CO2 Reactivity on Cobalt-Based Perovskites

Hwang, Jonathan; Rao, Reshma R.; Katayama, Yu; Lee, Dongkyu; Wang, Xiao Renshaw; Crumlin, Ethan J.; Venkatesan, Thirumalai; Lee, Ho Nyung; Shao-Horn, Yang

doi:10.1021/acs.jpcc.8b06104

Title: CO₂ Reactivity on Cobalt-Based Perovskites

Journal Article · Thu Aug 09 00:00:00 EDT 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b06104· OSTI ID:1483179

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Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Yamaguchi Univ., Yamaguchi (Japan)
Univ. of South Carolina, Columbia, SC (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Nanyang Technological Univ. (Singapore)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
NUSNNI-Nanocore (Singapore); National Univ. of Singapore (Singapore)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Understanding the interaction of CO₂ with perovskite metal oxide surfaces is crucial for the design of various perovskite (electro)chemical functionalities, such as solid oxide fuel cells, catalytic oxidation reactions, and gas sensing. In this study, we experimentally investigated the reactivity of CO₂ with a series of cobalt-based perovskites (i.e., LaCoO₃, La_0.4Sr_0.6CoO₃, SrCoO_2.5, and Pr_0.5Ba_0.5CoO_3–δ) by a combined ambient-pressure XPS (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) approach. Isobaric measurements by AP-XPS on epitaxial pulsed laser deposition-grown (100)-oriented thin films under 1 mTorr CO₂ showed the formation and uptake of adsorbed adventitious-like C–C/C–H, –CO species, monodentate carbonate, and bidentate (bi)carbonates. DRIFTS measurements on powder samples under CO₂ atmosphere revealed the presence of multiple configurations of carbonate in the asymmetric O–C–O stretching region with peak splittings of ~100 and ~300 cm^–1 correlated to the monodentate- and bidentate-bound carbonate adsorbates, respectively. The synergy between chemical state identification by AP-XPS and vibrational state detection by DRIFTS allows both the carbonaceous species type and the configuration to be identified. We further demonstrate that the surface chemistry of the A-site cation strongly influences CO₂ reactivity; the La, Sr, and Ba cations in the LaCoO₃, La_0.4Sr_0.6CoO₃, SrCoO_2.5, and Pr_0.5Ba_0.5CoO₃ thin films showed significant carbon adsorbate speciation. Additionally, we link the La_0.4Sr_0.6CoO₃ surface chemistry to its surface reactivity toward formation of bidentate (bi)carbonate species via exchange of lattice oxygen with carbonate oxygen. In conclusion, we show that the perovskite electronic structure ultimately dictates the driving force for formation of oxidized oxo-carbonaceous species (CO₃) versus reduced species (C–C/C–H). Furthermore, a higher O 2p-band center relative to the Fermi level was correlated with a higher degree of (bi)carbonate formation relative to the other carbonaceous species observed (C–C/C–H and –CO) due to a more facile charge transfer from oxygen states at the Fermi level to free CO₂ gas.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1483179

Journal Information:: Journal of Physical Chemistry. C, Vol. 122, Issue 35; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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