Direct dioxygen evolution in collisions of carbon dioxide with surfaces

Journal Article · 24 May 2019 · Nature Communications

DOI: https://doi.org/10.1038/s41467-019-10342-6 · OSTI ID:1610779

Yao, Yunxi ^[1]; Shushkov, Philip ^[1]; Miller, Thomas F.  ^[1]; Giapis, Konstantinos P.  ^[1]

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1. California Institute of Technology (CalTech), Pasadena, CA (United States)

The intramolecular conversion of CO₂ to molecular oxygen is an exotic reaction, rarely observed even with extreme optical or electronic excitation means. Here we show that this reaction occurs readily when CO₂ ions scatter from solid surfaces in a two-step sequential collision process at hyperthermal incidence energies. The produced O₂ is preferentially ionized by charge transfer from the surface over the predominant atomic oxygen product, leading to direct detection of both O₂⁺ and O₂^-. First-principles simulations of the collisional dynamics reveal that O₂ production proceeds via strongly-bent CO₂ configurations, without visiting other intermediates. Bent CO₂ provides dynamic access to the symmetric dissociation of CO2 to C+O2 with a calculated yield of 1 to 2% depending on molecular orientation. This unexpected collision-induced transformation of individual CO₂ molecules provides an accessible pathway for generating O₂ in astrophysical environments and may inspire plasmadriven electro- and photo-catalytic strategies for terrestrial CO₂ reduction.

• Research Organization: California Institute of Technology (CalTech), Pasadena, CA (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• Grant/Contract Number: SC0004993
• OSTI ID: 1610779
• Journal Information: Nature Communications, Vol. 10, Issue 1; ISSN 2041-1723
• Publisher: Nature Publishing GroupCopyright Statement
• Country of Publication: United States
• Language: English