Role of Fe decoration on the oxygen evolving state of Co3O4 nanocatalysts.

The production of green hydrogen through alkaline water electrolysis is the key technology for the future carbon-neutral industry. Nanocrystalline Co3O4 catalysts are highly promising electrocatalysts for the oxygen evolution reaction and their activity strongly benefits from Fe surface decoration. However, limited knowledge of decisive catalyst motifs at the atomic level during oxygen evolution prevents their knowledge-driven optimization. Here, we employ a variety of operando spectroscopic methods to unveil how Fe decoration increases the catalytic activity of Co3O4 nanocatalysts as well as steer the (near-surface) active state formation. Our study shows a link of the termination-dependent Fe decoration to the activity enhancement and a significantly stronger Co3O4 near-surface (structural) adaptation under the reaction conditions. The near-surface Fe- and Co-O species accumulate an oxidative charge and undergo a reversible bond contraction during the catalytic process. Moreover, our work demonstrates the importance of low coordination surface sites on the Co3O4 host to ensure an efficient Fe-induced activity enhancement, providing another puzzle piece to facilitate optimized catalyst design.

Structural and Chemical Properties of NiOx Thin Films: Oxygen Vacancy Formation in O2 Atmosphere.

NiOx films on Si(111) were put in contact with oxygen at elevated temperatures. During heating and cooling in oxygen atmosphere Near Ambient Pressure (NAP)-XPS and -XAS and work function (WF) measurements reveal the creation and replenishing of oxygen vacancies in dependence of temperature. Oxygen vacancies manifest themselves as a distinct O1s feature at 528.9 eV on the low binding energy side of the main NiO peak as well as by a distinct deviation of the Ni2p3/2 spectral features from the typical NiO spectra. DFT calculations reveal that the presence of oxygen vacancies leads to a charge redistribution and altered bond lengths of the atoms surrounding the vacancies causing the observed spectral changes. Furthermore, we observed that a broadening of the lowest energy peak in the O K-edge spectra can be attributed to oxygen vacancies. In the presence of oxygen vacancies, the WF is lowered by 0.1 eV.

Structural and chemical properties of NiOx thin films: the role of oxygen vacancies in NiOOH formation in a H2O atmosphere.

NiOx films grown from 50 nm thick Ni on Si(111) were put in contact with oxygen and subsequently water vapor at elevated temperatures. Near ambient pressure (NAP)-XPS and -XAS reveal the formation of oxygen vacancies at elevated temperatures, followed by H2O dissociation and saturation of the oxygen vacancies with chemisorbing OH. Through repeated heating and cooling, OH-saturated oxygen vacancies act as precursors for the formation of thermally stable NiOOH on the sample surface. This is accompanied by a significant restructuring of the surface which increases the probability of NiOOH formation. Exposure of a thin NiOx film to H2O can lead to a partial reduction of NiOx to metallic Ni accompanied by a distinct shift of the NiOx spectra with respect to the Fermi edge. DFT calculations show that the formation of oxygen vacancies and subsequently Ni0 leads to a state within the band gap of NiO which pins the Fermi edge.

Synthesis of Few-Layered Transition-Metal Dichalcogenides by Ion Implantation of Chalcogen and Metal Species into Sapphire.

The growth of transition-metal dichalcogenides (TMDCs) has been performed so far using most established thin-film growth techniques (e.g., vapor phase transport, chemical vapor deposition, molecular beam epitaxy, etc.). However, because there exists no self-limiting mechanism for the growth of TMDCs, none of these techniques allows precise control of the number of TMDC layers over large substrate areas. Here, we explore the ion implantation of the parent TMDC atoms into a chemically neutral substrate for the synthesis of TMDC films. The idea is that once all of the ion-implanted species have reacted together, the synthesis reaction stops, thereby effectively stopping growth. In other words, even if there is no self-limiting mechanism, growth stops when the nutrients are exhausted. We have co-implanted Mo and S ions into c-oriented sapphire substrates using various doses corresponding to 1- to 5-layer atom counts. We find that the subsurface region of the sapphire substrates is amorphized by the ion implantation process, at least for implanted doses of 2-layer atom counts and over. For all doses, we have observed the formation of MoS2 material inside the sapphire after postimplantation annealing between 800 and 850 °C. We report that the order of implantation (i.e., whether S or Mo is implanted first) is an important parameter. More precisely, samples for which S is implanted first tend to yield thin crystals with a large lateral extension (more than 200 nm for 5-layer doses) and mainly located at the interface between the amorphized and crystalline sapphire. When Mo is first implanted, the MoS2 crystals still predominantly appear at the amorphous-crystalline interface (which is much rougher), but they are much thicker, suggesting a different nucleation mechanism.

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.

Interfacial Chemistry in the Electrocatalytic Hydrogenation of CO2 over C-Supported Cu-Based Systems.

Operando soft and hard X-ray spectroscopic techniques were used in combination with plane-wave density functional theory (DFT) simulations to rationalize the enhanced activities of Zn-containing Cu nanostructured electrocatalysts in the electrocatalytic CO2 hydrogenation reaction. We show that at a potential for CO2 hydrogenation, Zn is alloyed with Cu in the bulk of the nanoparticles with no metallic Zn segregated; at the interface, low reducible Cu(I)-O species are consumed. Additional spectroscopic features are observed, which are identified as various surface Cu(I) ligated species; these respond to the potential, revealing characteristic interfacial dynamics. Similar behavior was observed for the Fe-Cu system in its active state, confirming the general validity of this mechanism; however, the performance of this system deteriorates after successive applied cathodic potentials, as the hydrogen evolution reaction then becomes the main reaction pathway. In contrast to an active system, Cu(I)-O is now consumed at cathodic potentials and not reversibly reformed when the voltage is allowed to equilibrate at the open-circuit voltage; rather, only the oxidation to Cu(II) is observed. We show that the Cu-Zn system represents the optimal active ensembles with stabilized Cu(I)-O; DFT simulations rationalize this observation by indicating that Cu-Zn-O neighboring atoms are able to activate CO2, whereas Cu-Cu sites provide the supply of H atoms for the hydrogenation reaction. Our results demonstrate an electronic effect exerted by the heterometal, which depends on its intimate distribution within the Cu phase and confirms the general validity of these mechanistic insights for future electrocatalyst design strategies.

Structural Model for Transient Pt Oxidation during Fuel Cell Start-up Using Electrochemical X-ray Photoelectron Spectroscopy.

Potential spikes during the start-up and shutdown of fuel cells are a major cause of platinum electrocatalyst degradation, which limits the lifetime of the device. The electrochemical oxidation of platinum (Pt) that occurs on the cathode during the potential spikes plays a key role in this degradation process. However, the composition of the oxide species formed as well as their role in catalyst dissolution remains unclear. In this study, we employ a special arrangement of XPS (X-ray photoelectron spectroscopy), in which the platinum electrocatalyst is covered by a graphene spectroscopy window, making the in situ examination of the oxidation/reduction reaction under wet conditions possible. We use this assembly to investigate the change in the oxidation states of Pt within the potential window relevant to fuel cell operation. We show that above 1.1 VRHE (potential vs reversible hydrogen electrode), a mixed Ptδ+/Pt2+/Pt4+ surface oxide is formed, with an average oxidation state that gradually increases as the potential is increased. By comparing a model based on the XPS data to the oxidation charge measured during potential spikes, we show that our description of Pt oxidation is also valid during the transient conditions of fuel cell start-up and shutdown. This is due to the rapid Pt oxidation kinetics during the pulses. As a result of the irreversibility of Pt oxidation, some remnants of oxidized Pt remain at typical fuel cell operating potentials after a pulse.

Dynamics over a Cu-graphite electrode during the gas-phase CO2 reduction investigated by APXPS.

The electrocatalytic conversion of CO2 to fuels and chemicals using renewable energy is a key decarbonization technology. From a technological viewpoint, the realization of such process in the gas phase and at room temperature is considered advantageous as it allows one to circumvent the limited CO2 solubility in liquid electrolytes and CO2 transport across the electrical double layer. Yet, electrocatalysts' performances reported so far are promising but not satisfactory. To inform the design of new materials, in this study, we apply ambient pressure X-ray photoelectron and absorption spectroscopies coupled with on-line gas detection via mass spectrometry to investigate in situ performance and interface chemistry of an electrodeposited Cu on graphitic carbon support under conditions of CO2 reduction. We use the ISISS beamline at the synchrotron facility BESSY II of the HZB and the electrochemical cell based on polymeric electrolyte membrane previously developed. We show that under cathodic potential in which methanol is formed, a fraction of the electrode with a predominantly Cu(I) electronic structure undergoes reduction to metallic Cu. The C speciation is characterized by C-O and sp3 CH3 species whereas no atomic C was formed under this condition. We also show the important role of water in the formation of methanol from accumulated surface CH3 species.

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.

Insights into the electronic structure of hydroxyl on Ag(110) under near ambient conditions.

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.

X-ray Absorption Near-Edge Structure (XANES) at the O K-Edge of Bulk Co3O4: Experimental and Theoretical Studies.

We combine theoretical and experimental X-ray absorption near-edge spectroscopy (XANES) to probe the local environment around cationic sites of bulk spinel cobalt tetraoxide (Co3O4). Specifically, we analyse the oxygen K-edge spectrum. We find an excellent agreement between our calculated spectra based on the density functional theory and the projector augmented wave method, previous calculations as well as with the experiment. The oxygen K-edge spectrum shows a strong pre-edge peak which can be ascribed to dipole transitions from O 1s to O 2p states hybridized with the unoccupied 3d states of cobalt atoms. Also, since Co3O4 contains two types of Co atoms, i.e., Co3+ and Co2+, we find that contribution of Co2+ ions to the pre-edge peak is solely due to single spin-polarized t2g orbitals (dxz, dyz, and dxy) while that of Co3+ ions is due to spin-up and spin-down polarized eg orbitals (dx2-y2 and dz2). Furthermore, we deduce the magnetic moments on the Co3+ and Co2+ to be zero and 3.00 µB respectively. This is consistent with an earlier experimental study which found that the magnetic structure of Co3O4 consists of antiferromagnetically ordered Co2+ spins, each of which is surrounded by four nearest neighbours of oppositely directed spins.

Hydroxylation of Platinum Surface Oxides Induced by Water Vapor.

With its high stability and well-tuned binding strength for adsorbates, platinum is an excellent catalyst for a wide range of reactions. In applications like car exhaust purification, the oxidation of hydrocarbons, and fuel cells, platinum is exposed to highly oxidizing conditions, which often leads to the formation of surface oxides. To reveal the structure of these surface oxides, the oxidation of Pt in O2 has been widely studied. However, in most applications, H2O is also an important or even dominant part of the reaction mixture. Here, we investigate the interaction of H2O with Pt surface oxides using near-ambient-pressure X-ray photoelectron spectroscopy. We find that reversible hydroxylation readily occurs in H2O/O2 mixtures. Using time-resolved measurements, we show that O-OH exchange occurs on a time scale of seconds.

Near-Ambient Pressure XPS and MS Study of CO Oxidation over Model Pd-Au/HOPG Catalysts: The Effect of the Metal Ratio.

In this study, the dependence of the catalytic activity of highly oriented pyrolytic graphite (HOPG)-supported bimetallic Pd-Au catalysts towards the CO oxidation based on the Pd/Au atomic ratio was investigated. The activities of two model catalysts differing from each other in the initial Pd/Au atomic ratios appeared as distinctly different in terms of their ignition temperatures. More specifically, the PdAu-2 sample with a lower Pd/Au surface ratio (~0.75) was already active at temperatures less than 150 °C, while the PdAu-1 sample with a higher Pd/Au surface ratio (~1.0) became active only at temperatures above 200 °C. NAP XPS revealed that the exposure of the catalysts to a reaction mixture at RT induces the palladium surface segregation accompanied by an enrichment of the near-surface regions of the two-component Pd-Au alloy nanoparticles with Pd due to adsorption of CO on palladium atoms. The segregation extent depends on the initial Pd/Au surface ratio. The difference in activity between these two catalysts is determined by the presence or higher concentration of specific active Pd sites on the surface of bimetallic particles, i.e., by the ensemble effect. Upon cooling the sample down to room temperature, the reverse redistribution of the atomic composition within near-surface regions occurs, which switches the catalyst back into inactive state. This observation strongly suggests that the optimum active sites emerge under reaction conditions exclusively, involving both high temperature and a reactive atmosphere.

The Effect of Water on the 2-Propanol Oxidation Activity of Co-Substituted LaFe1- Cox O3 Perovskites.

Perovskites are interesting oxidation catalysts due to their chemical flexibility enabling the tuning of several properties. In this work, we synthesized LaFe1-x Cox O3 catalysts by co-precipitation and thermal decomposition, characterized them thoroughly and studied their 2-propanol oxidation activity under dry and wet conditions to bridge the knowledge gap between gas and liquid phase reactions. Transient tests showed a highly active, unstable low-temperature (LT) reaction channel in conversion profiles and a stable, less-active high-temperature (HT) channel. Cobalt incorporation had a positive effect on the activity. The effect of water was negative on the LT channel, whereas the HT channel activity was boosted for x>0.15. The boost may originate from a slower deactivation rate of the Co3+ sites under wet conditions and a higher amount of hydroxide species on the surface comparing wet to dry feeds. Water addition resulted in a slower deactivation for Co-rich catalysts and higher activity in the HT channel state.

Identification of the surface species in electrochemical promotion: ethylene oxidation over a Pt/YSZ catalyst.

The electrochemical promotion of the C2H4 + O2 total oxidation reaction over a Pt catalyst, interfaced to yttrium stabilized zirconia (YSZ), has been studied at 0.25 mbar and T = 650 K using near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) as an in situ method. The electrochemical promoter effect is linked to the presence of a several layers thick graphitic overlayer that forms on the Pt surface in the presence of C2H4. Our NAP-XPS investigation reveals that electrochemical pumping of the Pt/YSZ catalyst, using a positive potential, leads to the spillover of oxygen surface species from the YSZ support onto the surface of the Pt electrode. Based on the XP spectra, the spillover species on Pt is identical to oxygen chemisorbed from the gas-phase.

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.

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.