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Title: Light Makes a Surface Banana-Bond Split: Photodesorption of Molecular Hydrogen from RuO 2 (110)

The coordination of H2 to a metal center via polarization of its bond electron density, known as a Kubas complex, is the means by which H2 chemisorbs at Ru4+ sites on the rutile RuO2(110) surface. This distortion of electron density off an interatomic axis is often described as a ‘banana-bond.’ We show that the Ru-H2 banana-bond can be destabilized, and split, using visible light. Photodesorption of H2 (or D2) is evident by mass spectrometry and scanning tunneling microscopy. From time-dependent density functional theory, the key optical excitation splitting the Ru-H2 banana-bond involves an interband transition in RuO2 which effectively diminishes its Lewis acidity, and thereby weakening the Kubas complex. Such excitations are not expected to affect adsorbates on RuO2 given its metallic properties. Therefore, this common thermal co-catalyst employed in promoting water splitting is, itself, photo-active in the visible.
Authors:
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Publication Date:
OSTI Identifier:
1328832
Report Number(s):
PNNL-SA-117971
Journal ID: ISSN 0002-7863; 49642; 48287; KC0302010
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 138; Journal Issue: 28
Publisher:
American Chemical Society (ACS)
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
RuO2(110); hydrogen; photochemistry; desorption; theory; STM; Environmental Molecular Sciences Laboratory