Lewis-Acid Sites of TiO2 Surface for Adsorption of Organic Dye Having Pyridyl Group as Anchoring Unit

• Published in: Journal of physical chemistry. C Vol. 117; no. 32; pp. 16364 - 16370
• Main Authors: Harima, Yutaka, Fujita, Takuya, Kano, Yuta, Imae, Ichiro, Komaguchi, Kenji, Ooyama, Yousuke, Ohshita, Joji
• Format: Journal Article
• Language: English
• Published: Columbus, OH American Chemical Society 15.08.2013
• Subjects: Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Physics; Solid surfaces and solid-solid interfaces; Surfaces and interfaces; thin films and whiskers (structure and nonelectronic properties); Equilibrium constant; TDS; Organic dye; Adsorption site; Coadsorption; Pinning; Nanostructures; Infrared spectra; Pyridyl radicals; Langmuir isotherm; Surface structure; Adsorption; Adsorption structure; Electron paramagnetic resonance; Nanocrystal
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/jp405835y

Adsorption of an organic dye having a pyridyl group as an anchoring unit (NI4) is studied on nanocrystalline TiO2 surface by being compared with a similar dye having a carboxyl anchor (NI2). Adsorption of both dyes followed a Langmuir isotherm, and analysis of the isotherms showed that an adsorption equilibrium constant of NI4 is (1.1 ± 0.1) × 103 M–1, much smaller than (0.6 ± 0.05) × 105 M–1 for NI2, and amounts of adsorbed dyes at saturation are similar to each other: [(1.5 ± 0.2) and (1.7 ± 0.3)] × 1014 cm–2 for NI2 and NI4, respectively. Coadsorption experiments with 4-carboxy TEMPO (4CT) and either NI2 and NI4 revealed that the adsorption sites of NI2 and NI4 are different from each other. This was supported by measurements of average nearest-neighbor interspin distances of 4CT radicals coadsorbed on TiO2 by a spin-probe ESR technique. The above findings and elaborate FT-IR studies demonstrated that NI2 and NI4 adsorb, respectively, on Brønsted- and Lewis-acid sites of TiO2 surface. The number of Lewis-acid sites evaluated from the temperature-programmed desorption experiments of TiO2 was in good agreement with the amount of NI4 adsorbed on TiO2 at saturation, providing a further confirmation for Lewis-acid sites acting as a predominant adsorption site of NI4.