Carboxylic-acid adsorption on anatase TiO2 is a relevant process in many technological applications. Yet, despite several decades of investigations, the acid-proton localization—either on the molecule or on the surface—is still an open issue. By modeling the adsorption of formic acid on top of anatase(101) surfaces, we highlight the formation of a short strong hydrogen bond. In the 0 K limit, the acid-proton behavior is ruled by quantum delocalization effects in a single potential well, while at ambient conditions, the proton undergoes a rapid classical shuttling in a shallow two-well free-energy profile. This picture, supported by agreement with available experiments, shows that the anatase surface acts like a protecting group for the carboxylic acid functionality. Such a new conceptual insight might help rationalize chemical processes involving carboxylic acids on oxide surfaces.

The case of formic acid on (101) anatase TiO2: where is the acid proton?

Tabacchi, Gloria;Fabbiani, Marco;Fois, Ettore
2019-01-01

Abstract

Carboxylic-acid adsorption on anatase TiO2 is a relevant process in many technological applications. Yet, despite several decades of investigations, the acid-proton localization—either on the molecule or on the surface—is still an open issue. By modeling the adsorption of formic acid on top of anatase(101) surfaces, we highlight the formation of a short strong hydrogen bond. In the 0 K limit, the acid-proton behavior is ruled by quantum delocalization effects in a single potential well, while at ambient conditions, the proton undergoes a rapid classical shuttling in a shallow two-well free-energy profile. This picture, supported by agreement with available experiments, shows that the anatase surface acts like a protecting group for the carboxylic acid functionality. Such a new conceptual insight might help rationalize chemical processes involving carboxylic acids on oxide surfaces.
2019
https://doi.org/10.1002/anie.201909283
https://doi.org/10.1002/anie.201906709
https://link.growkudos.com/1hf9wsirdog
https://bit.ly/3uyaZ6r
Density functional calculations, Molecular dynamics, Surface chemistry, Vibrational Spectroscopy, zero point energy
Tabacchi, Gloria; Fabbiani, Marco; Mino, Lorenzo; Martra, Gianmario; Fois, Ettore
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11383/2080048
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