Correction to "Understanding Anomalous Gas-Phase Peak Shifts in Dip-and-Pull Ambient Pressure XPS Experiments".

[This corrects the article DOI: 10.1021/acs.jpcc.4c00113.].

In Situ Formation of Platinum-Carbon Catalysts in Propane Dehydrogenation.

The catalytic production of propylene via propane dehydrogenation (PDH) is a key reaction in the chemical industry. By combining operando transmission electron microscopy with density functional theory analysis, we show that the intercalation and ordering of carbon on Pt interstitials to form Pt-C solid solutions is relevant for increasing propylene production. More specifically, we found that at the point of enhanced propylene formation, the structure of platinum nanoparticles is transformed into a transient caesium chloride-type Pt-C polymorph. At more elevated temperatures, the zincblende and rock salt polymorphs seemingly coexist. When propylene production was highest, multiple crystal structures consisting of Pt and carbon were occasionally found to coexist in one individual nanoparticle, distorting the Pt lattice. Catalyst coking was detected at all stages of the reaction, but did initially not affect all particles. These findings could lead to the development of novel synthesis strategies towards tailoring highly efficient PDH catalysts.

On the Operando Structure of Ruthenium Oxides during the Oxygen Evolution Reaction in Acidic Media.

In the search for rational design strategies for oxygen evolution reaction (OER) catalysts, linking the catalyst structure to activity and stability is key. However, highly active catalysts such as IrOx and RuOx undergo structural changes under OER conditions, and hence, structure-activity-stability relationships need to take into account the operando structure of the catalyst. Under the highly anodic conditions of the oxygen evolution reaction (OER), electrocatalysts are often converted into an active form. Here, we studied this activation for amorphous and crystalline ruthenium oxide using X-ray absorption spectroscopy (XAS) and electrochemical scanning electron microscopy (EC-SEM). We tracked the evolution of surface oxygen species in ruthenium oxides while in parallel mapping the oxidation state of the Ru atoms to draw a complete picture of the oxidation events that lead to the OER active structure. Our data show that a large fraction of the OH groups in the oxide are deprotonated under OER conditions, leading to a highly oxidized active material. The oxidation is centered not only on the Ru atoms but also on the oxygen lattice. This oxygen lattice activation is particularly strong for amorphous RuOx. We propose that this property is key for the high activity and low stability observed for amorphous ruthenium oxide.

Assessment of the Degradation Mechanisms of Cu Electrodes during the CO2 Reduction Reaction.

Catalyst degradation and product selectivity changes are two of the key challenges in the electrochemical reduction of CO2 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 CO2 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 CO2 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 CO2 into hydrocarbons and oxygenated products.

The rise of electrochemical NAPXPS operated in the soft X-ray regime exemplified by the oxygen evolution reaction on IrOx electrocatalysts.

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.

Surface Electron-Hole Rich Species Active in the Electrocatalytic Water Oxidation.

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.

Isolated Pd atoms in a silver matrix: Spectroscopic and chemical properties.

Over the past decade, single-atom alloys (SAAs) have been a lively topic of research due to their potential for achieving novel catalytic properties and circumventing some known limitations of heterogeneous catalysts, such as scaling relationships. In researching SAAs, it is important to recognize experimental evidence of peculiarities in their electronic structure. When an isolated atom is embedded in a matrix of foreign atoms, it exhibits spectroscopic signatures that reflect its surrounding chemical environment. In the present work, using photoemission spectroscopy and computational chemistry, we discuss the experimental evidence from Ag0.98Pd0.02 SAAs that show free-atom-like characteristics in their electronic structure. In particular, the broad Pd4d valence band states of the bulk Pd metal become a narrow band in the alloy. The measured photoemission spectra were compared with the calculated photoemission signal of a free Pd atom in the gas phase with very good agreement, suggesting that the Pd4d states in the alloy exhibit very weak hybridization with their surroundings and are therefore electronically isolated. Since AgPd alloys are known for their superior performance in the industrially relevant semi-hydrogenation of acetylene, we considered whether it is worthwhile to drive the dilution of Pd in the inert Ag host to the single-atom level. We conclude that although site-isolation provides beneficial electronic structure changes to the Pd centers due to the difficulty in activating H2 on Ag, utilizing such SAAs in acetylene semi-hydrogenation would require either a higher Pd concentration to bring isolated sites sufficiently close together or an H2-activating support.

Molecular Analysis of the Unusual Stability of an IrNbOx Catalyst for the Electrochemical Water Oxidation to Molecular Oxygen (OER).

Adoption of proton exchange membrane (PEM) water electrolysis technology on a global level will demand a significant reduction of today's iridium loadings in the anode catalyst layers of PEM electrolyzers. However, new catalyst and electrode designs with reduced Ir content have been suffering from limited stability caused by (electro)chemical degradation. This has remained a serious impediment to a wider commercialization of larger-scale PEM electrolysis technology. In this combined DFT computational and experimental study, we investigate a novel family of iridium-niobium mixed metal oxide thin-film catalysts for the oxygen evolution reaction (OER), some of which exhibit greatly enhanced stability, such as minimized voltage degradation and reduced Ir dissolution with respect to the industry benchmark IrOx catalyst. More specifically, we report an unusually durable IrNbOx electrocatalyst with improved catalytic performance compared to an IrOx benchmark catalyst prepared in-house and a commercial benchmark catalyst (Umicore Elyst Ir75 0480) at significantly reduced Ir catalyst cost. Catalyst stability was assessed by conventional and newly developed accelerated degradation tests, and the mechanistic origins were analyzed and are discussed. To achieve this, the IrNbOx mixed metal oxide catalyst and its water splitting kinetics were investigated by a host of techniques such as synchrotron-based NEXAFS analysis and XPS, electrochemistry, and ab initio DFT calculations as well as STEM-EDX cross-sectional analysis. These analyses highlight a number of important structural differences to other recently reported bimetallic OER catalysts in the literature. On the methodological side, we introduce, validate, and utilize a new, nondestructive XRF-based catalyst stability monitoring technique that will benefit future catalyst development. Furthermore, the present study identifies new specific catalysts and experimental strategies for stepwise reducing the Ir demand of PEM water electrolyzers on their long way toward adoption at a larger scale.

Key role of chemistry versus bias in electrocatalytic oxygen evolution.

The oxygen evolution reaction has an important role in many alternative-energy schemes because it supplies the protons and electrons required for converting renewable electricity into chemical fuels1-3. Electrocatalysts accelerate the reaction by facilitating the required electron transfer4, as well as the formation and rupture of chemical bonds5. This involvement in fundamentally different processes results in complex electrochemical kinetics that can be challenging to understand and control, and that typically depends exponentially on overpotential1,2,6,7. Such behaviour emerges when the applied bias drives the reaction in line with the phenomenological Butler-Volmer theory, which focuses on electron transfer8, enabling the use of Tafel analysis to gain mechanistic insight under quasi-equilibrium9-11 or steady-state assumptions12. However, the charging of catalyst surfaces under bias also affects bond formation and rupture13-15, the effect of which on the electrocatalytic rate is not accounted for by the phenomenological Tafel analysis8 and is often unknown. Here we report pulse voltammetry and operando X-ray absorption spectroscopy measurements on iridium oxide to show that the applied bias does not act directly on the reaction coordinate, but affects the electrocatalytically generated current through charge accumulation in the catalyst. We find that the activation free energy decreases linearly with the amount of oxidative charge stored, and show that this relationship underlies electrocatalytic performance and can be evaluated using measurement and computation. We anticipate that these findings and our methodology will help to better understand other electrocatalytic materials and design systems with improved performance.

On the Activity/Selectivity and Phase Stability of Thermally Grown Copper Oxides during the Electrocatalytic Reduction of CO2.

Revealing the active nature of oxide-derived copper is of key importance to understand its remarkable catalytic performance during the cathodic CO2 reduction reaction (CO2RR) to produce valuable hydrocarbons. Using advanced spectroscopy, electron microscopy, and electrochemically active surface area characterization techniques, the electronic structure and the changes in the morphology/roughness of thermally oxidized copper thin films were revealed during CO2RR. For this purpose, we developed an in situ cell for X-ray spectroscopy that could be operated accurately in the presence of gases or liquids to clarify the role of the initial thermal oxide phase and its active phase during the electrocatalytic reduction of CO2. It was found that the Cu(I) species formed during the thermal treatment are readily reduced to Cu0 during the CO2RR, whereas Cu(II) species are hardly reduced. In addition, Cu(II) oxide electrode dissolution was found to yield a porous/void structure, where the lack of electrical connection between isolated islands prohibits the CO2RR. Therefore, the active/stable phase for CO2RR is metallic copper, independent of its initial phase, with a significant change in its morphology upon its reduction yielding the formation of a rougher surface with a higher number of underco-ordinated sites. Thus, the initial thermal oxidation of copper in air controls the reaction activity/selectivity because of the changes induced in the electrode surface morphology/roughness and the presence of more undercoordinated sites during the CO2RR.

Revealing the Active Phase of Copper during the Electroreduction of CO2 in Aqueous Electrolyte by Correlating In Situ X-ray Spectroscopy and In Situ Electron Microscopy.

The variation in the morphology and electronic structure of copper during the electroreduction of CO2 into valuable hydrocarbons and alcohols was revealed by combining in situ surface- and bulk-sensitive X-ray spectroscopies with electrochemical scanning electron microscopy. These experiments proved that the electrified interface surface and near-surface are dominated by reduced copper. The selectivity to the formation of the key C-C bond is enhanced at higher cathodic potentials as a consequence of increased copper metallicity. In addition, the reduction of the copper oxide electrode and oxygen loss in the lattice reconstructs the electrode to yield a rougher surface with more uncoordinated sites, which controls the dissociation barrier of water and CO2. Thus, according to these results, copper oxide species can only be stabilized kinetically under CO2 reduction reaction conditions.

Formation of a 2D Meta-stable Oxide by Differential Oxidation of AgCu Alloys.

Metal alloy catalysts can develop complex surface structures when exposed to reactive atmospheres. The structures of the resulting surfaces have intricate relationships with a myriad of factors, such as the affinity of the individual alloying elements to the components of the gas atmosphere and the bond strengths of the multitude of low-energy surface compounds that can be formed. Identifying the atomic structure of such surfaces is a prerequisite for establishing structure-property relationships, as well as for modeling such catalysts in ab initio calculations. Here, we show that an alloy, consisting of an oxophilic metal (Cu) diluted into a noble metal (Ag), forms a meta-stable two-dimensional oxide monolayer, when the alloy is subjected to oxidative reaction conditions. The presence of this oxide is correlated with selectivity in the corresponding test reaction of ethylene epoxidation. In the present study, using a combination of in situ, ex situ, and theoretical methods (NAP-XPS, XPEEM, LEED, and DFT), we determine the structure to be a two-dimensional analogue of Cu2O, resembling a single lattice plane of Cu2O. The overlayer holds a pseudo-epitaxial relationship with the underlying noble metal. Spectroscopic evidence shows that the oxide's electronic structure is qualitatively distinct from its three-dimensional counterpart, and because of weak electronic coupling with the underlying noble metal, it exhibits metallic properties. These findings provide precise details of this peculiar structure and valuable insights into how alloying can enhance catalytic properties.

Evolution of Oxygen-Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In†Situ Soft X-Ray Spectroscopy.

Manganese oxide (MnOx ) electrocatalysts are examined herein by in situ soft X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) during the oxidation of water buffered by borate (pH 9.2) at potentials from 0.75 to 2.25 V vs. the reversible hydrogen electrode. Correlation of L-edge XAS data with previous mechanistic studies indicates MnIV is the highest oxidation state involved in the catalytic mechanism. MnOx is transformed into birnessite at 1.45 V and does not undergo further structural phase changes. At potentials beyond this transformation, RIXS spectra show progressive enhancement of charge transfer transitions from oxygen to manganese. Theoretical analysis of these data indicates increased hybridization of the Mn-O orbitals and withdrawal of electron density from the O ligand shell. In situ XAS experiments at the O K-edge provide complementary evidence for such a transition. This step is crucial for the formation of O2 from water.

Are multiple oxygen species selective in ethylene epoxidation on silver?

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 (Oads) 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 Oads 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 Oads 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.

Ethylene Epoxidation at the Phase Transition of Copper Oxides.

Catalytic materials tend to be metastable. When a material becomes metastable close to a thermodynamic phase transition it can exhibit unique catalytic behavior. Using in situ photoemission spectroscopy and online product analysis, we have found that close to the Cu2O-CuO phase transition there is a boost in activity for a kinetically driven reaction, ethylene epoxidation, giving rise to a 20-fold selectivity enhancement relative to the selectivity observed far from the phase transition. By tuning conditions toward low oxygen chemical potential, this metastable state and the resulting enhanced selectivity can be sustained. Using density functional theory, we find that metastable O precursors to the CuO phase can account for the selectivity enhancements near the phase transition.

In situ observation of reactive oxygen species forming on oxygen-evolving iridium surfaces.

Water splitting performed in acidic media relies on the exceptional performance of iridium-based materials to catalyze the oxygen evolution reaction (OER). In the present work, we use in situ X-ray photoemission and absorption spectroscopy to resolve the long-standing debate about surface species present in iridium-based catalysts during the OER. We find that the surface of an initially metallic iridium model electrode converts into a mixed-valent, conductive iridium oxide matrix during the OER, which contains OII- and electrophilic OI- species. We observe a positive correlation between the OI- concentration and the evolved oxygen, suggesting that these electrophilic oxygen sites may be involved in catalyzing the OER. We can understand this observation by analogy with photosystem II; their electrophilicity renders the OI- species active in O-O bond formation, i.e. the likely potential- and rate-determining step of the OER. The ability of amorphous iridium oxyhydroxides to easily host such reactive, electrophilic species can explain their superior performance when compared to plain iridium metal or crystalline rutile-type IrO2.

Reactive oxygen species in iridium-based OER catalysts.

Tremendous effort has been devoted towards elucidating the fundamental reasons for the higher activity of hydrated amorphous IrIII/IV oxyhydroxides (IrO x ) in the oxygen evolution reaction (OER) in comparison with their crystalline counterpart, rutile-type IrO2, by focusing on the metal oxidation state. Here we demonstrate that, through an analogy to photosystem II, the nature of this reactive species is not solely a property of the metal but is intimately tied to the electronic structure of oxygen. We use a combination of synchrotron-based X-ray photoemission and absorption spectroscopies, ab initio calculations, and microcalorimetry to show that holes in the O 2p states in amorphous IrO x give rise to a weakly bound oxygen that is extremely susceptible to nucleophilic attack, reacting stoichiometrically with CO already at room temperature. As such, we expect this species to play the critical role of the electrophilic oxygen involved in O-O bond formation in the electrocatalytic OER on IrO x . We propose that the dynamic nature of the Ir framework in amorphous IrO x imparts the flexibility in Ir oxidation state required for the formation of this active electrophilic oxygen.

Thermodynamic and spectroscopic properties of oxygen on silver under an oxygen atmosphere.

We report on a combined density functional theory and the experimental study of the O1s binding energies and X-ray Absorption Near Edge Structure (XANES) of a variety of oxygen species on Ag(111) and Ag(110) surfaces. Our theoretical spectra agree with our measured results for known structures, including the p(N× 1) reconstruction of the Ag(110) surface and the p(4 × 4) reconstruction of the Ag(111) surface. Combining the O1s binding energy and XANES spectra yields unique spectroscopic fingerprints, allowing us to show that unreconstructed atomic oxygen is likely not present on either surface under equilibrium conditions at oxygen chemical potentials typical for ethylene epoxidation. Furthermore, we find no adsorbed or dissolved atomic species whose calculated spectroscopic features agree with those measured for the oxygen species believed to catalyze the partial oxidation of ethylene.

Adsorbate induced vacancy formation on silver surfaces.

The energy required to form and remove vacancies on metal surfaces mediates the rate of mass transport during a wide range of processes. These energies are known to be sensitive to environmental conditions. Here, we use electronic structure density functional theory calculations to show that the surface vacancy formation energy of silver changes markedly in the presence of adsorbed and dissolved oxygen. We found that adsorbed atomic oxygen can reduce the surface vacancy formation energy of the Ag(111) surface by more than 30%, whereas surface vacancy formation becomes exothermic in the presence of pure subsurface oxygen. We went on to show that the total directionality of the topologically defined bond paths can be used to understand these changes. The resulting structure-property relationship was used to predict the behavior of silver in different atmospheres. We show that the surface vacancy formation energy decreases when electronegative elements are adsorbed on the surface, but that it can increase when electropositive elements are adsorbed.