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Mechanisms of the surface-confined Ullmann-reaction on semiconducting TiO2(110) surfaces

AuthorsBrede, Jens; Abadia, Mikel; Kolmer, Marek; Vasseur, Guillaume; Zajac, Lukasz; Verdini, Alberto; Floreano, Luca; Ortega, J. Enrique ; Rogero, Celia
Issue Date2017
CitationECSCD-13 (2017)
AbstractWe have recently demonstrated the synthesis of poly(p-phenylene) (PPP) nanowires from dibromo-pterphenyl (DBTP) precursors on the reduced rTiO2(110) surface under ultra-high vacuum (UHV) conditions. Here, we address the influence of the degree of reduction of the TiO2(110) substrate on the polymerization reaction by temperature dependent XPS. Specifically, we identified that the Ti catalyzed aryl-aryl homo-coupling reaction pathway is strongly suppressed on nearly stoichiometric surfaces. Moreover, we find evidence for a reaction pathways that either facilitate the homo-coupling via proton up-take or lead to the formation of phenyl-ether-groups. Finally, we present a control experiment where the homo-coupling reaction was deliberately induced by adding trace amounts of a metal catalyst at room temperature leading to substantially increased reaction yield and nanowire arrays in unprecedented quality even on (near) stoichiometric sTiO2(110) surfaces. ARPES data showing the transition of the non-dispersing DBTP HOMO into the characteristic PPP p-band on TiO2(110) surfaces with different reduction levels as characterized by the in-gap DS state intensity.
DescriptionResumen del póster presentado a la 13th European Conference on Surface Crystallography and Dynamics, celebrada en Donostia-San Sebastián (España) del 19 al 21 de junio de 2017.
Appears in Collections:(CFM) Comunicaciones congresos
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