Hydrogen Bonds and H3O+Formation at the Water Interface with Formic Acid Covered Anatase TiO2

Research output: Contribution to journalArticlepeer-review

6 Scopus citations


Carboxylic acid-modified TiO2 surfaces in aqueous environment are of widespread interest, yet atomic-scale understanding of their structure is limited. We here investigate formic acid (FA) on anatase TiO2 (101) (A-101) in contact with water using density functional theory (DFT) and ab initio molecular dynamics (AIMD). Isolated FA molecules adsorbed in a deprotonated bridging bidentate (BD) form on A-101 are found to remain stable at the interface with water, with the acid proton transferred to a surface oxygen to form a surface bridging hydroxyl (ObrH). With increasing FA coverage, adsorbed monolayers of only BD and successively of alternating monodentate (MD) and BD species give rise to a higher concentration of surface ObrH's. Simulations of these adsorbed monolayers in water environment show that some protons are released from the surface ObrH's to water resulting in a negatively charged surface with nearby solvated H3O+ ions. These results provide insight into the complex acid-base equilibrium between an oxide surface, adsorbates and water and can also help obtain a better understanding of the wetting properties of chemically modified TiO2 surfaces.

Original languageEnglish (US)
Pages (from-to)6840-6846
Number of pages7
JournalJournal of Physical Chemistry Letters
Issue number29
StatePublished - Jul 29 2021

All Science Journal Classification (ASJC) codes

  • General Materials Science
  • Physical and Theoretical Chemistry


Dive into the research topics of 'Hydrogen Bonds and H3O+Formation at the Water Interface with Formic Acid Covered Anatase TiO2'. Together they form a unique fingerprint.

Cite this