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Increasing the UV and extending into the visible the optical response of TiO2 through surface activation with highly stable Cu5 clusters

AuthorsLara Castells, María Pilar de ; Hauser, Andreas W.; Martín Ramallo-López, José; Buceta, David; Giovanetti, Lisandro J.; Lopez-Quintela, Manuel Arturo; Requejo, Félix G.
Issue Date16-Feb-2019
PublisherRoyal Society of Chemistry (UK)
CitationJournal of Materials Chemistry A, 2019
AbstractThe decoration of semiconductors with subnanometer-sized clusters of metal atoms can have a strong impact on the optical properties of the support. The changes induced differ greatly from effects known for their well-studied, metallic counterparts in the nanometer range. In this work, we study the deposition of Cu5 clusters on a TiO2 surface and investigate their influence on the photon-absorption properties of TiO2 nanoparticles via the computational modeling of a decorated rutile TiO2(110) surface. Our findings are further supported by selected experiments using diffuse reflectance and X-ray absorption spectroscopy. The Cu5 cluster donates an electron to TiO2, leading to the formation of a small polaron Ti3+ 3d1 state and depopulation of Cu(3d) orbitals, successfully explaining the absorption spectroscopy measurements at the K-edge of copper. A monolayer of highly stable and well fixated Cu5 clusters is formed, which is not only enhancing the overall absorption, but is also extending the absorption profile into the visible region of the solar spectrum via a direct photo-induced electron transfer and formation of a charge-separated state.
Description15 pags., 6 figs.
Publisher version (URL)http://dx.doi.org/10.1039/C9TA00994A
Appears in Collections:(CFMAC-IFF) Artículos
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