Grinter, DC; Woolcot, T; Pang, C-L; Thornton, G; (2014) Ordered Carboxylates on TiO (110) Formed at Aqueous Interfaces. The Journal of Physical Chemistry Letters , 5 (24) 4265 - 4269. 10.1021/jz502249j.

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Abstract

As models for probing the interactions between TiO2 surfaces and the dye molecules employed in dye-sensitized solar cells, carboxylic acids are an important class of molecules. In this work we present a scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) study of three small carboxylic acids (formic, acetic, and benzoic) that were reacted with the TiO2(110) surface via a dipping procedure. The three molecules display quite different adsorption behavior, illustrating the different inter-adsorbate interactions that can occur. After exposure to a 10 mM solution, formic acid forms a rather disordered formate overlayer with two distinct binding geometries. Acetic acid forms a well-ordered (2 × 1) acetate overlayer similar to that observed following deposition from vapor. Benzoic acid forms a (2 × 2) overlayer which is stabilized by intermolecular interactions between the phenyl groups.

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