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Hydrophobic cluster structures in aqueous ethanol solutions at different concentrations have been investigated by soft X-ray absorption spectroscopy (XAS). In the O K-edge XAS, we have found that hydrogen bond structures among water molecules are enhanced in the middle-concentration region by the hydrophobic interaction of the ethyl groups in ethanol. In the C K-edge XAS, the lower energy features arise from a transition from the terminal methyl C 1s electron to an unoccupied orbital of 3s Rydberg character, which is sensitive to the nearest-neighbor intermolecular interactions. From the comparison of C K-edge XAS with the inner-shell calculations, we have found that ethanol clusters are easily formed in the middle-concentration region due to the hydrophobic interaction of the ethyl group in ethanol, resulting in the enhancement of the hydrogen bond structures among water molecules. This behavior is different from aqueous methanol solutions, where the methanol-water mixed clusters are more predominant in the middle-concentration region due to the relatively weak hydrophobic interactions of the methyl group in methanol.

ACS catalysis 12, 3256 - 3268 (2022). doi:10.1021/acscatal.1c05169, Co oxides and oxyhydroxides have been studied extensively in the past as promising electrocatalysts for the oxygen evolution reaction (OER) in neutral to alkaline media. Earlier studies showed the formation of an ultrathin CoO$_x$(OH)$_y$ skin layer on Co$_3$O$_4$ at potentials above 1.15 V vs reversible hydrogen electrode (RHE), but the precise influence of this skin layer on the OER reactivity is still under debate. We present here a systematic study of epitaxial spinel-type Co$_3$O$_4$ films with defined (111) orientation, prepared on different substrates by electrodeposition or physical vapor deposition. The OER overpotential of these samples may vary up to 120 mV, corresponding to two orders of magnitude differences in current density, which cannot be accounted for by differences in the electrochemically active surface area. We demonstrate by a careful analysis of operando surface X-ray diffraction measurements that these differences are clearly correlated with the average thickness of the skin layer. The OER reactivity increases with the amount of formed skin layer, indicating that the entire three-dimensional skin layer is an OER-active interphase. Furthermore, a scaling relationship between the reaction centers in the skin layer and the OER activity is established. It suggests that two lattice sites are involved in the OER mechanism., Published by ACS, Washington, DC

Understanding the chemical past of our Sun and how life appeared on Earth is no mean feat. The best strategy we can adopt is to study newborn stars located in an environment similar to the one in which our Sun was born and assess their chemical content. In particular, hot corinos are prime targets since recent studies showed correlations between interstellar Complex Organic Molecules (iCOMs) abundances from hot corinos and comets. The ORion ALMA New GEneration Survey (ORANGES) aims to assess the number of hot corinos in the closest and best analogue to our Sun's birth environment, the OMC-2/3 filament. In this context, we investigated the chemical nature of 19 solar-mass protostars and found that 26\% of our sample sources shows warm methanol emission indicative of hot corinos. Compared to the Perseus low-mass star-forming region, where the PErseus ALMA CHEmistry Survey (PEACHES) detected $\sim 60$\% of hot corinos, the latter seem to be relatively scarce in the OMC-2/3 filament. While this suggests that the chemical nature of protostars in Orion and Perseus is different, improved statistics are needed in order to consolidate this result. If the two regions are truly different, this would indicate that the environment is likely playing a role in shaping the chemical composition of protostars., Comment: 16 pages, 8 figures, Accepted in ApJ

Imai et al., The chemical diversity of low-mass protostellar sources has so far been recognized, and environmental effects are invoked as its origin. In this context, observations of isolated protostellar sources without the influence of nearby objects are of particular importance. Here, we report the chemical and physical structures of the low-mass Class 0 protostellar source IRAS 16544−1604 in the Bok globule CB 68, based on 1.3 mm Atacama Large Millimeter/submillimeter Array observations at a spatial resolution of ∼70 au that were conducted as part of the large program FAUST. Three interstellar saturated complex organic molecules (iCOMs), CH3OH, HCOOCH3, and CH3OCH3, are detected toward the protostar. The rotation temperature and the emitting region size for CH3OH are derived to be 131 ± 11 K and ∼10 au, respectively. The detection of iCOMs in close proximity to the protostar indicates that CB 68 harbors a hot corino. The kinematic structure of the C18O, CH3OH, and OCS lines is explained by an infalling–rotating envelope model, and the protostellar mass and the radius of the centrifugal barrier are estimated to be 0.08–0.30 M⊙ and, This paper makes use of the following ALMA data: ADS/JAO.ALMA#2016.1.01376.S. ALMA is a partnership of ESO (representing its member states), NSF (USA) and NINS (Japan), together with NRC (Canada), NSC and ASIAA (Taiwan), and KASI (Republic of Korea), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO and NAOJ. The authors acknowledge financial support from JSPS and MAEE under the Japan–France Integrated Action Program (SAKURA: 25765VC). D.J. is supported by NRC Canada and by an NSERC Discovery Grant. E.B. and G.B. acknowledge funding from the European Research Council under the European Union's Horizon 2020 research and innovation program, for the project "The Dawn of Organic Chemistry," grant agreement No. 741002. G.B. acknowledges support from the PID2020-117710GB-I00 grant funded by MCIN/AEI/10.13039/501100011033 and from the Unit of Excellence María de Maeztu 2020–2023 award to the Institute of Cosmos Sciences (CEX2019-00918-M). I.J.-S. has received partial support from the Spanish State Research Agency (AEI) through project Nos. PID2019-105552RB-C41 and MDM-2017-0737 Unidad de Excelencia "Maria de Maeztu" - Centro de Astrobiologia (CSIC-INTA). This study is supported by grants-in-aid from the Ministry of Education, Culture, Sports, Science, and Technology of Japan (18H05222, 18J11010, 19H05069, 19K14753, and 21K13954).

We present ALMA high-angular resolution ($\sim$ 50 au) observations of the Class I binary system SVS13-A. We report images of SVS13-A in numerous interstellar complex organic molecules: CH$_{\rm 3}$OH, $^{13}$CH$_{\rm 3}$OH, CH$_{\rm 3}$CHO, CH$_{\rm 3}$OCH$_{\rm 3}$, and NH$_{\rm 2}$CHO. Two hot corinos at different velocities are imaged in VLA4A (V$_{sys}$= +7.7 km s$^{-1}$) and VLA4B (V$_{sys}$= +8.5 km s$^{-1}$). From a non-LTE analysis of methanol lines we derive a gas density of 3 $\times$ 10$^8$ cm$^{-3}$, and gas temperatures of 140 K and 170 K for VLA4A and VLA4B, respectively. For the other species the column densities are derived from a LTE analysis. Formamide, which is the only N-bearing species detected in our observations, is more prominent around VLA4A, while dimethyl ether, methanol and acetaldehyde are associated with both VLA4A and VLA4B. We derive in the two hot corinos abundance ratios of $\sim$ 1 for CH$_{\rm 3}$OH, $^{13}$CH$_{\rm 3}$OH, and CH$_{\rm 3}$OCH$_{\rm 3}$, $\sim$ 2 for CH$_{\rm 3}$CHO, and $\sim$ 4 for NH$_{\rm 2}$CHO. The present dataset supports a chemical segregation between the different species inside the binary system. The emerging picture is that of an onion-like structure of the two SVS13-A hot corinos, caused by the different binding energies of the species, also supported by ad hoc quantum chemistry calculations. In addition, the comparison between molecular and dust maps suggests that the interstellar complex organic molecules emission originates from slow shocks produced by accretion streamers impacting the VLA4A and VLA4B disks and enriching the gas-phase component., Comment: 20 pages, 14 figures

Context. Hot corinos are compact regions around solar-mass protostellar objects that are very rich in interstellar Complex Organic Molecules (iCOMs). How the abundance of these molecules is affected by the environmental physical conditions is still an open question. More specifically, addressing this point is key to understand our own chemical origins since the Solar System formed in a large cluster of low- to high-mass stars and was therefore subject to external heating and ultraviolet irradiation which may have shaped the chemistry of its early formation stages. Aims. The goal of this high resolution study is to determine the abundance ratios of iCOMs in HOPS-108, which is a Class 0 protostar and a hot corino candidate located in the nearest Solar System analogue, the protostellar cluster OMC-2 FIR 4, in Orion. We aim to compare the abundance ratios to those found in other hot corinos, which are all located in less crowded environments, in order to understand the impact of environmental conditions on hot corinos’ chemistry. Methods. We observed the OMC-2 FIR 4 proto-cluster using the Band 6 of the Atacama Large (sub-)Millimetre Array in Cycle 4 with an angular resolution of ~0.′′28 (110 au). We determined the abundances and temperature of the species using local thermodynamic equilibrium (LTE) and non-LTE analysis. Results. Our results reveal a rich organic chemistry towards HOPS-108, asserting that it is a hot corino where the following iCOMs are detected: CH3OH, HCOOCH3, CH3OCH3, CH318OH, CH2DOH, CH3COCH3, CH3CHO, CH3CN, 13CH3CN, C2H5CN, and NH2CHO. Remarkably, we find a possible enhancement in the HCOOCH3 abundance with respect to other known hot corinos. Indeed, the [CH3OCH3]/[HCOOCH3] abundance ratio in this source is ~0.2 and, within the uncertainties, it deviates from the known correlation marginally where [CH3OCH3]/[HCOOCH3] ~1. A relatively low [CH2DOH]/[CH3OH] abundance ratio of ~0.02 is also obtained, which is in agreement with that found in another Orion source, HH212, suggesting a higher gas temperature during the early phases of ice mantle formation. Conclusions. The [CH3OCH3]/[HCOOCH3] and [CH2DOH]/[CH3OH] abundance ratios in HOPS-108 might result from different physical conditions in the Orion molecular complex compared to other regions. The former ratio cannot be reproduced with current chemical models, highlighting the importance of improving the chemical networks with theoretical calculations. More hot corinos located in heavily clustered regions such as Orion should be targeted in order to measure these ratios and evaluate whether they are an environmental product or whether HOPS-108 is an exceptional hot corino overall.

To substitute the standard carbon fiber reinforced epoxy composite, sustainable and renewable alternative fibers are investigated for the use of high-pressure vessel through a finite element model. The standard T700S carbon fiber pressure vessel exhibits a minimum burst pressure of 1483 bar on the first layer oriented at 90°. The burst occurs in the central part showing a safe burst and the radial deformation reaches 1.12 mm. Several alternative fibers (basalt, E-glass, flax and recycled T700S carbon) are compared to the T700S carbon fiber. It results of lower burst pressures and none of the alternative composites caters for the minimum pressure threshold of 1400 bar. According to the storage pressure and in respect of the mechanical requirements, hybrid vessels integrating alternative and T700S carbon fibers are proposed to improve physical, environmental and economic performances. From an economic point of view, the optimal vessels are the E-glass/T700S carbon hybrid vessel and E-glass vessel for 700 and 350 bar, respectively. Regarding the environmental impact, the most suitable fibers are basalt/T700S carbon for a 700-bar storage and E-glass for 350 bar. Concerning the vessel mass, T700S carbon composite stays obviously the best candidate for a 700-bar storage but at 350 bar T700S carbon/flax fibers composite appears to be more efficient.

To understand the origin of the diversity observed in exoplanetary systems, it is crucial to characterize the early stages of their formation, represented by Solar-type protostars. Likely, the gaseous chemical content of these objects directly depends on the composition of the dust grain mantles formed before the collapse. Directly retrieving the ice mantle composition is challenging, but it can be done indirectly by observing the major components, such as NH3 and CH3OH at cm wavelengths, once they are released into the gas-phase during the warm protostellar stage. We observed several CH3OH and NH3 lines toward three Class 0 protostars in NGC1333 (IRAS 4A1, IRAS 4A2, and IRAS 4B), at high angular resolution (1"; ~300 au) with the VLA interferometer at 24-26 GHz. Using a non-LTE LVG analysis, we derived a similar NH3/CH3OH abundance ratio in the three protostars (, accepted in ApJ Letters

To date, about two dozen low-mass embedded protostars exhibit rich spectra with lines of complex organic molecule (COM). These protostars seem to possess different enrichment in COMs. However, the statistics of COM abundance in low-mass protostars are limited by the scarcity of observations. This study introduces the Perseus ALMA Chemistry Survey (PEACHES), which aims at unbiasedly characterizing the chemistry of COMs toward the embedded (Class 0/I) protostars in the Perseus molecular cloud. Of 50 embedded protostars surveyed, 58% of them have emission from COMs. A 56%, 32%, and 40% of the protostars have CH$_3$OH, CH$_3$OCHO, and N-bearing COMs, respectively. The detectability of COMs depends neither on the averaged continuum brightness temperature, a proxy of the H$_2$ column density, nor on the bolometric luminosity and the bolometric temperature. For the protostars with detected COMs, CH$_3$OH has a tight correlation with CH$_3$CN, spanning more than two orders of magnitude in column densities normalized by the continuum brightness temperature, suggesting a chemical relation between CH$_3$OH and CH$_3$CN and a large chemical diversity in the PEACHES samples at the same time. A similar trend with more scatter is also found between all identified COMs, hinting at a common chemistry for the sources with COMs. The correlation between COMs is insensitive to the protostellar properties, such as the bolometric luminosity and the bolometric temperature. The abundance of larger COMs (CH$_3$OCHO and CH$_3$OCH$_3$) relative to that of smaller COMs (CH$_3$OH and CH$_3$CN) increases with the inferred gas column density, hinting at an efficient production of complex species in denser envelopes., 55 pages, 9 tables, 24 figures. Updated after publication in ApJ. Figure 18 appears as a figure set in ApJ

We have observed the very low-mass Class 0 protostar IRAS 15398−3359 at scales ranging from 50 to 1800 au, as part of the Atacama Large Millimeter/Submillimeter Array Large Program FAUST. We uncover a linear feature, visible in H2CO, SO, and C18O line emission, which extends from the source in a direction almost perpendicular to the known active outflow. Molecular line emission from H2CO, SO, SiO, and CH3OH further reveals an arc-like structure connected to the outer end of the linear feature and separated from the protostar, IRAS 15398−3359, by 1200 au. The arc-like structure is blueshifted with respect to the systemic velocity. A velocity gradient of 1.2 km s−1 over 1200 au along the linear feature seen in the H2CO emission connects the protostar and the arc-like structure kinematically. SO, SiO, and CH3OH are known to trace shocks, and we interpret the arc-like structure as a relic shock region produced by an outflow previously launched by IRAS 15398−3359. The velocity gradient along the linear structure can be explained as relic outflow motion. The origins of the newly observed arc-like structure and extended linear feature are discussed in relation to turbulent motions within the protostellar core and episodic accretion events during the earliest stage of protostellar evolution. The authors thank the anonymous reviewer for invaluable comments. They are also grateful to Hauyu Baobab Liu for useful discussions. This paper makes use of the following ALMA data set: ADS/JAO.ALMA#2018.1.01205.L (PI: Satoshi Yamamoto). ALMA is a partnership of the ESO (representing its member states), the NSF (USA) and NINS (Japan), together with the NRC (Canada) and the NSC and ASIAA (Taiwan), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by the ESO, the AUI/NRAO, and the NAOJ. The authors thank to the ALMA staff for their excellent support. This work is supported by the projects PRIN-INAF-MAIN-STREAM 2017 Protoplanetary disks seen through the eyes of new-generation instruments, ARIEL and the astrochemical link between circumstellar disks and planets, and the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programmes: The Dawn of Organic Chemistry (DOC), grant agreement No. 741002, and Astro-Chemistry Origins (ACO), grant No. 811312. The National Radio Astronomy Observatory is a facility of the National Science Foundation operated under cooperative agreement by Associated Universities, Inc. I.J.-S. has received partial support from the Spanish FEDER (project number ESP2017-86582-C4-1-R) and the State Research Agency (AEI; project number PID2019-105552RB-C41). D.J. is supported by NRC Canada and by an NSERC Discovery Grant. This project is also supported by a Grant-in-Aid from Japan Society for the Promotion of Science (KAKENHI: Nos. 18H05222, 19H05069, 19K14753). Yuki Okoda thanks the Advanced Leading Graduate Course for Photon Science (ALPS) and Japan Society for the Promotion of Science (JSPS) for financial support. Peerreview

The gas associated with the early stages of star formation contains traces of a large variety of molecular species, many of which are organic in nature. Interestingly, we observe a substantial chemical diversity among protostars, with some objects being enriched in what astrochemists label interstellar complex organic molecules (iCOMs), such as methyl formate (HCOOCH3), while others are overabundant in unsaturated carbon chains such as C4H. What is the cause of this diversity? And where should we place the proto-solar-system in this chemical context: was it rich in iCOMs, or in carbon chains, or in both? Thanks to the development of sensitive broadband (sub-)millimetre instrumentation, both in single-dish telescopes and interferometers, we are currently witnessing big steps forward in this area. The present contribution summarises what we have learnt, in the past decade or so, about the molecular contents in solar-mass protostellar sources, and suggests a few guidelines to stimulate progress in the field.

The spectral energy distribution (SED) in the millimetre (mm) to centimetre (cm) range is a useful tool for characterising the dust in protostellar envelopes as well as free-free emission from the protostar and outflow. While many studies have been carried out towards low- and high-mass protostars, little exists so far about solar-type protostars in high-mass star-forming regions, which are likely to be representatives of the conditions where the Solar System was born. We focus here on the OMC-2/3 solar-type protostars, which are bounded by nearby HII regions and which are, therefore, potentially affected by the high-UV illumination. We aim to understand whether the small-scale structure ($\leq$1000 au) and the evolutionary status of these solar-type protostars are affected by the nearby HII regions, as is the case for the large-scale ($\leq$10$^4$ au) gas chemical composition. We used ALMA in the 1.3 mm band (246.2 GHz) to image the continuum of 16 OMC-2/3 solar-type protostars, with an angular resolution of 0.25$''$ (100 au). We completed our data with archival data from the VANDAM survey of Orion Protostars at 333 and 32.9 GHz, respectively, to construct the dust SED, extract several dust parameters and to assess whether free-free emission is contaminating their dust SED in the cm range. From the mm to cm range dust SED, we found low dust emissivity spectral indexes ($\beta < 1$) for the majority of our source sample and free-free emission towards only 5 of the 16 sample sources. We were also able to confirm or correct the evolutionary status of the source sample. Finally, we did not find any dependence of the source dust parameters on their location in the OMC-2/3 filament. Our results show that the small-scale dust properties of the OMC-2/3 protostars are not affected by the high- UV illumination from the nearby HII regions., Comment: 30 pages, 14 figures, Accepted for publication in A&A

We present the first census of the interstellar Complex Organic Molecules (iCOMs) in the low-mass Class I protostar SVS13-A, obtained by analysing data from the IRAM-30m Large Project ASAI (Astrochemical Surveys At IRAM). They consist of an high-sensitivity unbiased spectral survey at the 1mm, 2mm and 3mm IRAM bands. We detected five iCOMs: acetaldehyde (CH$_3$CHO), methyl formate (HCOOCH$_3$), dimethyl ether (CH$_3$OCH$_3$), ethanol (CH$_3$CH$_2$OH) and formamide (NH$_2$CHO). In addition we searched for other iCOMs and ketene (H$_2$CCO), formic acid (HCOOH) and methoxy (CH$_3$O), whose only ketene was detected. The numerous detected lines, from 5 to 37 depending on the species, cover a large upper level energy range, between 15 and 254 K. This allowed us to carry out a rotational diagram analysis and derive rotational temperatures between 35 and 110 K, and column densities between $3\times 10^{15}$ and $1\times 10^{17}$ cm$^{-2}$ on the 0."3 size previously determined by interferometric observations of glycolaldehyde. These new observations clearly demonstrate the presence of a rich chemistry in the hot corino towards SVS13-A. The measured iCOMs abundances were compared to other Class 0 and I hot corinos, as well as comets, previously published in the literature. We find evidence that (i) SVS13-A is as chemically rich as younger Class 0 protostars, and (ii) the iCOMs relative abundances do not substantially evolve during the protostellar phase., Comment: 24 pages, MNRAS in press

The chemical composition of protostellar jets and its origin are still badly understood. More observational constraints are needed to make progress. With that objective, we have carried out a systematic search for molecular species in the jet of Cep E-mm, a template for intermediate-mass Class 0 protostars, associated with a luminous, high-velocity outflow. We made use of an unbiased spectral line survey in the range 72-350 GHz obtained with the IRAM 30m telescope, complementary observations of the CO $J$=3-2 transition with the JCMT, and observations at 1" angular resolution of the CO $J$=2-1 transition with the IRAM Plateau de Bure interferometer. In addition to CO, we have detected rotational transitions from SiO, SO, H$_2$CO, CS, HCO$^{+}$ and HCN. A strong chemical differentiation is observed in the southern and northern lobes of the jet. Radiative transfer analysis in the Large Velocity Gradient approximation yields typical molecular abundances of the order of $10^{-8}$ for all molecular species other than CO. Overall, the jets exhibit an unusual chemical composition, as CS, SO and H$_2$CO are found to be the most abundant species, with a typical abundance of (3-4)$\times 10^{-8}$. The transverse size of the CO jet emission estimated from interferometric observations is about 1000 au, suggesting that we are detecting emission from a turbulent layer of gas entrained by the jet in its propagation and not the jet itself. We propose that some molecular species could be the signatures of the specific photochemistry driven by the UV radiation field generated in the turbulent envelope., 14 pages, 11 figures, accepted to publication on MNRAS

Iron-group oxides are among the best earth abundant catalysts for the oxygen evolution reaction (OER) in alkaline and neutral electrolytes [1],[2]. Such oxides have been prepared with an amorphous or a crystalline structure, using thermal salt decomposition [3], autoclave synthesis [4], photochemical reactions [5], sol-gel synthesis [6], metal electrodeposition and subsequent oxidation, [7] and direct oxide electrodeposition [1], [8]. This work focuses on well-defined epitaxial CoOx [9] electrocatalysts grown by direct electrodeposition on Au(111) according to an approach similar to that introduced by Switzer [8]. The growth modes of catalysts and the mechanisms of deposition will be discussed based on electrochemical characterizations, XRD characterizations and microscopic observations. In particular to explain that CoOOH may be obtained at a potential of +1V/RHE by oxidation of a Co(II) complex diluted in an alkaline solution while thermodynamics predicts that Co3O4 should be formed. The electrochemical properties in pre-OER and within OER will be discussed as a function of the surface structure and morphology of layers. In particular to show that the large pseudocapacitance measured at the electrode is not related to its ECSA but to electrical charging within the bulk of the electrode. [1] M. W. Kanan and D. G. Nocera, Science 321, 1072 (2008). [2] C. C. L. McCrory, S. Jung, I. M. Ferrer et al., Journal of the American Chemical Society 137, 4347 (2015). [3] C. Pirovano and S. Trasatti, Journal of Electroanalytical Chemistry and Interfacial Electrochemistry 180, 171 (1984). [4] D. Yuming, H. Kun, Y. Lin et al., Nanotechnology 18, 435602 (2007). [5] S. R. Alvarado, Y. Guo, T. P. A. Ruberu et al., The Journal of Physical Chemistry C 116, 10382 (2012). [6] A. Bergmann, E. Martinez-Moreno, D. Teschner et al., Nature Communications 6, 8625 (2015). [7] M. W. Louie and A. T. Bell, Journal of the American Chemical Society 135, 12329 (2013). [8] J. A. Koza, Z. He, A. S. Miller et al., Chem. Mat. 24, 3567 (2012). [9] F. Reikowski, F. Maroun, I. Pacheco et al., ACS Catalysis 9, 3811 (2019).

Iron-group oxides are among the best precious-metal-free catalyst for the oxygen evolution reaction (OER) in alkaline media [1] and thus of great interest for large-scale electrochemical water splitting into O2 and H2. A wide variety of different catalysts, based on oxides of Co, Fe, and Ni, have been synthesized and studied, exhibiting rather diverse nanoscale morphologies and usually an unknown surface structure. This makes it difficult to compare their reactivity and correlate it with ab initio theoretical studies, which hinders the development of clear structure-reactivity relationships and unambiguous determination of the OER reaction mechanism. In this work we report in situ and operando surface x-ray diffraction (SXRD) studies of well-defined Co3O4 and b-CoOOH electrocatalysts [2]. Ultrathin epitaxial films (10-20 nm thickness) of these materials were electrodeposited on Au single crystals from a dilute Co(II) tartrate solution of pH 14, using a modified version of the procedure described in Ref. [3]. Characterization by SXRD and AFM revealed that epitaxial Co3O4(111) and β-CoOOH(001) deposits were obtained in 2 M and 5 M NaOH, respectively. The film orientation is independent of the substrate and in the surface plane aligned with the Au(111) and Au(001) substrate lattice. The β-CoOOH(001) film deposits were found to be smooth with clearly visible atomic steps. The Co3O4 films exhibits a more island-like morphology, which can be controlled by the deposition parameters. The potential-dependent structure of these model oxide electrocatalysts during cyclic voltammograms was studied at pH values between 7 and 13 over a wide potential range up to OER current densities of 150 mA/cm2. For this, a custom designed electrochemical cell was used that allows high-resolution SXRD characterization together with electrochemical and optical reflectivity measurements while gas evolution proceeds. The two oxide materials show very different behavior. The CoOOH(001) samples were perfectly stable over a wide potential range. In the case of Co3O4(111), fast and fully reversible structural changes are observed, in good agreement with a previous operando study of polycrystalline Co3O4 catalysts [4]. Specifically, the near surface region of Co3O4(111) is converted to a new phase, which is assigned to highly disordered CoOOH. This restructuring starts at potentials 300 mV negative of the onset of the OER, indicating that the process is related to the thermodynamically predicted Co3O4 / β-CoOOH(001) transition rather than to the catalytic reaction. The formed skin layer is of defined thickness, which changes linearly with applied potential. In addition, continuous changes of the Co3O4 unit cell volume are found over a wide potential range, which are assigned to changes in the oxide bulk, related to the pseudo-capacitive charging current in the pre-OER potential range. The kinetics of these structural changes is fast and highly reversible. Furthermore, systematic studies of Co3O4(111) films with different morphology show a smaller skin layer thickness and lower magnitude of the bulk oxide changes for smoother deposits, suggesting an important role of more open oxide facets for the structural conversion. Surprisingly, the catalytic activity of the skin layer covered Co3O4(111) and that of the smooth β-CoOOH(001) are almost identical, if the true microscopic surface area is taken into account. This indicates that the number of OER active sites on the two oxides is similar, despite the very different defect density, and is at variance with previous suggestions that di-µ-oxo bridged Co cations are exclusively responsible for the OER activity of Co oxides. For the smooth β-CoOOH(001) a turnover frequency of 4.2 s-1 per surface atom is determined at an overpotential of 400 mV, which exceeds that estimated in most studies of polycrystalline Co oxide electrocatalysts. [1] C. C. L. McCrory et al., Journal of the American Chemical Society 2015, 137, 4347. [2] F. Reikowski, et al., ACS Catalysis, 2019, 9, 3811 [3] J. A. Koza et al., Chem. Mat. 2012, 24, 3567. [4] A. Bergmann, et al., Nature Communications, 2015, 6, 8625. Figure 1