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Iridium and ruthenium and their oxides/hydroxides are the best candidates for the oxygen evolution reaction under harsh acidic conditions owing to the low overpotentials observed for Ru- and Ir-based anodes and the high corrosion resistance of Ir-oxides. Herein, by means of cutting edge operando surface and bulk sensitive X-ray spectroscopy techniques, specifically designed electrode nanofabrication and ab initio DFT calculations, we were able to reveal the electronic structure of the active IrOx centers (i.e., oxidation state) during electrocatalytic oxidation of water in the surface and bulk of high-performance Ir-based catalysts. We found the oxygen evolution reaction is controlled by the formation of empty Ir 5d states in the surface ascribed to the formation of formally IrV species leading to the appearance of electron-deficient oxygen species bound to single iridium atoms (μ1-O and μ1-OH) that are responsible for water activation and oxidation. Oxygen bound to three iridium centers (μ3-O) remains the dominant species in the bulk but do not participate directly in the electrocatalytic reaction, suggesting bulk oxidation is limited. In addition a high coverage of a μ1-OO (peroxo) species during the OER is excluded. Moreover, we provide the first photoelectron spectroscopic evidence in bulk electrolyte that the higher surface-to-bulk ratio in thinner electrodes enhances the material usage involving the precipitation of a significant part of the electrode surface and near-surface active species.

Starting from subsurface Zr0-doped “inverse” Pd and bulk-intermetallic Pd0Zr0 model catalyst precursors, we investigated the dry reforming reaction of methane (DRM) using synchrotron-based near ambient pressure in-situ X-ray photoelectron spectroscopy (NAP-XPS), in-situ X-ray diffraction and catalytic testing in an ultrahigh-vacuum-compatible recirculating batch reactor cell. Both intermetallic precursors develop a Pd0–ZrO2 phase boundary under realistic DRM conditions, whereby the oxidative segregation of ZrO2 from bulk intermetallic PdxZry leads to a highly active composite layer of carbide-modified Pd0 metal nanoparticles in contact with tetragonal ZrO2. This active state exhibits reaction rates exceeding those of a conventional supported Pd–ZrO2 reference catalyst and its high activity is unambiguously linked to the fast conversion of the highly reactive carbidic/dissolved C-species inside Pd0 toward CO at the Pd/ZrO2 phase boundary, which serves the role of providing efficient CO2 activation sites. In contrast, the near-surface intermetallic precursor decomposes toward ZrO2 islands at the surface of a quasi-infinite Pd0 metal bulk. Strongly delayed Pd carbide accumulation and thus carbon resegregation under reaction conditions leads to a much less active interfacial ZrO2–Pd0 state.

Starting from subsurface Zr0-doped “inverse” Pd and bulk-intermetallic Pd0Zr0 model catalyst precursors, we investigated the dry reforming reaction of methane (DRM) using synchrotron-based near ambient pressure in-situ X-ray photoelectron spectroscopy (NAP-XPS), in-situ X-ray diffraction and catalytic testing in an ultrahigh-vacuum-compatible recirculating batch reactor cell. Both intermetallic precursors develop a Pd0–ZrO2 phase boundary under realistic DRM conditions, whereby the oxidative segregation of ZrO2 from bulk intermetallic PdxZry leads to a highly active composite layer of carbide-modified Pd0 metal nanoparticles in contact with tetragonal ZrO2. This active state exhibits reaction rates exceeding those of a conventional supported Pd–ZrO2 reference catalyst and its high activity is unambiguously linked to the fast conversion of the highly reactive carbidic/dissolved C-species inside Pd0 toward CO at the Pd/ZrO2 phase boundary, which serves the role of providing efficient CO2 activation sites. In contrast, the near-surface intermetallic precursor decomposes toward ZrO2 islands at the surface of a quasi-infinite Pd0 metal bulk. Strongly delayed Pd carbide accumulation and thus carbon resegregation under reaction conditions leads to a much less active interfacial ZrO2–Pd0 state.

We study the changes in the crystallographic phases and in the chemical states during the iron exsolution process of lanthanum strontium ferrite (LSF, La0.6Sr0.4FeO3-δ). By using thin films of orthorhombic LSF, grown epitaxially on NaCl(001) and rhombohedral LSF powder, the materials gap is bridged. The orthorhombic material transforms into a fluorite structure after the exsolution has begun, which further hinders this process. For the powder material, by a combination of in situ core level spectroscopy and ex situ neutron diffraction, we could directly highlight differences in the Fe chemical nature between surface and bulk: whereas the bulk contains Fe(iv) in the fully oxidized state, the surface spectra can be described perfectly by the sole presence of Fe(iii). We also present corresponding magnetic and oxygen vacancy concentration data of reduced rhombohedral LSF that did not undergo a phase transformation to the cubic perovskite system based on neutron diffraction data.

We study the changes in the crystallographic phases and in the chemical states during the iron exsolution process of lanthanum strontium ferrite (LSF, La0.6Sr0.4FeO3-δ). By using thin films of orthorhombic LSF, grown epitaxially on NaCl(001) and rhombohedral LSF powder, the materials gap is bridged. The orthorhombic material transforms into a fluorite structure after the exsolution has begun, which further hinders this process. For the powder material, by a combination of in situ core level spectroscopy and ex situ neutron diffraction, we could directly highlight differences in the Fe chemical nature between surface and bulk: whereas the bulk contains Fe(iv) in the fully oxidized state, the surface spectra can be described perfectly by the sole presence of Fe(iii). We also present corresponding magnetic and oxygen vacancy concentration data of reduced rhombohedral LSF that did not undergo a phase transformation to the cubic perovskite system based on neutron diffraction data.

For the direct reduction of CO2 and H2O in solid oxide electrolysis cells (SOECs) with cermet electrodes toward methane, a fundamental understanding of the role of elemental carbon as a key intermediate within the reaction pathway is of eminent interest. The present synchrotron-based in situ near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) study shows that alloying of Ni/yttria-stabilized-zirconia (YSZ) cermet electrodes with Cu can be used to control the electrochemical accumulation of interfacial carbon and to optimize its reactivity toward CO2. In the presence of syngas, sufficiently high cathodic potentials induce excess methane on the studied Ni/yttria-stabilized-zirconia (YSZ)-, NiCu/YSZ- and Pt/gadolinium-doped-ceria (GDC) cermet systems. The hydrogenation of carbon, resulting from CO activation at the triple-phase boundary of Pt/GDC, is most efficient. [ABSTRACT FROM AUTHOR]

Advanced in situ X‐ray absorption spectroscopy characterization of electrochemically co‐electrodeposited bi‐element copper alloy electrodes shows that zinc yields the formation of a stable cationic Cu species during the electroreduction of CO2 at high cathodic polarization. In contrast, the formation/stabilization of cationic Cu species in copper oxides, or doping Cu with another element, like Ni, is not possible. It is found that the pure and mixed Cu:Zn electrodes behave similarly in term of electrocatalytic selectivity to multi‐carbon products. At higher Zn concentrations the electrode behaves like the pure Zn catalyst, which indicates that the Cu cationic species do not have a significant influence on the selectivity to multi‐carbon products. It is found that in the non‐monotonically distribution of products is dominated in term of surface energy in which copper prefers the surface. Otherwise, this work highlights the importance of in situ characterization to uncover the mechanisms mediating the catalytic reactions in contrast to ex situ or post mortem analysis, which can be a source of misinterpretation. [ABSTRACT FROM AUTHOR]

The development of redox stable oxide perovskite – based electrodes for cost-effective symmetric solid oxide fuel cells (SOFCs) that can work at intermediate temperatures and compete with state-of-the-art cathodes and anodes is becoming a concrete possibility. The Ni-doped STF perovskite Sr0.93Ti0.3Fe0.63Ni0.07O3−δ meets such requirements by exsolving catalytically active Ni–Fe nanoparticles in reducing atmospheres that boost anode performance. This work aims at clarifying whether exsolution is a reversible process, which could extend the lifetime of SOFCs. Element-specific synchrotron – based near-ambient pressure X-ray photoelectron and absorption spectroscopies are key to understanding the exsolution/reoxidation processes of the Ni–Fe nanoparticles during redox cycling in the atmosphere. This study reveals that Ni exsolves easily, dragging along the more stable Fe to form nanoalloyed Ni–Fe even under mild reducing conditions. A significant Sr-surface segregation indicates that the initial Sr-deficiency cannot fully compensate for the B-site cation depletion during exsolution. Switching to an oxidizing atmosphere results in a reoxidation-induced reconstruction of the electrode, in which a Fe- and Sr-rich oxide layer forms on the surface, leaving the Ni segregated from the perovskite. This reoxidized electrode shows a significantly improved cathode response in comparison to the pristine perovskite, indicating changes in the mechanisms that activate the oxygen reduction reaction. [ABSTRACT FROM AUTHOR]

Adsorbed hydroxyl is a key intermediate present in many catalytic reactions and electrochemical processes. In particular, hydroxyl adsorbed on noble metal surfaces has attracted attention due to its role in water-gas shift, selective oxidation of hydrocarbons and water splitting. In this work, from a well-defined oxygen covered Ag(110) surface with O-p(2 × 1) reconstruction, we prepared a fully hydroxylated surface phase in equilibrium with water and oxygen in the gas phase under near ambient conditions. In situ soft X-ray spectroscopy combined with density functional theory revealed distinctive modifications in the electronic structure of the adsorbate layer upon hydroxylation. We show that both the core and valence electronic states of OH adsorbates have higher binding energies relative to the Fermi level than the states for the O adsorbate. The OH orbitals interact with the d band of Ag giving rise to hybridized orbitals with bonding and anti-bonding symmetry, with larger energy splitting than the oxygen adsorbate. [ABSTRACT FROM AUTHOR]

Photoelectron spectroscopy offers detailed information about the electronic structure and chemical composition of surfaces, owing to the short distance that the photoelectrons can escape from a dense medium. Unfortunately, photoelectron based spectroscopies are not directly compatible with the liquids required to investigate electrochemical processes, especially in the soft X-ray regime. To overcome this issue, different approaches based on photoelectron spectroscopy have been developed in our group over the last few years. The performance and the degree of information provided by these approaches are compared with those of the well established bulk sensitive spectroscopic approach of total fluorescence yield detection, where the surface information gained from this approach is enhanced using samples with large surface to bulk ratios. The operation of these approaches is exemplified and compared using the oxygen evolution reaction on IrOx catalysts. We found that all the approaches, if properly applied, provide similar information about surface oxygen speciation. However, using resonant photoemission spectroscopy, we were able to prove that speciation is more involved and complex than previously thought during the oxygen evolution reaction on IrOx based electrocatalysts. We found that the electrified solid–liquid interface is composed of different oxygen species, where the terminal oxygen atoms on iridium are the active species, yielding the formation of peroxo species and, finally, dioxygen as the reaction product. Thus, the oxygen–oxygen bond formation is dominated by peroxo species formation along the reaction pathway. Furthermore, the methodologies discussed here open up opportunities to investigate electrified solid–liquid interfaces in a multitude of electrochemical processes with unprecedented speciation capabilities, which are not accessible by one-dimensional X-ray spectroscopies. [ABSTRACT FROM AUTHOR]

Operando X-ray Photoelectron and Absorption Spectroscopy (XPS and XAS) using soft (up to 2 KeV) and tender (2-10 KeV) X-rays applied to study functional materials for energy conversion has gone through great development in the last years and several approaches to different cell designs combined with instrumentation development now allow successful characterization of electrode-electrolyte interfaces under working conditions. An overview of the current state and challenges are presented along with an outlook into the direction that future development should take, which we expect would allow us to expand and complete our understanding of the liquid-solid electrochemical interfaces. [ABSTRACT FROM AUTHOR]

In direct methanol fuel cells (DMFCs), the methanol crossover from the anode to the cathode is a major cause of power density loss because of the overpotential arising due to the parasitic reaction of methanol oxidation at the cathode. Catalysts modified with S have shown better methanol tolerance; however, the preparation routes often require high temperatures or pressures and very long times, making these expensive and unlikely to be used in large scale. Here, we report on a single-step low-temperature method used to prepare a carbon-supported PtxSy catalyst. Moreover, we show that the catalyst shows lower depolarization in the presence of methanol and study the effect of reductive thermal treatment and electrochemical potential cycling. [ABSTRACT FROM AUTHOR]

We study the changes in the crystallographic phases and in the chemical states during the iron exsolution process of lanthanum strontium ferrite (LSF, La0.6Sr0.4FeO3−δ). By using thin films of orthorhombic LSF, grown epitaxially on NaCl(001) and rhombohedral LSF powder, the materials gap is bridged. The orthorhombic material transforms into a fluorite structure after the exsolution has begun, which further hinders this process. For the powder material, by a combination of in situ core level spectroscopy and ex situ neutron diffraction, we could directly highlight differences in the Fe chemical nature between surface and bulk: whereas the bulk contains Fe(iv) in the fully oxidized state, the surface spectra can be described perfectly by the sole presence of Fe(iii). We also present corresponding magnetic and oxygen vacancy concentration data of reduced rhombohedral LSF that did not undergo a phase transformation to the cubic perovskite system based on neutron diffraction data. [ABSTRACT FROM AUTHOR]

Although the relevance of electronic effects in the electrocatalysis of the oxygen reduction reaction has been recognized, the impossibility of separating the effects of composition and particle size for Pt-based materials has hindered establishing clear activity–property relationships. Herein, we report a systematic study based on induced changes via the interactions of pure Pt nanoparticles with transition metal oxide/carbon supports (Pt/MOx/C catalysts, MOx = CeO2, SnO2, TiO2, ZrO2 and WO3). A thorough analysis of aberration-corrected HR-STEM images demonstrated that Pt particles are similar in size and shape for all catalysts, while the direct probing of electronic properties by in situ X-ray absorption spectroscopy evidenced charge transfer between Pt and the supports. This approach allowed ascribing the changes in electrocatalytic activity for oxygen reduction solely to the variations in the electronic vacancy of the Pt 5d band resulting from the interactions between the metal nanoparticles and the supports containing different transition metal oxides. Oxygen reduction was studied in acid and in alkaline solutions, and linear correlations between the kinetic current densities and the Pt 5d band vacancy of pure Pt nanoparticles were found in both media. Possible first steps of the reduction of oxygen are discussed to explain the trends observed. The results, evidencing that enhanced ORR activity on Pt particles is promoted by a lower 5d band vacancy in acid solutions and by a higher one in alkaline medium, provide new insights on the fundamental aspects of oxygen reduction, and open up new possibilities to develop catalysts with enhanced activity for fuel cell cathodes by tuning their electronic properties. [ABSTRACT FROM AUTHOR]

C‐saturated Pd0 nanoparticles with an extended phase boundary to ZrO2 evolve from a Pd0Zr0 precatalyst under CH4 dry reforming conditions. This highly active catalyst state fosters bifunctional action: CO2 is efficiently activated at oxidic phase boundary sites and PdxC provides fast supply of C‐atoms toward the latter. ZrO2‐promoted methane dry reforming on PdxC: C‐saturated Pd0 nanoparticles with extended phase boundary to ZrO2 evolve from a Pd0Zr0 precatalyst under CH4 dry reforming conditions. This highly active catalyst state fosters bifunctional action: CO2 is efficiently activated at oxidic phase boundary sites and PdxC provides fast supply of C‐atoms toward the latter. [ABSTRACT FROM AUTHOR]

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Two single crystalline surfaces of Au vicinal to the (111) plane were modified with Pt and studied using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) in ultra-high vacuum environment. The vicinal surfaces studied are Au(332) and Au(887) and different Pt coverage (ϑPt) were deposited on each surface. From STM images we determine that Pt deposits on both surfaces as nanoislands with heights ranging from 1 ML to 3 ML depending on ϑPt. On both surfaces the early growth of Pt ad-islands occurs at the lower part of the step edge, with Pt ad-atoms being incorporated into the steps in some cases. XPS results indicate that partial alloying of Pt occurs at the interface at room temperature and at all coverage, as suggested by the negative chemical shift of Pt 4f core line, indicating an upward shift of the d-band center of the alloyed Pt. Also, the existence of a segregated Pt phase especially at higher coverage is detected by XPS. Sample annealing indicates that the temperature rise promotes a further incorporation of Pt atoms into the Au substrate as supported by STM and XPS results. Additionally, the catalytic activity of different PtAu systems reported in the literature for some electrochemical reactions is discussed considering our findings. [ABSTRACT FROM AUTHOR]

Catalyst degradation and product selectivity changes are two of the key challenges in the electrochemical reduction of CO 2 on copper electrodes. Yet, these aspects are often overlooked. Here, we combine in situ X-ray spectroscopy, in situ electron microscopy, and ex situ characterization techniques to follow the long-term evolution of the catalyst morphology, electronic structure, surface composition, activity, and product selectivity of Cu nanosized crystals during the CO 2 reduction reaction. We found no changes in the electronic structure of the electrode under cathodic potentiostatic control over time, nor was there any build-up of contaminants. In contrast, the electrode morphology is modified by prolonged CO 2 electroreduction, which transforms the initially faceted Cu particles into a rough/rounded structure. In conjunction with these morphological changes, the current increases and the selectivity changes from value-added hydrocarbons to less valuable side reaction products, i.e. , hydrogen and CO. Hence, our results suggest that the stabilization of a faceted Cu morphology is pivotal for ensuring optimal long-term performance in the selective reduction of CO 2 into hydrocarbons and oxygenated products.

Photoelectron spectroscopy offers detailed information about the electronic structure and chemical composition of surfaces, owing to the short distance that the photoelectrons can escape from a dense medium. Unfortunately, photoelectron based spectroscopies are not directly compatible with the liquids required to investigate electrochemical processes, especially in the soft X-ray regime. To overcome this issue, different approaches based on photoelectron spectroscopy have been developed in our group over the last few years. The performance and the degree of information provided by these approaches are compared with those of the well established bulk sensitive spectroscopic approach of total fluorescence yield detection, where the surface information gained from this approach is enhanced using samples with large surface to bulk ratios. The operation of these approaches is exemplified and compared using the oxygen evolution reaction on IrO x catalysts. We found that all the approaches, if properly applied, provide similar information about surface oxygen speciation. However, using resonant photoemission spectroscopy, we were able to prove that speciation is more involved and complex than previously thought during the oxygen evolution reaction on IrO x based electrocatalysts. We found that the electrified solid-liquid interface is composed of different oxygen species, where the terminal oxygen atoms on iridium are the active species, yielding the formation of peroxo species and, finally, dioxygen as the reaction product. Thus, the oxygen-oxygen bond formation is dominated by peroxo species formation along the reaction pathway. Furthermore, the methodologies discussed here open up opportunities to investigate electrified solid-liquid interfaces in a multitude of electrochemical processes with unprecedented speciation capabilities, which are not accessible by one-dimensional X-ray spectroscopies.

We study the changes in the crystallographic phases and in the chemical states during the iron exsolution process of lanthanum strontium ferrite (LSF, La0.6Sr0.4FeO3-δ). By using thin films of orthorhombic LSF, grown epitaxially on NaCl(001) and rhombohedral LSF powder, the materials gap is bridged. The orthorhombic material transforms into a fluorite structure after the exsolution has begun, which further hinders this process. For the powder material, by a combination of in situ core level spectroscopy and ex situ neutron diffraction, we could directly highlight differences in the Fe chemical nature between surface and bulk: whereas the bulk contains Fe(iv) in the fully oxidized state, the surface spectra can be described perfectly by the sole presence of Fe(iii). We also present corresponding magnetic and oxygen vacancy concentration data of reduced rhombohedral LSF that did not undergo a phase transformation to the cubic perovskite system based on neutron diffraction data.

C-saturated Pd 0 nanoparticles with an extended phase boundary to ZrO 2 evolve from a Pd 0 Zr 0 precatalyst under CH 4 dry reforming conditions. This highly active catalyst state fosters bifunctional action: CO 2 is efficiently activated at oxidic phase boundary sites and Pd x C provides fast supply of C-atoms toward the latter., (© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The nature of the oxygen species active in ethylene epoxidation is a long-standing question. While the structure of the oxygen species that participates in total oxidation (nucleophilic oxygen) is known the atomic structure of the selective species (electrophilic oxygen) is still debated. Here, we use both in situ and UHV X-ray Photoelectron Spectroscopy (XPS) to study the interaction of oxygen with a silver surface. We show experimental evidence that the unreconstructed adsorbed atomic oxygen (O ads ) often argued to be active in epoxidation has a binding energy (BE) ≤ 528 eV, showing a core-level shift to lower BE with respect to the O-reconstructions, as previously predicted by DFT. Thus, contrary to the frequent assignment, adsorbed atomic oxygen cannot account for the electrophilic oxygen species with an O 1s BE of 530-531 eV, thought to be the active species in ethylene epoxidation. Moreover, we show that O ads is present at very low O-coverages during in situ XPS measurements and that it can be obtained at slightly higher coverages in UHV at low temperature. DFT calculations support that only low coverages of O ads are stable. The highly reactive species is titrated by background gases even at low temperature in UHV conditions. Our findings suggest that at least two different species could participate in the partial oxidation of ethylene on silver.

We report in this paper the effect of temperature on the oscillatory electro-oxidation of methanol on polycrystalline platinum in aqueous sulfuric acid media. Potential oscillations were studied under galvanostatic control and at four temperatures ranging from 5 to 35 degrees C. For a given temperature, the departure from thermodynamic equilibrium does not affect the oscillation period and results in a slight increase of the oscillation amplitude. Apparent activation energies were also evaluated in voltammetric and chronoamperometric experiments and were compared to those obtained under oscillatory conditions. In any case, the apparent activation energies values fell into the region between 50 and 70 kJ mol(-1). Specifically under oscillatory conditions an apparent activation energy of 60 +/- 3 kJ mol(-1) and a temperature coefficient q10 of about 2.3 were observed. The present findings extend our recently published report (J. Phys. Chem. A, 2008, 112, 4617) on the temperature effect on the oscillatory electro-oxidation of formic acid. We found that, despite the fact that both studies were carried out under similar conditions, unlike the case of formic acid, only conventional, Arrhenius, dynamics was observed for methanol.