Bart van der Linden

Artificial Photosynthesis over Crystalline TiO2-Based Catalysts: Fact or Fiction?

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.

Electronic origins of photocatalytic activity in d 0 metal organic frameworks

Metal-organic frameworks (MOFs) containing d0 metals such as NH2-MIL-125(Ti), NH2-UiO-66(Zr) and NH2-UiO-66(Hf) are among the most studied MOFs for photocatalytic applications. Despite structural similarities, we demonstrate that the electronic properties of these MOFs are markedly different. As revealed by quantum chemistry, EPR measurements and transient absorption spectroscopy, the highest occupied and lowest unoccupied orbitals of NH2-MIL-125(Ti) promote a long lived ligand-to-metal charge transfer upon photoexcitation, making this material suitable for photocatalytic applications. In contrast, in case of UiO materials, the d-orbitals of Zr and Hf, are too low in binding energy and thus cannot overlap with the π* orbital of the ligand, making both frontier orbitals localized at the organic linker. This electronic reconfiguration results in short exciton lifetimes and diminishes photocatalytic performance. These results highlight the importance of orbital contributions at the band edges and delineate future directions in the development of photo-active hybrid solids.