) at 230 °C for 10 h. Cobalt nanoparticles were characterized before and after treatment using transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). TEM images of identical locations on the model catalyst showed a loss of some small crystallites and decrease in size of some crystallites. Sintering is dominated by an Ostwald ripening mechanism using our model catalyst under the present conditions. Complementary XPS measurements confirm the loss of Co dispersion. Therefore, the loss of small Co nanoparticles causes a rapid loss of metal surface area when exposed to model FTS conditions.

Formation of CH x (O) monomers and C 1 products (CH 4 , CH 2 O, and CH 3 OH) on C-terminated χ-Fe 5 C 2 (0 0 1) (Hagg carbide) surfaces of different carbon contents was investigated using periodic DFT simulations. Methane (CH 4 ) as well as monomer (CH x ) formation follows a Mars–van Krevelen-like cycle starting with the hydrogenation of surface carbidic carbon, which is regenerated by subsequent CO dissociation, while oxygen is removed as H 2 O. In cases where surface carbon is readily available, the apparent barrier for CH 4 formation was found to be ∼95 kJ/mol. However, different rate-determining steps show that different propagation mechanisms may be possible for actual chain growth, depending on the carbon content of the surface. Hydrogen addition to CO forms formyl (HCO), which is a precursor for both H-assisted CO activation and oxygenate formation. Further hydrogenation of HCO yields adsorbed formaldehyde and methoxy, rather than hydroxymethyl (HCOH) that would give C–O bond splitting. Full hydrogenation to gas-phase methanol faces a high barrier, suggesting that CH x O species may be involved in higher oxygenate formation in a full Fischer–Tropsch mechanism or that the C–O bond does not break until the CHO fragment has been incorporated in a C 2 species, a route for which precedents are available in the literature.

A systematic study was carried out to investigate the response of monodisperse supported Fe and FeMn nanoparticles to treatments in O2, H2 and H2/CO at temperatures between 270 and 400°C. Uniform size (7–14 nm), Fe and mixed FeMn nanoparticles were synthesised by applying thermal decomposition of Fe- and Mn-oleate complexes in a high boiling point solvent. By combining X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) analysis, the phase composition and morphology of the model catalysts were studied. Energy-dispersive X-ray analysis shows that the catalyst particles have the expected composition of Fe and Mn. Well-defined crystallite phases [maghemite (γ-Fe2O3) and mixed FeMn-spinel] were observed after calcination at 350°C in Ar/O2 using XPS analysis. Upon subsequent treatments in H2 and H2/CO the crystal phases changed from maghemite (γ-Fe2O3) to metallic Fe, Fe carbide and graphitic C. Using Mn as a promoter influences the nanoparti...

The reduction of Cu-promoted Fe model catalysts was investigated using X-ray photoelectron spectroscopy (XPS) and indirect nanoplasmonic sensing (INPS). The catalysts were prepared by evaporation of 1 nm thick Fe particle films onto quartz wafers, followed by deposition of 0, 0.2, or 0.02 nm of Cu (i.e., 0, 2, or 19 wt %) as a promoter. For the XPS measurements, a reaction cell with in vacuo transfer to the measurement chamber was used. The catalysts were first oxidized at 400 degrees C in Ar/O-2, achieving fully oxidized Fe2O3 and CuO. Subsequently, the samples were heated to temperatures between 100 and 400 degrees C in pure H-2, and the resulting change in oxidation state was measured. Fe2O3 was found to be reduced to Fe3O4 at 225 degrees C and to a mixed state of FeO and metallic Fe at 275 degrees C. The corresponding temperatures for Cu-promoted Fe catalysts were 100 degrees C lower. In the absence of FeOx, Cu was reduced to metallic Cu, via Cu2O, at temperatures between 125 and 175 degrees C. In addition to the XPS measurements, INPS was used to obtain more detailed insight into the reduction process, both in pure H-2 and in wet H-2, containing 0.8 vol % H2O. These in situ experiments show that the presence of H2O increases the reduction temperature by 36 degrees C or more, depending on the amount of Cu promoter used, where the catalyst with the industrially relevant 2 wt % promoter material exhibits the smallest increase. The INPS measurements also demonstrate that increasing the amount of Cu promoter decreases the Fe2O3 reduction temperature, in both dry and wet H-2. Together, XPS and INPS offer a powerful combination for monitoring the oxidation state of flat model catalysts during pretreatments, an approach that can equally well be used during catalytic reaction conditions.

Sintering of nanoparticles is an important contributor to loss of activity in heterogeneous catalysts, such as those used for controlling harmful emissions from automobiles. But mechanistic details, such as the rates of atom emission or the nature of the mobile species, remain poorly understood. Herein we report a novel approach that allows direct measurement of atom emission from nanoparticles. We use model catalyst samples and a novel reactor that allows the same region of the sample to be observed after short-term heat treatments (seconds) under conditions relevant to diesel oxidation catalysts (DOCs). Monometallic Pd is very stable and does not sinter when heated in air (T ⩽ 800 °C). Pt sinters readily in air, and at high temperatures (⩾800 °C) mobile Pt species emitted to the vapor phase cause the formation of large, faceted particles. In Pt–Pd nanoparticles, Pd slows the rate of emission of atoms to the vapor phase due to the formation of an alloy. However, the role of Pd in Pt DOCs in air is quite complex: at low temperatures, Pt enhances the rate of Pd sintering (which otherwise would be stable as an oxide), while at higher temperature Pd helps to slow the rate of Pt sintering. DFT calculations show that the barrier for atom emission to the vapor phase is much greater than the barrier for emitting atoms to the support. Hence, vapor-phase transport becomes significant only at high temperatures while diffusion of adatoms on the support dominates at lower temperatures.

The activation processes of [CuII(bdmpza)2] in the water oxidation reaction were investigated using cyclic voltammetry and chronoamperometry. Two different paths wherein CuO is formed were distinguished. [CuII(bdmpza)2] can be oxidized at high potentials to form CuO, which was observed by a slight increase in catalytic current over time. When [CuII(bdmpza)2] is initially reduced at low potentials, a more active water oxidation catalyst is generated, yielding high catalytic currents from the moment a sufficient potential is applied. This work highlights the importance of catalyst pre-treatment and the choice of the experimental conditions in water oxidation catalysis using copper complexes.

Using scanning tunneling microscopy (STM), we characterize the atomic-scale details of ultrathin films of iron carbide (FexCy) on Au(111) synthesized as a potential model system for the active iron carbide phase in iron Fischer-Tropsch synthesis (FTS) catalysts. The experiments show that room-temperature exposure of Fe islands gas to C2H4deposited on the clean Au(111) surface results in partly converted Fe/FexCyislands. Multistep flash-heating treatment of the partly converted Fe/FexCyislands at 523 and 773 K results in pure highly crystalline FexCyislands with in-plane nearest-neighbor distances of 0.315 ± 0.005 nm. On the basis of the atom-resolved STM data, we propose that C2H4dissociates at Fe island edges, after which the carbon diffuses inward into the interstitial region between the Fe and the Au substrate to form an FexCysurface that may be a good starting point for the investigation of iron carbide surfaces present under FTS conditions.

Nucleation and morphology development during the early stages of chemical vapor deposition (CVD) processes are believed to be of major importance for the overall film properties. Here, the authors have investigated the nucleation of tin oxide films, comparing different tin precursors (tin tetrachloride (TTC) and monobutyl tin trichloride (MBTC)) and focusing on the effect of methanol addition on the film morphology. Employing electron transparent silicon oxide membranes as substrates and combining transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis on the same set of samples, we describe a detailed picture of nucleation behavior and film growth during early stages of film formation. Our main conclusion is that methanol addition during deposition acts as surfactant, lowering the surface energy of the substrate and resulting in a higher nucleation grain density. Based on these results, we propose a film growth model based on surface energy to explain morphology differences in tin oxide films resulting from methanol addition. cop. 2014 Elsevier B.V.

This paper describes a novel form of dynamic operation named pulsed activation method. It can be viewed as a form of periodic operation in which very fast temperature pulsing is used to induce chemical reactions directly and locally as needed. The main goal in this method is to activate catalytic reactions at will and within a time scale such that physical transport related dynamics cannot follow. A proof of principle experimental setup has been built to realize pulsed activation on heterogenous catalytic reactions. The temperature of the catalytic surface is pulsed at higher frequencies and amplitudes than have been reported before. As an example, oxidation of CO over a Pt catalyst is investigated.

This study investigates the production of hydrogen from the electrochemical reforming of short-chain alcohols (methanol, ethanol, iso-propanol) and their mixtures. High surface gas diffusion Pt/C electrodes were interfaced to a Nafion polymeric membrane. The assembly separated the two chambers of an electrochemical reactor, which were filled with anolyte (alcohol�+�H2O or alcohol�+�H2SO4) and catholyte (H2SO4) aqueous solutions. The half-reactions, which take place upon polarization, are the alcohol electrooxidation and the hydrogen evolution reaction at the anode and cathode, respectively. A standard Ag/AgCl reference electrode was introduced for monitoring the individual anodic and cathodic overpotentials. Our results show that roughly 75% of the total potential losses are due to sluggish kinetics of the alcohol electrooxidation reaction. Anodic overpotential becomes larger as the number of C-atoms in the alcohol increases, while a slight dependence on the pH was observed upon changing the acidity of the anolyte solution. In the case of alcohol mixtures, it is the largest alcohol that dictates the overall cell performance.

International audience; Twelve commercially available bisphosphine ligands have been evaluated in rhodium-catalyzed hydroformylation reactions. All ligands exhibited high chemoselectivities for aldehyde formation. The highest enantioselectivity (53% ee) of styrene hydroformylation was achieved with (S)-BTFM-Garphos (L7) substituted with electron withdrawing substituents. High pressure NMR (HP-NMR) spectroscopy and in situ high pressure IR spectroscopy (HP-IR) were used to study the resting states of the catalyst species in the reactions. The ligand effect on the structures of the observable species was examined. Both electronic and steric factors were considered to contribute to the performance of the various ligands. The results showed that decreasing the phosphine basicity increased the enantioselectivity, while in the systems studied here the steric character plays a less important role than the electronic features in achieving good regioselectivities.

The adsorption and decomposition of acetaldehyde and acetic acid were studied on Rh(100) to gain insight into the interaction of aldehyde and carboxyl groups of biomass-derived molecules with the surface. Temperature-programmed reaction spectroscopy (TPRS) was used to monitor gaseous reaction products, whereas Reflection absorption infrared spectroscopy (RAIRS) was used to determine the nature of surface intermediates and reaction paths. The role of adsorbate interactions in oxygenate decomposition chemistry was also investigated by varying the surface coverage. Acetaldehyde adsorbs in an η2(C, O) configuration for all coverages, where the carbonyl group binds to the surface via the C and O atoms. Decomposition occurs below room temperature (180-280 K) via C-H and C-C bond breaking, which releases CO, H, and CHx species on the surface. At low coverage, CHx dehydrogenation dominates and surface carbon is produced alongside H2 and CO. At high coverage, about 60% of the CHx hydrogenates to form methane, whereas only 40% of the CHx decomposes further to surface carbon. Acetic acid adsorbs dissociatively on the Rh(100) surface via O-H bond scission, forming a mixture of mono- and bidentate acetate. The decomposition of acetate proceeds via two different pathways: (i) deoxygenation via C-O and C-C bond scissions and (ii) decarboxylation via C-C bond scission. At low coverage, the decarboxylation pathway dominates, a process that occurs at slightly above room temperature (280-360 K) and produces CO2 and CHx, where the latter decomposes further to surface carbon and H2. At high coverage, both decarboxylation and deoxygenation occur, slightly, above room temperature (280-360 K). The resulting O adatoms produced in the deoxygenation path react with surface hydrogen or CO to form water and CO2, respectively. The CHx species dehydrogenate to surface carbon for all coverages. Our findings suggest that oxygenates with a C=O functionality and an alkyl end react on the Rh(100) surface to produce synthesis gas and small hydrocarbons whereas CO2 and synthesis gas are produced when oxygenates with a COOH functionality and an alkyl end react with the Rh(100) surface. For both cases, carbon accumulation occurs on the surface.

Olivine ((Mg,Fe)2SiO4) has been extensively explored as an active bed material for catalytic cracking of tars during gasification of biomass in dual fluidized bed reactors. It is known that both the elemental composition, addition of Fe and high temperature calcinations influence the catalytic properties of this mineral. However, it is not clear how olivine responds to the fairly hostile environments present during gasification or what chemical state Fe takes during operation. We have investigated the stability of Austrian olivine under model conditions, resembling those in a gasifier. Powder samples were heated to 750 °C in a quartz-tube flow-reactor and sequentially exposed to oxidizing (O2, H2O, CO2) or reducing gases (CO, H2) or mixtures thereof, for various durations of time. Significant changes in phase composition of the material, depending on the gas composition and the duration of the treatments, were found using X-ray photo-electron spectroscopy (XPS), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and scanning electron microscopy (SEM). A large fraction of the Fe in the investigated material is present as free Fe-phases, which are sensitive to changes in the gas environment. After exposure to oxidizing gases, the free Fe phases are: Fe2O3 and Fe3O4 or MgFe2O4. Upon exposure to reducing gases, the iron oxides are converted into Fe0 and Fe3C and formation of graphitic carbon is observed. In addition, the elemental composition of the surface changes dramatically depending on the gas composition. After exposure to oxidizing environments, the amount of Fe at the surface is twice as high as after reduction. Both the change in chemical state of the Fe-phases, the amount of surface Fe and the build-up of surface carbon are fast processes under the applied conditions and significant changes are observed on the time scale of one minute. These observations have important implications for olivine as a tar cracking catalyst, especially when used in dual fluidized bed gasifiers. The fast reduction of the iron oxides upon switching from oxidizing to reducing conditions shows that olivine transports oxygen from the combustor into the gasifier. Furthermore, the catalytic properties of Fe depend strongly on its chemical state. Therefore, the catalytic function of olivine depends strongly on the gas environment and on the catalysts residence time in the gasifier. Finally, both the decreasing amount of surface-Fe and the carbon deposition observed after exposing olivine to reducing conditions can result in significant catalyst deactivation.

A series of ferrocenyl-functionalized β-diketonato manganese(III) complexes, [Mn(FcCOCHCOR)3] with R = CF3, CH3, Ph (phenyl) and Fc (ferrocenyl) was subjected to a systematic XPS study of the Mn 2p3/2 and Fe 2p3/2 core-level photoelectron lines and their satellite structures. A charge-transfer process from the β-diketonato ligand to the Mn(III) metal center is responsible for the prominent shake-up satellite peaks of the Mn 2p photoelectron lines and the shake-down satellite peaks of the Fe 2p photoelectron lines. Multiplet splitting simulations of the photoelectron lines of the Mn(III) center of [Mn(FcCOCHCOR)3] resemble the calculated Mn 2p3/2 envelope of Mn3+ ions well, indicating the Mn(III) centers are in the high spin state. XPS spectra of complexes with unsymmetrical β-diketonato ligands (i.e., R not Fc) were described with two sets of multiplet splitting peaks representing fac and the more stable mer isomers respectively. Stronger electron-donating ligands stabilize fac more than mer isomers. The sum of group electronegativities, σχR, of the β-diketonato pendant side groups influences the binding energies of the multiplet splitting and charge transfer peaks in both Mn and Fe 2p3/2 photoelectron lines, the ratio of satellite to main peak intensities, and the degree of covalence of the Mn-O bond.