Light Makes a Surface Banana-Bond Split: Photodesorption of Molecular Hydrogen from RuO2(110)

Michael A. Henderson, Rentao Mu, Arjun Dahal, Igor Lyubinetsky, Zdenek Dohnálek, Vassiliki Alexandra Glezakou, Roger Rousseau

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

The coordination of H2 to a metal center via polarization of its σ 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 complex involves an interband transition in RuO2 which effectively diminishes its Lewis acidity, thereby weakening the Kubas complex. Such excitations are not expected to affect adsorbates on RuO2 given its metallic properties. Therefore, this common thermal cocatalyst employed in photocatalysis is, itself, photoactive.

Original languageEnglish
Pages (from-to)8714-8717
Number of pages4
JournalJournal of the American Chemical Society
Volume138
Issue number28
DOIs
StatePublished - Jul 20 2016
Externally publishedYes

Funding

This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences and performed in EMSL, a national scientific user facility sponsored by the Department of Energys Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle.

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