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

Wen, Bo; Selloni, Annabella

doi:10.1021/acs.jpclett.1c01886

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

Journal Article · Mon Jul 19 00:00:00 EDT 2021 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.1c01886· OSTI ID:1838124

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Princeton Univ., NJ (United States); Henan Univ., Kaifeng (China); Princeton University
Princeton Univ., NJ (United States)

Carboxylic acid-modified TiO₂ surfaces in aqueous environment are of widespread interest, yet atomic-scale understanding of their structure is limited. In this work, we 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 (O_brH). 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 O_brH’s. Simulations of these adsorbed monolayers in water environment show that some protons are released from the surface O_brH’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.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0007347; SC0019394; AC02-05CH11231

OSTI ID:: 1838124

Alternate ID(s):: OSTI ID: 1994995

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 29 Vol. 12; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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