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The efficiency of electrolysis is reduced due to the sluggish oxygen evolution reaction (OER). Besides catalyst properties, electrocatalytic activity also depends on the interaction of the electrocatalyst with the electrolyte. Here, we show that the addition of small amounts of Li+ to Fe-free NaOH or KOH electrolytes activates NiFeOOH for the OER compared to single-cation electrolytes. Moreover, the activation was maintained when the solution was returned to pure NaOH. Importantly, we show that the origin of activation by Li+ cations is primarily non-kinetic in nature, as the OER onset for the mixed electrolyte does not change and the Tafel slope at low current density is ~30â mV/dec in both electrolytes. However, the increase of the apparent Tafel slope remains lower at increasing current densities in the presence of Li+. Based on electrochemical quartz crystal microbalance and in situ X-ray absorption spectroscopy measurements, we show that this reduction of non-kinetic effects is due to enhanced intercalation of sodium, water and hydroxide. This enhanced electrolyte penetration facilitates the OER, especially at higher current densities and for increased catalyst loading. Our work shows that mixed electrolytes where distinct cations can have different roles provide a simple and promising strategy towards improved OER rates.
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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.
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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.
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For electrocatalysts with a layered structure, ion intercalation is a common phenomenon. Gaining reliable information about the intercalation of ions from the electrolyte is indispensable for a better understanding of the catalytic performance of these electrocatalysts. Here, we take a holistic approach for following intercalation processes by studying the dynamics of the catalyst, water molecules, and ions during intercalation using operando soft X-ray absorption spectroscopy (XAS). Sodium and oxygen K-edge and nickel L-edge spectra were used to investigate the Na+ intercalation in a Ni0.8Fe0.2Ox electrocatalyst during the oxygen evolution reaction (OER) in NaOH (0.1 M). The Na K-edge spectra show an irreversible intensity increase upon initial potential cycling and a reversible intensity increase at the intercalation potential, 1.45 VRHE, coinciding with an increase in the Ni oxidation state. Simultaneously, the O K-edge spectra show that the Na+ intercalation does not significantly impact the hydration of the catalyst.
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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.
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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.
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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.
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Electrochemistry is a promising building block for the global transition to a sustainable energy market. Particularly the electroreduction of CO2 and the electrolysis of water might be strategic elements for chemical energy conversion. The reactions of interest are inner-sphere reactions, which occur on the surface of the electrode, and the biased interface between the electrode surface and the electrolyte is of central importance to the reactivity of an electrode. However, a potential-dependent observation of this buried interface is challenging, which slows the development of catalyst materials. Here we describe a sample architecture using a graphene blanket that allows surface sensitive studies of biased electrochemical interfaces. At the examples of near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and environmental scanning electron microscopy (ESEM), we show that the combination of a graphene blanket and a permeable membrane leads to the formation of a liquid thin film between them. This liquid thin film is stable against a water partial pressure below 1 mbar. These properties of the sample assembly extend the study of solid-liquid interfaces to highly surface sensitive techniques, such as electron spectroscopy/microscopy. In fact, photoelectrons with an effective attenuation length of only 10 Å can be detected, which is close to the absolute minimum possible in aqueous solutions. The in-situ cells and the sample preparation necessary to employ our method are comparatively simple. Transferring this approach to other surface sensitive measurement techniques should therefore be straightforward. We see our approach as a starting point for more studies on electrochemical interfaces and surface processes under applied potential. Such studies would be of high value for the rational design of electrocatalysts.
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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.
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The hydrodesulfurization process is one of the cornerstones of the chemical industry, removing harmful sulfur from oil to produce clean hydrocarbons. The reaction is catalyzed by the edges of MoS2 nanoislands and is operated in hydrogen-oil mixtures at 5-160 bar and 260-380 °C. Until now, it has remained unclear how these harsh conditions affect the structure of the catalyst. Using a special-purpose high-pressure scanning tunneling microscope, we provide direct observations of an active MoS2 model catalyst under reaction conditions. We show that the active edge sites adapt their sulfur, hydrogen, and hydrocarbon coverages depending on the gas environment. By comparing these observations to density functional theory calculations, we propose that the dominant edge structure during the desulfurization of CH3SH contains a mixture of adsorbed sulfur and CH3SH.
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While continuum descriptions of oxide film growth are well established, the local structural dynamics during oxide growth are largely unexplored. Here, we investigate this using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) for the example of alumina film growth on NiAl(110) following NO2 exposure. To maintain a well-defined system, we have adopted a cyclic growth approach of NO2 adsorption and annealing. NO2 adsorption at 693 K results in the formation of a vacancy island pattern in the NiAl(110) substrate, which is filled with AlOx by diffusion of O through the alumina film. The patches of AlOx coalesce to form smooth terraces upon annealing to 1200 K. By repeated cycling, we have grown films of up to 0.9 nm thick. While peak shifts in the XPS spectra indicate that the film maintains its insulating character upon thickening, our STM data show that there is a finite density of states within the band gap. The thickening of the alumina film is accompanied by the formation of trenches in the surface, which we interpret to be the result of film stress relief.
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A combined X-ray and scanning tunneling microscopy (STM) instrument is presented that enables the local detection of X-ray absorption on surfaces in a gas environment. To suppress the collection of ion currents generated in the gas phase, coaxially shielded STM tips were used. The conductive outer shield of the coaxial tips can be biased to deflect ions away from the tip core. When tunneling, the X-ray-induced current is separated from the regular, 'topographic' tunneling current using a novel high-speed separation scheme. We demonstrate the capabilities of the instrument by measuring the local X-ray-induced current on Au(1â¯1â¯1) in 800â¯mbar Ar.
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We have developed a new instrument combining a scanning probe microscope (SPM) and an X-ray scattering platform for ambient-pressure catalysis studies. The two instruments are integrated with a flow reactor and an ultra-high vacuum system that can be mounted easily on the diffractometer at a synchrotron end station. This makes it possible to perform SPM and X-ray scattering experiments in the same instrument under identical conditions that are relevant for catalysis.