Mn-promoted MoS2 catalysts for CO2 hydrogenation: enhanced methanol selectivity due to MoS2/MnOx interfaces.

Considering the alarming scenario of climate change, CO2 hydrogenation to methanol is considered a key process for phasing out fossil fuels by means of CO2 utilization. In this context, MoS2 catalysts have recently shown to be promising catalysts for this reaction, especially in the presence of abundant basal-plane sulfur vacancies and due to synergistic mechanisms with other phases. In this work, Mn-promoted MoS2 prepared by a hydrothermal method presents considerable selectivity for CO2 hydrogenation to methanol in comparison with pure MoS2 and other promoters such as K and Co. Interestingly, if CO is used as a carbon source for the reaction, methanol production is remarkably lower, which suggests the absence of a CO intermediate during CO2 hydrogenation to methanol. After optimization of synthesis parameters, a methanol selectivity of 64% is achieved at a CO2 conversion of 2.8% under 180 °C. According to material characterization by X-ray Diffraction and X-ray Absorption, the Mn promoter is present mainly in the form of MnO and MnCO3 phases, with the latter undergoing convertion to MnO upon H2 pretreatment. However, following exposure to reaction conditions, X-ray photoelectron spectroscopy suggests that higher oxidation states of Mn may be present at the surface, suggesting that the improved catalytic activity for CO2 hydrogenation to methanol arises from a synergy between MoS2 and MnOx at the catalyst surface.

Engineering surface dipoles on mixed conducting oxides with ultra-thin oxide decoration layers.

Improving materials for energy conversion and storage devices is deeply connected with an optimization of their surfaces and surface modification is a promising strategy on the way to enhance modern energy technologies. This study shows that surface modification with ultra-thin oxide layers allows for a systematic tailoring of the surface dipole and the work function of mixed ionic and electronic conducting oxides, and it introduces the ionic potential of surface cations as a readily accessible descriptor for these effects. The combination of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) illustrates that basic oxides with a lower ionic potential than the host material induce a positive surface charge and reduce the work function of the host material and vice versa. As a proof of concept that this strategy is widely applicable to tailor surface properties, we examined the effect of ultra-thin decoration layers on the oxygen exchange kinetics of pristine mixed conducting oxide thin films in very clean conditions by means of in-situ impedance spectroscopy during pulsed laser deposition (i-PLD). The study shows that basic decorations with a reduced surface work function lead to a substantial acceleration of the oxygen exchange on the surfaces of diverse materials.

Dynamic behaviour of platinum and copper dopants in gold nanoclusters supported on ceria catalysts.

Understanding the behaviour of active catalyst sites at the atomic level is crucial for optimizing catalytic performance. Here, the evolution of Pt and Cu dopants in Au25 clusters on CeO2 supports is investigated in the water-gas shift (WGS) reaction, using operando XAFS and DRIFTS. Different behaviour is observed for the Cu and Pt dopants during the pretreatment and reaction. The Cu migrates and builds clusters on the support, whereas the Pt creates single-atom active sites on the surface of the cluster, leading to better performance. Doping with both metals induces strong interactions and pretreatment and reaction conditions lead to the growth of the Au clusters, thereby affecting their catalytic behaviour. This highlights importance of understanding the behaviour of atoms at different stages of catalyst evolution. These insights into the atomic dynamics at the different stages are crucial for the precise optimisation of catalysts, which ultimately enables improved catalytic performance.

Crystal-Orientation-Dependent Oxygen Exchange Kinetics on Mixed Conducting Thin-Film Surfaces Investigated by In Situ Studies.

The oxygen exchange kinetics and the surface chemistry of epitaxially grown, dense La0.6Sr0.4CoO3-δ (LSC) thin films in three different orientations, (001), (110), and (111), were investigated by means of in situ impedance spectroscopy during pulsed laser deposition (i-PLD) and near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS). i-PLD measurements showed that pristine LSC surfaces exhibit very fast surface exchange kinetics but revealed no significant differences between the specific orientations. However, as soon as the surfaces were in contact with acidic, gaseous impurities, such as S-containing compounds in nominally pure measurement atmospheres, NAP-XPS measurements revealed that the (001) orientation is substantially more susceptible to the formation of sulfate adsorbates and a concomitant performance decrease. This result is further substantiated by a stronger increase of the work function on (001)-oriented LSC surfaces upon sulfate adsorbate formation and by a faster performance degradation of these surfaces in ex situ measurement setups. This phenomenon has potentially gone unnoticed in the discussion of the interplay between the crystal orientation and the oxygen exchange kinetics and might have far-reaching implications for real solid oxide cell electrodes, where porous materials exhibit a wide variety of differently oriented and reconstructed surfaces.

Improving and degrading the oxygen exchange kinetics of La0.6Sr0.4CoO3-δ by Sr decoration.

Minimizing the overpotential at the air electrode of solid oxide fuel cells (SOFC) is one of the key challenges regarding a broad applicability of this technology. Next to novel materials and geometry optimization, surface modification is a promising and flexible method to alter the oxygen exchange kinetics at SOFC cathode surfaces. Despite extensive research, the mechanism behind the effect of surface decorations is still under debate. Moreover, for Sr decoration, previous studies yielded conflicting results, reporting either a beneficial or a detrimental impact on the oxygen exchange kinetics. In this contribution, in situ impedance spectroscopy during pulsed laser deposition was used to investigate the effect of Sr containing decorations under different deposition conditions. Depending on deposition temperature and interactions with the gas phase, opposing effects of Sr decoration were found. In combination with near-ambient pressure X-ray photoelectron spectroscopy and non-ambient X-ray diffractometry, it was possible to trace this phenomenon back to different chemical environments of the surface Sr. At high temperatures, Sr is deposited as SrO, which can have a beneficial effect on the oxygen exchange kinetics. At low temperatures, SrCO3 adsorbates are formed from trace amounts of CO2 in the measurement atmosphere, causing a decrease of the oxygen exchange rate. These results are in excellent agreement with the concept of surface acidity as a descriptor for the effect of surface decorations, providing further insight into the oxygen exchange kinetics on SOFC cathode surfaces and its degradation. In addition, this study shows that Sr segregation itself initially does not lead to performance degradation but that segregated SrO readily reacts with acidic compounds, reducing the catalytic capability of mixed conducting oxides.

Surface Decorations on Mixed Ionic and Electronic Conductors: Effects on Surface Potential, Defects, and the Oxygen Exchange Kinetics.

The oxygen exchange kinetics of epitaxial Pr0.1Ce0.9O2-δ electrodes was modified by decoration with submonolayer amounts of different basic (SrO, CaO) and acidic (SnO2, TiO2) binary oxides. The oxygen exchange reaction (OER) rate and the total conductivity were measured by in situ PLD impedance spectroscopy (i-PLD), which allows to directly track changes of electrochemical properties after each deposited pulse of surface decoration. The surface chemistry of the electrodes was investigated by near-ambient pressure XPS measurements (NAP-XPS) at elevated temperatures and by low-energy ion scattering (LEIS). While a significant alteration of the OER rate was observed after decoration with binary oxides, the pO2 dependence of the surface exchange resistance and its activation energy were not affected, suggesting that surface decorations do not alter the fundamental OER mechanism. Furthermore, the total conductivity of the thin films does not change upon decoration, indicating that defect concentration changes are limited to the surface layer. This is confirmed by NAP-XPS measurements which find only minor changes of the Pr-oxidation state upon decoration. NAP-XPS was further employed to investigate changes of the surface potential step on decorated surfaces. From a mechanistic point of view, our results indicate a correlation between the surface potential and the altered oxygen exchange activity. Oxidic decorations induce a surface charge which depends on their acidity (acidic oxides lead to a negative surface charge), affecting surface defect concentrations, any existing surface potential step, potentially adsorption dynamics, and consequently also the OER kinetics.

Exsolved catalyst particles as a plaything of atmosphere and electrochemistry.

A new type of catalyst preparation yields its active sites not by infiltration but exsolution of reducible transition metals of its own host lattice. These exsolution catalysts offer a high dispersion of catalytically active particles, slow agglomeration, and the possibility of reactivation after poisoning due to redox cycling. The formation of exsolved particles by partial decomposition of the host lattice can be driven by applying a sufficiently reducing atmosphere, elevated temperatures but also by a cathodic bias voltage (provided the host perovskite is an electrode on an oxide ion conducting electrolyte). In addition, such an electrochemical polarisation can change the oxidation state and thus the catalytic activity of exsolved particles. In this work, we investigate the electrochemical switching between an active and an inactive state of iron particles exsolved from thin film mixed conducting model electrodes, namely La0.6Sr0.4FeO3-δ (LSF) and Nd0.6Ca0.4FeO3-δ (NCF), in humid hydrogen atmospheres. We show that the transition between two activity states exhibits a hysteresis-like behaviour in the electrochemical I-V characteristics. Ambient pressure XPS measurements proofed that this hysteresis is linked to the oxidation and reduction of iron particles. Furthermore, it is demonstrated that the surface kinetics of the host material itself has only a negligible impact on the particle exsolution, and that the main impact factors are the surrounding atmosphere as well as the applied electrochemical overpotential. In particular, we suggest a 'kinetic competition' between gas atmosphere and oxygen chemical potential in the mixed conducting electrode and discuss possible ways of how this process takes place.

Electronic and ionic effects of sulphur and other acidic adsorbates on the surface of an SOFC cathode material.

The effects of sulphur adsorbates and other typical solid oxide fuel cell (SOFC) poisons on the electronic and ionic properties of an SrO-terminated (La,Sr)CoO3 (LSC) surface and on its oxygen exchange kinetics have been investigated experimentally with near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), low energy ion scattering (LEIS) and impedance spectroscopy as well as computationally with density functional theory (DFT). The experiment shows that trace amounts of sulphur in measurement atmospheres form SO2- 4 adsorbates and strongly deactivate a pristine LSC surface. They induce a work function increase, indicating a changing surface potential and a surface dipole. DFT calculations reveal that the main participants in these charge transfer processes are not sub-surface transition metals, but surface oxygen atoms. The study further shows that sulphate adsorbates strongly affect oxygen vacancy formation energies in the LSC (sub-)surface, thus affecting defect concentrations and oxygen transport properties. To generalize these results, the investigation was extended to other acidic oxides which are technologically relevant as SOFC cathode poisons, such as CO2 and CrO3. The results unveil a clear correlation of work function changes and redistributed charge with the Smith acidity of the adsorbed oxide and clarify fundamental mechanistic details of atomic surface modifications. The impact of acidic adsorbates on various aspects of the oxygen exchange reaction rate is discussed in detail.

Exsolution on perovskite oxides: morphology and anchorage of nanoparticles.

Perovskites are very promising materials for a wide range of applications (such as catalysis, solid oxide fuel cells…) due to beneficial general properties (e.g. stability at high temperatures) and tunability - doping both A- and B-site cations opens the path to a materials design approach that allows specific properties to be finely tuned towards applications. A major asset of perovskites is the ability to form nanoparticles on the surface under certain conditions in a process called "exsolution". Exsolution leads to the decoration of the material's surface with finely dispersed nanoparticles (which can be metallic or oxidic - depending on the experimental conditions) made from B-site cations of the perovskite lattice (here, doping comes into play, as B-site doping allows control over the constitution of the nanoparticles). In fact, the ability to undergo exsolution is one of the main reasons that perovskites are currently a hot topic of intensive research in catalysis and related fields. Exsolution on perovskites has been heavily researched in the last couple of years: various potential catalysts have been tested with different reactions, the oxide backbone materials and the exsolved nanoparticles have been investigated with a multitude of different methods, and the effect of different exsolution parameters on the resulting nanoparticles has been studied. Despite all this, to our knowledge no comprehensive effort was made so far to evaluate these studies with respect to the effect that the exsolution conditions have on anchorage and morphology of the nanoparticles. Therefore, this highlight aims to provide an overview of nanoparticles exsolved from oxide-based perovskites with a focus on the conditions leading to nanoparticle exsolution.

Closed-Pore Formation in Oxygen Electrodes for Solid Oxide Electrolysis Cells Investigated by Impedance Spectroscopy.

Electrochemical impedance spectroscopy was used to investigate the chemical capacitance of La0.6Sr0.4CoO3-δ (LSC) thin-film electrodes under anodic polarization (i.e., in the electrolysis mode). For this purpose, electrodes with different microstructures were prepared via pulsed-laser deposition. Analysis of dense electrodes and electrodes with open porosity revealed decreasing chemical capacitances with increasing anodic overpotentials, as expected from defect chemical considerations. However, extremely high chemical capacitance peaks with values in the range of 104 F/cm3 at overpotentials of >140 mV were obtained after annealing for several hours in synthetic air and/or after applying high anodic bias voltages of >750 mV. From the results of several surface analysis techniques and transmission electron microscopy, it is concluded that closed pores develop upon both of these treatments: (i) During annealing, initially open pores get closed by SrSO4, which forms due to strontium segregation in measurement gases with minute traces of sulfur. (ii) The bias treatment causes mechanical failure and morphological changes including closed pores in the bulk of dense films. Under anodic polarization, high-pressure oxygen accumulates in those closed pores, and this causes the capacitance peak. Model calculations based on a real-gas equation allow us to properly predict the experimentally obtained capacitance increase. We demonstrate that analysis of the chemical capacitance of oxygen electrodes in solid oxide electrolysis cells can thus be used as a nondestructive observation tool to detect and quantify closed porosity with a lower detection limit between 10-4 and 10-3.

Structural evolution after oxidative pretreatment and CO oxidation of Au nanoclusters with different ligand shell composition: a view on the Au core.

The reactivity of supported monolayer protected Au nanoclusters is directly affected by their structural dynamics under pretreatment and reaction conditions. The effect of different types of ligands of Au clusters supported on CeO2 on their core structure evolution, under oxidative pretreatment and CO oxidation reaction, was investigated. X-ray absorption and X-ray photoelectron spectroscopy studies revealed that the clusters evolve to a similar core structure above 250 °C in all the cases, indicating the active role of the ligand-support interaction in the reaction.

Doped metal clusters as bimetallic AuCo nanocatalysts: insights into structural dynamics and correlation with catalytic activity by in situ spectroscopy.

Co-doped Au25 nanoclusters with different numbers of doping atoms were synthesized and supported on CeO2. The catalytic properties were studied in the CO oxidation reaction. In all cases, an enhancement in catalytic activity was observed compared to the pure Au25 nanocluster catalyst. Interestingly, a different catalytic performance was obtained depending on the number of Co atoms within the cluster. This was related to the mobility of atoms within the cluster's structure under pretreatment and reaction conditions, resulting in active CoAu nanoalloy sites. The evolution of the doped Au clusters into nanoalloys with well-distributed Co atoms within the Au cluster structure was revealed by combined XAFS, DRIFTS, and XPS studies. Overall, these studies contribute to a better understanding of the dynamics of doped nanoclusters on supports upon pretreatment and reaction, which is key information for the future development and application of bimetallic nanocluster (nanoalloy) catalysts.

In situ techniques reveal the true capabilities of SOFC cathode materials and their sudden degradation due to omnipresent sulfur trace impurities.

In this study, five different mixed conducting cathode materials were grown as dense thin films by pulsed laser deposition (PLD) and characterized via in situ impedance spectroscopy directly after growth inside the PLD chamber (i-PLD). This technique enables quantification of the oxygen reduction kinetics on pristine and contaminant-free mixed conducting surfaces. The measurements reveal excellent catalytic performance of all pristine materials with polarization resistances being up to two orders of magnitude lower than those previously reported in the literature. For instance, on dense La0.6Sr0.4CoO3-δ thin films, an area specific surface resistance of ∼0.2 Ω cm2 at 600 °C in synthetic air was found, while values usually >1 Ω cm2 are measured in conventional ex situ measurement setups. While surfaces after i-PLD measurements were very clean, ambient pressure X-ray photoelectron spectroscopy (AP-XPS) measurements found that all samples measured in other setups were contaminated with sulfate adsorbates. In situ impedance spectroscopy during AP-XPS revealed that already trace amounts of sulfur present in high purity gases accumulate quickly on pristine surfaces and lead to strongly increased surface polarization resistances, even before the formation of a SrSO4 secondary phase. Accordingly, the inherent excellent catalytic properties of this important class of materials were often inaccessible so far. As a proof of concept, the fast kinetics observed on sulfate-free surfaces were also realized in ex situ measurements with a gas purification setup and further reduces the sulfur concentration in the high purity gas.

The state of zinc in methanol synthesis over a Zn/ZnO/Cu(211) model catalyst.

The active chemical state of zinc (Zn) in a zinc-copper (Zn-Cu) catalyst during carbon dioxide/carbon monoxide (CO2/CO) hydrogenation has been debated to be Zn oxide (ZnO) nanoparticles, metallic Zn, or a Zn-Cu surface alloy. We used x-ray photoelectron spectroscopy at 180 to 500 millibar to probe the nature of Zn and reaction intermediates during CO2/CO hydrogenation over Zn/ZnO/Cu(211), where the temperature is sufficiently high for the reaction to rapidly turn over, thus creating an almost adsorbate-free surface. Tuning of the grazing incidence angle makes it possible to achieve either surface or bulk sensitivity. Hydrogenation of CO2 gives preference to ZnO in the form of clusters or nanoparticles, whereas in pure CO a surface Zn-Cu alloy becomes more prominent. The results reveal a specific role of CO in the formation of the Zn-Cu surface alloy as an active phase that facilitates efficient CO2 methanol synthesis.

Performance modulation through selective, homogenous surface doping of lanthanum strontium ferrite electrodes revealed by in situ PLD impedance measurements.

Accelerating the oxygen reduction kinetics of solid oxide fuel cell (SOFC) cathodes is crucial to improve their efficiency and thus to provide the basis for an economically feasible application of intermediate temperature SOFCs. In this work, minor amounts of Pt were doped into lanthanum strontium ferrite (LSF) thin film electrodes to modulate the material's oxygen exchange performance. Surprisingly, Pt was found to be incorporated on the B-site of the perovskite electrode as non metallic Pt4+. The polarization resistance of LSF thin film electrodes with and without additional Pt surface doping was compared directly after film growth employing in situ electrochemical impedance spectroscopy inside a PLD chamber (i-PLD). This technique enables observation of the polarization resistance of pristine electrodes unaltered by degradation or any external contamination of the electrode surface. Moreover, growth of multi-layers of materials with different compositions on the very same single crystalline electrolyte substrate combined with in situ impedance measurements allow excellent comparability of different materials. Even a 5 nm layer of Pt doped LSF (1.5 at% Pt), i.e. a Pt loading of 80 ng cm-2, improved the polarization resistance by a factor of about 2.5. In addition, p(O2) and temperature dependent impedance measurements on both pure and Pt doped LSF were performed in situ and obtained similar activation energies and p(O2) dependence of the polarization resistance, which allow us to make far reaching mechanistic conclusions indicating that Pt4+ introduces additional active sites.

Hybrid carbon spherogels: carbon encapsulation of nano-titania.

Extraordinarily homogeneous, freestanding titania-loaded carbon spherogels can be obtained using Ti(acac)2(OiPr)2 in the polystyrene sphere templated resorcinol-formaldehyde gelation. Thereby, a distinct, crystalline titania layer is achieved inside every hollow sphere building unit. These hybrid carbon spherogels allow capitalizing on carbon's electrical conductivity and the lithium-ion intercalation capacity of titania.

Interplay between CO Disproportionation and Oxidation: On the Origin of the CO Reaction Onset on Atomic Layer Deposition-Grown Pt/ZrO2 Model Catalysts.

Pt/ZrO2 model catalysts were prepared by atomic layer deposition (ALD) and examined at mbar pressure by operando sum frequency generation (SFG) spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) combined with differentially pumped mass spectrometry (MS). ALD enables creating model systems ranging from Pt nanoparticles to bulk-like thin films. Polarization-dependent SFG of CO adsorption reveals both the adsorption configuration and the Pt particle morphology. By combining experimental data with ab initio density functional theory (DFT) calculations, we show that the CO reaction onset is determined by a delicate balance between CO disproportionation (Boudouard reaction) and oxidation. CO disproportionation occurs on low-coordinated Pt sites, but only at high CO coverages and when the remaining C atom is stabilized by a favorable coordination. Thus, under the current conditions, initial CO oxidation is found to be strongly influenced by the removal of carbon deposits formed through disproportionation mechanisms rather than being determined by the CO and oxygen inherent activity. Accordingly, at variance with the general expectation, rough Pt nanoparticles are seemingly less active than smoother Pt films. The applied approach enables bridging both the "materials and pressure gaps".

An ultrahigh vacuum-compatible reaction cell for model catalysis under atmospheric pressure flow conditions.

Atmospheric pressure reactions on model catalysts are typically performed in so-called high-pressure cells, with product analysis performed by gas chromatography (GC) or mass spectrometry (MS). However, in most cases, these cells have a large volume (liters) so that the reactions on catalysts with only cm2 surface area can be carried out only in the (recirculated) batch mode to accumulate sufficient product amounts. Herein, we describe a novel small-volume (milliliters) catalytic reactor that enables kinetic studies under atmospheric pressure flow conditions. The cell is located inside an ultrahigh vacuum chamber that is deliberately limited to basic functions. Model catalyst samples are mounted inside the reactor cell, which is locked to an oven for external heating and closed by using an extendable/retractable gas dosing tube. Reactant and product analyses are performed by both micro-GC and MS. The functionality of the new design is demonstrated by catalytic ethylene (C2H4) hydrogenation on polycrystalline Pt and Pd foils.

Ca-doped rare earth perovskite materials for tailored exsolution of metal nanoparticles.

Perovskite-type oxide materials (nominal composition ABO3) are a very versatile class of materials, and their properties are tuneable by varying and doping A- and B-site cations. When the B-site contains easily reducible cations (e.g. Fe, Co or Ni), these can exsolve under reducing conditions and form metallic nanoparticles on the surface. This process is very interesting as a novel route for the preparation of catalysts, since oxide surfaces decorated with finely dispersed catalytically active (often metallic) nanoparticles are a key requirement for excellent catalyst performance. Five doped perovskites, namely, La0.9Ca0.1FeO3-δ, La0.6Ca0.4FeO3-δ, Nd0.9Ca0.1FeO3-δ, Nd0.6Ca0.4FeO3-δ and Nd0.6Ca0.4Fe0.9Co0.1O3-δ, have been synthesized and characterized by experimental and theoretical methods with respect to their crystal structures, electronic properties, morphology and exsolution behaviour. All are capable of exsolving Fe and/or Co. Special emphasis has been placed on the influence of the A-site elemental composition on structure and exsolution capability. Using Nd instead of La increased structural distortions and, at the same time, hindered exsolution. Increasing the amount of Ca doping also increased distortions and additionally changed the Fe oxidation states, resulting in exsolution being shifted to higher temperatures as well. Using the easily reducible element Co as the B-site dopant significantly facilitated the exsolution process and led to much smaller and homogeneously distributed exsolved particles. Therefore, the Co-doped perovskite is a promising material for applications in catalysis, even more so as Co is catalytically a highly active element. The results show that fine-tuning of the perovskite composition will allow tailored exsolution of nanoparticles, which can be used for highly sophisticated catalyst design.

Dynamics of Pd Dopant Atoms inside Au Nanoclusters during Catalytic CO Oxidation.

Doping gold nanoclusters with palladium has been reported to increase their catalytic activity and stability. PdAu24 nanoclusters, with the Pd dopant atom located at the center of the Au cluster core, were supported on titania and applied in catalytic CO oxidation, showing significantly higher activity than supported monometallic Au25 nanoclusters. After pretreatment, operando DRIFTS spectroscopy detected CO adsorbed on Pd during CO oxidation, indicating migration of the Pd dopant atom from the Au cluster core to the cluster surface. Increasing the number of Pd dopant atoms in the Au structure led to incorporation of Pd mostly in the S-(M-S) n protecting staples, as evidenced by in situ XAFS. A combination of oxidative and reductive thermal pretreatment resulted in the formation of isolated Pd surface sites within the Au surface. The combined analysis of in situ XAFS, operando DRIFTS, and ex situ XPS thus revealed the structural evolution of bimetallic PdAu nanoclusters, yielding a Pd single-site catalyst of 2.7 nm average particle size with improved CO oxidation activity.