Molten Salt Flux Synthesis, Crystal Facet Design, Characterization, Electronic Structure, and Catalytic Properties of Perovskite Cobaltite

Autor: Xiyang Wang, Shouhua Feng, Wei Ma, Shuang Li, Zhongyuan Liu, Long Yuan, Keke Huang
Rok vydání: 2018
Předmět:
Zdroj: ACS Applied Materials & Interfaces. 10:28219-28231
ISSN: 1944-8252
1944-8244
DOI: 10.1021/acsami.8b08621
Popis: We present a simple and cost-effective molten salt synthetic route toward phase-pure perovskite cobaltite microcrystallines and successfully regulate different crystal facets for perovskite LaCoO3 by the strong interaction between Cl- anions and Sr2+ cations in molten salt system and polar plane. We then take LaCoO3 (100 and 110), LaCoO3 (111), and La0.7Sr0.3CoO3 (111) as comparison models, and we characterize their crystal structure, morphology, composition, electronic state, and catalytic properties. X-ray photoelectron spectroscopy (XPS) shows that the prepared samples with high-energy (111) crystal facets contain more surface oxygen species and active Co ions than La enrichment perovskite LaCoO3 (110 and 100) on the surface. Furthermore, combining with ambient-pressure XAS, valence band spectroscopy, and density functional calculations, we find that exposed high-energy (111) crystal facets and doping Sr ions can enhance the hybridization between Co cations and O anions and their O p-band center is closer to the Fermi level, compared with that of LaCoO3 (100 and 110). As expected, the samples with high-energy (111) crystal facets show better CO oxidation activity than LaCoO3 (100 and 110), and La0.7Sr0.3CoO3 (111) exhibits the highest catalytic activity. Our findings provide a new avenue to prepare high-energy facet perovskite catalysts and we also clearly reveal the relationship between surface electronic structure and intrinsic CO oxidation activity of perovskite cobaltite.
Databáze: OpenAIRE