In this work the oxidation states assumed by Ir in oxide systems used as heterogeneous catalysts for water oxidation are determined by means of in situ X-ray Absorption Spectroscopy (XAS). Using a highly hydrated iridium oxide film allows the maximum number of Ir sites to be involved in the electrochemical processes occurring at the catalysts during water oxidation (oxygen evolution reaction, OER). X-ray Absorption Near Edge Structure (XANES) spectra clearly indicate the co-existence of Ir(III) and Ir(V) at the electrode potentials where OER occurs. This represents a fundamental step both in the understanding of the water oxidation mechanism catalysed by heterogeneous Ir oxide systems, and in the possible tailoring of electrocatalysts for OER.

High-entropy oxides based on transition metals, such as Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2O (TM-HEO), have recently drawn special attention as potential anodes in lithium-ion batteries due to high specific capacity and cycling reversibility. However, the lithiation/delithiation mechanism of such systems is still controversial and not clearly addressed. Here, we report on an operando XAS investigation into TM-HEO-based anodes for lithium-ion cells during the first lithiation/delithiation cycle. This material showed a high specific capacity exceeding 600 mAh g^–1 at 0.1 C and Coulombic efficiency very close to unity. The combination of functional and advanced spectroscopic studies revealed complex charging mechanisms, developing through the reduction of transition-metal (TM) cations, which triggers the conversion reaction below 1.0 V. The conversion is irreversible and incomplete, leading to the final collapse of the HEO rock-salt structure. Other redox processes are therefore discussed and called to account for the observed cycling behavior of the TM-HEO-based anode. Despite the irreversible phenomena, the HEO cubic structure remains intact for ∼60% of lithiation capacity, so proving the beneficial role of the configuration entropy in enhancing the stability of the HEO rock-salt structure during the redox phenomena.

The mechanisms of CO oxidation on the Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O high entropy oxide were studied by means of operando soft X-ray absorption spectroscopy. We found that Cu is the active metal, and that Cu(II) can be rapidly reduced to Cu(I) by CO when the temperature is larger than 130 °C. Co and Ni do not have any role in this respect. The Cu(II) oxidation state can be easily but slowly recovered by treating the sample in O2 at ca. 250 °C. However, it should be noted that CuO is readily and irreversibly reduced to Cu(I) if treated in CO at T>100 °C. Thus, the main conclusion of this work is that the high configurational entropy of Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O stabilizes the rock-salt structure and permits the oxidation/reduction of Cu to be reversible, thus permitting the catalytic cycle to take place.

The phonon dispersions of ${\mathrm{Nd}}_{1.86}{\mathrm{Ce}}_{0.14}{\mathrm{CuO}}_{4+\delta }$ along the $[\xi ,0,0\mathrm{}]$ direction have been determined by inelastic x-ray scattering. Compared to the undoped parent compound, the two highest longitudinal phonon branches, associated with the Cu-O bond stretching and out-of-plane oxygen vibration, are shifted to lower energies. Moreover, an anomalous softening of the bond-stretching band is observed at about $\mathbf{q}=(0.2,0,0)$. These signatures provide evidence for strong electron-phonon coupling in this electron-doped high-temperature superconductor.