RESUMEN
We employed operando soft X-ray absorption spectroscopy (XAS) to monitor the changes in the valence states and spin properties of LaMn1-x Co x O3 catalysts subjected to a mixture of CO and O2 at ambient pressure. Guided by simulations based on charge transfer multiplet theory, we quantitatively analyze the Mn and Co 2p XAS as well as the oxygen K-edge XAS spectra during the reaction process. The Mn sites are particularly sensitive to the catalytic reaction, displaying dynamics in their oxidation state. When Co doping is introduced (x ≤ 0.5), Mn oxidizes from Mn2+ to Mn3+ and Mn4+, while Co largely maintains a valence state of Co2+. In the case of LaCoO3, we identify high-spin and low-spin Co3+ species combined with Co2+. Our investigation underscores the importance to consider the spin and valence states of catalyst materials under operando conditions.
RESUMEN
We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3/LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67Sr0.33MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2Nb3O10 nanosheet-buffered 100 nm SiNx membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiNx membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO3 film.
RESUMEN
This work presents a spectroscopic and photocatalytic comparison of water splitting using yttrium iron garnet (Y3Fe5O12, YIG) and hematite (α-Fe2O3) photoanodes. Despite similar electronic structures, YIG significantly outperforms widely studied hematite, displaying more than an order of magnitude increase in photocurrent density. Probing the charge and spin dynamics by ultrafast, surface-sensitive XUV spectroscopy reveals that the enhanced performance arises from (1) reduced polaron formation in YIG compared to hematite and (2) an intrinsic spin polarization of catalytic photocurrents in YIG. Ultrafast XUV measurements show a reduction in the formation of surface electron polarons compared to hematite due to site-dependent electron-phonon coupling. This leads to spin polarized photocurrents in YIG where efficient charge separation occurs on the Td sub-lattice compared to fast trapping and electron/hole pair recombination on the Oh sub-lattice. These lattice-dependent dynamics result in a long-lived spin aligned hole population at the YIG surface, which is directly observed using XUV magnetic circular dichroism. Comparison of the Fe M2,3 and O L1-edges show that spin aligned holes are hybridized between O 2p and Fe 3d valence band states, and these holes are responsible for highly efficient, spin selective water oxidation by YIG. Together, these results point to YIG as a new platform for highly efficient, spin selective photocatalysis.
