Pivotal Role of Holes in Photocatalytic CO₂ Reduction on TiO₂.

ABSTRACT: Evidence is provided that in a gas-solid photocatalytic reaction the removal of photogenerated holes from a titania (TiO₂ ) photocatalyst is always detrimental for photocatalytic CO₂ reduction. The coupling of the reaction to a sacrificial oxidation reaction hinders or entirely prohibits the formation of CH₄ as a reduction product. This agrees with earlier work in which the detrimental effect of oxygen-evolving cocatalysts was demonstrated. Photocatalytic alcohol oxidation or even overall water splitting proceeds in these reaction systems, but carbon-containing products from CO₂ reduction are no longer observed. H₂ addition is also detrimental, either because it scavenges holes or because it is not an efficient proton donor on TiO₂ . The results are discussed in light of previously suggested reaction mechanisms for photocatalytic CO₂ reduction. The formation of CH₄ from CO₂ is likely not a linear sequence of reduction steps but includes oxidative elementary steps. Furthermore, new hypotheses on the origin of the required protons are suggested.

SUBMITTER: Moustakas NG 

PROVIDER: S-EPMC9299149 | biostudies-literature |

REPOSITORIES: biostudies-literature