Advancements in Liquid Jet Technology and X-ray Spectroscopy for Understanding Energy Conversion Materials during Operation.

ConspectusWater splitting is intensively studied for sustainable and effective energy storage in green/alternative energy harvesting-storage-release cycles. In this work, we present our recent developments for combining liquid jet microtechnology with different types of soft X-ray spectroscopy at high-flux X-ray sources, in particular developed for studying the oxygen evolution reaction (OER). We are particularly interested in the development of in situ photon-in/photon-out techniques, such as in situ resonant inelastic X-ray scattering (RIXS) techniques at high-repetition-frequency X-ray sources, pointing toward operando capabilities. The pilot catalytic systems we use are perovskites having the general structure ABO 3 with lanthanides or group II elements at the A sites and transition metals at the B sites. Depending on the chemical substitutions of ABO 3 , their catalytic activity for OER can be tuned by varying the composition.In this work, we present our in situ RIXS studies of the manganese L-edge of perovskites during OER. We have developed various X-ray spectroscopy approaches like transmission zone plate-, reflection zone plate-, and grating-based emission spectroscopy techniques. Combined with tunable incident X-ray energies, we yield complementary information about changing (inverse) X-ray absorption features of the perovskites, allowing us to deduce element- and oxidation-state-specific chemical monitoring of the catalyst. Adding liquid jet technology, we monitor element- and oxidation-state-specific interactions of the catalyst with water adsorbate during OER. By comparing the different technical spectroscopy approaches combined with high-repetition-frequency experiments at synchrotrons and free-electron lasers, we conclude that the combination of liquid jet with low-resolution zone-plate-based X-ray spectroscopy is sufficient for element- and oxidation-state-specific chemical monitoring during OER and easy to handle.For an in-depth study of OER mechanisms, however, including the characterization of catalyst-water adsorbate in terms of their charge transfer properties and especially valence intermediates formed during OER, high-resolution spectroscopy tools based on a combination of liquid jets with gratings bear bigger potential since they allow resolution of otherwise-overlapping X-ray spectroscopy transitions. Common for all of these experimental approaches is the conclusion that without the versatile developments of liquid jets and liquid beam technologies, elaborate experiments such as high-repetition experiments at high-flux X-ray sources (like synchrotrons or free-electron lasers) would hardly be possible. Such experiments allow sample refreshment for every single X-ray shot for repetition frequencies of up to 5 MHz, so that it is possible (a) to study X-ray-radiation-sensitive samples and also (b) to utilize novel types of flux-hungry X-ray spectroscopy tools like photon-in/photon-out X-ray spectroscopy to study the OER.