In the search for rational design strategies for oxygenevolutionreaction (OER) catalysts, linking the catalyst structure to activityand stability is key. However, highly active catalysts such as... Show moreIn the search for rational design strategies for oxygenevolutionreaction (OER) catalysts, linking the catalyst structure to activityand stability is key. However, highly active catalysts such as IrO x and RuO x undergostructural changes under OER conditions, and hence, structure-activity-stabilityrelationships need to take into account the operando structure ofthe catalyst. Under the highly anodic conditions of the oxygen evolutionreaction (OER), electrocatalysts are often converted into an activeform. Here, we studied this activation for amorphous and crystallineruthenium oxide using X-ray absorption spectroscopy (XAS) and electrochemicalscanning electron microscopy (EC-SEM). We tracked the evolution ofsurface oxygen species in ruthenium oxides while in parallel mappingthe oxidation state of the Ru atoms to draw a complete picture ofthe oxidation events that lead to the OER active structure. Our datashow that a large fraction of the OH groups in the oxide are deprotonatedunder OER conditions, leading to a highly oxidized active material.The oxidation is centered not only on the Ru atoms but also on theoxygen lattice. This oxygen lattice activation is particularly strongfor amorphous RuO x . We propose that thisproperty is key for the high activity and low stability observed foramorphous ruthenium oxide. Show less
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... Show morePhotoelectron 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. Show less
Velasco-Velez, J.J.; Jones, T.E.; Streibel, V.; Havecker, M.; Chuang, C.H.; Frevel, L.; ... ; Knop-Gericke, A. 2019
An electrode for the oxygen evolution reaction based on a conductive bi-layered free standing graphene support functionalized with iridium nanoparticles was fabricated and characterized by means of... Show moreAn electrode for the oxygen evolution reaction based on a conductive bi-layered free standing graphene support functionalized with iridium nanoparticles was fabricated and characterized by means of potentiometric and advanced X-ray spectroscopic techniques. It was found that the electrocatalytic activity of iridium nanoparticles is associated to the formation of Ir 5d electron holes. Strong Ir 5d and O 2p hybridization, however, leads to a concomitant increase O 2p hole character, making oxygen electron deficient and susceptible to nucleophilic attack by water. Consequently, more efficient electrocatalysts can be synthesized by increasing the number of electron-holes shared between the metal d and oxygen 2p. Show less
Vakili, M.; Kitaura, F.-S.; Feng, Y.; Yepes, G.; Zhao, C.; Chuang, C.H.; Hahn, C. 2017
A flat Friedmann–Robertson–Walker universe dominated by a cosmological constant (Λ) and cold dark matter (CDM) has been the working model preferred by cosmologists since the discovery of cosmic... Show moreA flat Friedmann–Robertson–Walker universe dominated by a cosmological constant (Λ) and cold dark matter (CDM) has been the working model preferred by cosmologists since the discovery of cosmic acceleration1,2. However, tensions of various degrees of significance are known to be present among existing datasets within the ΛCDM framework3,4,5,6,7,8,9,10,11. In particular, the Lyman-α forest measurement of the baryon acoustic oscillations (BAO) by the Baryon Oscillation Spectroscopic Survey3 prefers a smaller value of the matter density fraction Ω M than that preferred by cosmic microwave background (CMB). Also, the recently measured value of the Hubble constant, H 0 = 73.24 ± 1.74 km s−1 Mpc−1 (ref. 12), is 3.4σ higher than the 66.93 ± 0.62 km s−1 Mpc−1 inferred from the Planck CMB data7. In this work, we investigate whether these tensions can be interpreted as evidence for a non-constant dynamical dark energy. Using the Kullback–Leibler divergence13 to quantify the tension between datasets, we find that the tensions are relieved by an evolving dark energy, with the dynamical dark energy model preferred at a 3.5σ significance level based on the improvement in the fit alone. While, at present, the Bayesian evidence for the dynamical dark energy is insufficient to favour it over ΛCDM, we show that, if the current best-fit dark energy happened to be the true model, it would be decisively detected by the upcoming Dark Energy Spectroscopic Instrument survey14. Show less
