HIPPIE is a soft X-ray beamline on the 3 GeV electron storage ring of the MAX IV Laboratory, equipped with a novel ambient-pressure X-ray photoelectron spectroscopy (APXPS) instrument. The endstation is dedicated to performing in situ and operando X-ray photoelectron spectroscopy experiments in the presence of a controlled gaseous atmosphere at pressures up to 30 mbar [1 mbar = 100 Pa] as well as under ultra-high-vacuum conditions. The photon energy range is 250 to 2200 eV in planar polarization and with photon fluxes >1012 photons s−1 (500 mA ring current) at a resolving power of greater than 10000 and up to a maximum of 32000. The endstation currently provides two sample environments: a catalysis cell and an electrochemical/liquid cell. The former allows APXPS measurements of solid samples in the presence of a gaseous atmosphere (with a mixture of up to eight gases and a vapour of a liquid) and simultaneous analysis of the inlet/outlet gas composition by online mass spectrometry. The latter is a more versatile setup primarily designed for APXPS at the solid–liquid (dip-and-pull setup) or liquid–gas (liquid microjet) interfaces under full electrochemical control, and it can also be used as an open port for adhoc-designed non-standard APXPS experiments with different sample environments. The catalysis cell can be further equipped with an IR reflection–absorption spectrometer, allowing for simultaneous APXPS and IR spectroscopy of the samples. The endstation is set up to easily accommodate further sample environments.
The cooling dynamics of glass-embedded noble metal nanoparticles with diameters ranging from 4 to 26 nm were studied using ultrafast pump-probe spectroscopy. Measurements were performed probing away from the surface plasmon resonance of the nanoparticles to avoid spurious effects due to glass heating around the particle. In these conditions, the time-domain data reflect the cooling kinetics of the nanoparticle. Cooling dynamics are shown to be controlled by both thermal resistance at the nanoparticle-glass interface and heat diffusion in the glass matrix. Moreover, the interface conductances are deduced from the experiments and found to be correlated with the acoustic impedance mismatch at the metal/glass interface.
Corrosion is the main factor limiting the lifetime of metallic materials, and a fundamental understanding of the governing mechanism and surface processes is difficult to achieve since the thin oxide films at the metal–liquid interface governing passivity are notoriously challenging to study. In this work, a combination of synchrotron‐based techniques and electrochemical methods is used to investigate the passive film breakdown of a Ni–Cr–Mo alloy, which is used in many industrial applications. This alloy is found to be active toward oxygen evolution reaction (OER), and the OER onset coincides with the loss of passivity and severe metal dissolution. The OER mechanism involves the oxidation of Mo4+ sites in the oxide film to Mo6+ that can be dissolved, which results in passivity breakdown. This is fundamentally different from typical transpassive breakdown of Cr‐containing alloys where Cr6+ is postulated to be dissolved at high anodic potentials, which is not observed here. At high current densities, OER also leads to acidification of the solution near the surface, further triggering metal dissolution. The OER plays an important role in the mechanism of passivity breakdown of Ni–Cr–Mo alloys due to their catalytic activity, and this effect needs to be considered when studying the corrosion of catalytically active alloys.
Carbon nanomaterials’ reactivity towards oxygen is very poor, limiting their potential applications. However, nitrogen doping is an established way to introduce active sites that facilitate interaction with gases. This boosts the materials’ reactivity for bio-/gas sensing and enhances their catalytic performance for the oxygen reduction reaction. Despite this interest, the role of differently bonded nitrogen dopants in the interaction with oxygen is obscured by experimental challenges and has so far resisted clear conclusions. We study the interaction of molecular oxygen with graphene doped via nitrogen plasma by in situ high-resolution synchrotron techniques, supported by density functional theory core level simulations. The interaction leads to oxygen dissociation and the formation of carbon-oxygen single bonds on graphene, along with a band gap opening and a rounding of the Dirac cone. The change of the N 1 s core level signal indicates that graphitic nitrogen is involved in the observed mechanism: the adsorbed oxygen molecule is dissociated and the two O atoms chemisorb with epoxy bonds to the nearest carbon neighbours of the graphitic nitrogen. Our findings help resolve existing controversies and offer compelling new evidence of the ORR pathway.