intermediates in charge transfer processes in solar water splitting. [7] Chromium oxides are well known for their flexible redox state, [1c] and are promising materials for energy conversion and storage applications. They find use as corrosion protection layers for photoelectrochemistry, [8] and are also used as photocatalysts themselves. [9] Of particular interest is the LaCrO 3 perovskite family, where substituting Sr 2+ for La 3+ can dramatically alter the electronic structure and induce p-type electrical conductivity, [10] resulting in some compositions of La (1-x) Sr x CrO 3 (LSCO) being promising p-type transparent conductive oxides. [10c,11] Devices operating at high temperatures take advantage of the redox stability of LSCO [10a] and oxygen transport properties, [12] such as cathodes and interconnects for solid oxide fuel cells (SOFCs). [13] In all these applications, the surface chemistry of LSCO can dramatically impact material performance, motivating in situ spectroscopic investigations in oxidizing and reducing environments.We present a study of chromium valence and surface speciation of (001)-oriented La (1-x) Sr x CrO 3 where x = 0.12 (Sr12), x = 0.5 (Sr50), x = 0.75 (Sr75), and x = 1 (Sr100) in oxygen gas and water vapor environments. The study of single-crystal thin films enables quantification of surface speciation without convolution from grain boundaries or surface roughness. Using ambient pressure X-ray photoelectron spectroscopy (AP-XPS), [14] The oxidation and reduction of metal oxides and their interaction with the environment play a critical role in material stability and the ability to catalyze reactions. The local change in valence and formation of surface adsorbates affect the oxide electronic structure and chemical reactivity, yet are challenging to probe experimentally. In this paper a detailed study of the oxidation and reduction of Cr in the perovskite oxide family of La (1-x) Sr x CrO 3 using ambient pressure X-ray photoelectron spectroscopy is presented. The incorporation of Sr increases the propensity to oxidize at the surface, leading to the presence of Cr 4+ and Cr 6+ principally confined to the top unit cell when in equilibrium with O 2 gas. These acidic sites are readily reduced to Cr 3+ in equilibrium with H 2 O vapor, and the resultant amount of hydroxyls formed from the dissociation of H 2 O is directly proportional to the density of surface sites formerly oxidized. The quantification of the redox stability of La (1-x) Sr x CrO 3 and the relationship between the extent of oxidation, reduction, and hydroxylation with Sr yield important insight into the surface functionality during electrochemical applications.
Surface Chemistry