High-affinity adsorption leads to molecularly ordered interfaces on TiO2 in air and solution

• Published in: Science (American Association for the Advancement of Science) 2018-08, Vol.361 (6404), p.786-789
• Main Authors: Balajka Jan, Hines, Melissa A, DeBenedetti, William J, Komora Mojmir, Pavelec Jiri, Schmid, Michael, Diebold Ulrike
• Format: Article
• Language: English
• Subjects: Acids; Adsorbates; Adsorbed water; Adsorption; Affinity; Alcohol; Alcohols; Carboxylic acids; Hydrophobicity; Interfaces; Microscopy; Monolayers; Organic acids; Photocatalysis; Photoelectron spectroscopy; Scanning tunneling microscopy; Self-assembled monolayers; Self-assembly; Spectroscopy; Spectrum analysis; Surface chemistry; Titanium; Titanium dioxide; Vacuum; Water
• ISSN: 0036-8075; 1095-9203
• DOI: 10.1126/science.aat6752

A preference for acidsWhen titanium dioxide surfaces are exposed to water under ambient conditions, an ordered overlayer forms. Balajka et al. studied this process with scanning tunneling microscopy and x-ray photoelectron spectroscopy for water adsorption under vacuum conditions and in air (see the Perspective by Park). The ordered overlayer was only formed in air, the result of the adsorption of organic acids (formic and acetic acids). Although other species such as alcohols were present in much higher concentrations in air, the bidentate adsorption and entropic effects favored acid adsorption.Science, this issue p. 786; see also p. 753Researchers around the world have observed the formation of molecularly ordered structures of unknown origin on the surface of titanium dioxide (TiO2) photocatalysts exposed to air and solution. Using a combination of atomic-scale microscopy and spectroscopy, we show that TiO2 selectively adsorbs atmospheric carboxylic acids that are typically present in parts-per-billion concentrations while effectively repelling other adsorbates, such as alcohols, that are present in much higher concentrations. The high affinity of the surface for carboxylic acids is attributed to their bidentate binding. These self-assembled monolayers have the unusual property of being both hydrophobic and highly water-soluble, which may contribute to the self-cleaning properties of TiO2. This finding is relevant to TiO2 photocatalysis, because the self-assembled carboxylate monolayers block the undercoordinated surface cation sites typically implicated in photocatalysis.