Issue 4, 2011

High-pressure reactivity of clathrate hydrates by two-photon dissociation of water

Abstract

It is shown that photoinduced reactions are observed at room temperature and pressure of few tenths of gigapascal in clathrate hydrates of CO and of model hydrocarbons under mild irradiation at 350 nm with power in the 50–610 mW range. The reactions are triggered by highly reactive OH radicals produced by two-photon excitation of the lowest electronic excited state of water having dissociative character. The formation of CO2 is observed in all the reactions involving carbonaceous clathrate hydrates, and direct or indirect evidence for the formation of molecular hydrogen is obtained. The CO2 produced in the reactions can be sequestered as a clathrate hydrate whose stability range seems to extend to room temperature at pressures of 0.5–0.6 GPa. Although the N2 hydrate is stable up to 0.9 GPa under irradiation, a partial cleavage of the N–N triple bond is produced once the hydrate decomposes at 0.1 GPa.

Graphical abstract: High-pressure reactivity of clathrate hydrates by two-photon dissociation of water

Article information

Article type
Perspective
Submitted
26 Jul 2010
Accepted
27 Oct 2010
First published
13 Dec 2010

Phys. Chem. Chem. Phys., 2011,13, 1264-1275

High-pressure reactivity of clathrate hydrates by two-photon dissociation of water

M. Ceppatelli, R. Bini and V. Schettino, Phys. Chem. Chem. Phys., 2011, 13, 1264 DOI: 10.1039/C0CP01318H

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