The interaction between hexahydroxytriphenylene and the rutile TiO2(110)-(1×1) surface at UHV conditions

Abstract: The interaction between 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and the rutile TiO2(110)–(1×1) surface under ultrahigh vacuum (UHV) conditions was investigated using X-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and density functional theory (DFT) calculations. The NEXAFS results showed that HHTP molecules formed a submonolayer and a monolayer that aligned along the [001]-direction with, respectively, a more or less flat downward orientation and a more upright orientation to the TiO2 surface. The HHTP molecules that aligned along the [001]-direction were most likely grafted onto the TiO2(110) surface by a bidentate bridge between each of the oxygen atoms of one of the catechol units within the HHTP molecule and two adjacent Ti(5f)4+ ions on the TiO2(110) surface. The coordination is non-dissociative in the case of the submonolayer, but dissociative in the monolayer, according to the analysis of the C1s XPS, UPS, C1s NEXAFS data and complementary DFT calculations. [Copyright &y& Elsevier]