Influence of LaFeO3 Surface Termination on Water Reactivity

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.; Thevuthasan, Suntharampillai; Ihm, Kyuwook; Crumlin, Ethan J.; Chambers, Scott A.

doi:10.1021/acs.jpclett.7b00195

Influence of LaFeO₃ Surface Termination on Water Reactivity

Journal Article · Thu Feb 16 00:00:00 EST 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b00195· OSTI ID:1343949

^[1]; ^[2]; ^[1]; Thevuthasan, Suntharampillai ^[1]; Ihm, Kyuwook ^[3]; ^[4]; Chambers, Scott A. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate; Auburn Univ., AL (United States). Dept. of Physics
Pohang Accelerator Lab. (PAL) (Korea, Republic of)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO₃ in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecular water at lower relative humidity than its FeO₂-terminated counterpart. But, the FeO₂-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

Grant/Contract Number:: AC02-05CH11231; AC05-76RL01830

OSTI ID:: 1343949

Alternate ID(s):: OSTI ID: 1347856
OSTI ID: 1379758

Report Number(s):: PNNL-SA--123478

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 5 Vol. 8; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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