Artificial photosynthesis over crystalline TiO2-based catalysts: Fact or fiction?
Journal
Journal of the American Chemical Society
Journal Volume
132
Journal Issue
24
Pages
8398-8406
Date Issued
2010
Author(s)
Abstract
The mechanism of photocatalytic conversion of CO(2) and H(2)O over copper oxide promoted titania, Cu(I)/TiO(2), was investigated by means of in situ DRIFT spectroscopy in combination with isotopically labeled (13)CO(2). In addition to small amounts of (13)CO, (12)CO was demonstrated to be the primary product of the reaction by the 2115 cm(-1) Cu(I)-CO signature, indicating that carbon residues on the catalyst surface are involved in reactions with predominantly photocatalytically activated surface adsorbed water. This was confirmed by prolonged exposure of the catalyst to light and water vapor, which significantly reduced the amount of CO formed in a subsequent experiment in the DRIFT cell. In addition, formation of carboxylates and (bi)carbonates was observed by exposure of the Cu(I)/TiO(2) surface to CO(2) in the dark. These carboxylates and (bi)carbonates decompose upon light irradiation, yielding predominantly CO(2). At the same time a novel carbonate species is produced (having a main absorption at approximately 1395 cm(-1)) by adsorption of photocatalytically produced CO on the Cu(I)/TiO(2) surface, most likely through a reverse Boudouard reaction of photocatalytically activated CO(2) with carbon residues. The finding that carbon residues are involved in photocatalytic water activation and CO(2) reduction might have important implications for the rates of artificial photosynthesis reported in many studies in the literature, in particular those using photoactive materials synthesized with carbon containing precursors.
SDGs
Type
journal article