Interfacial acidity on the strontium titanate surface: a scaling paradigm and the role of the hydrogen bond

Chapleski, Jr., Robert C.; Chowdhury, Azhad U.; Mason, Kyle R.; Sacci, Robert L.; Doughty, Benjamin; Roy, Sharani

doi:10.1039/d1cp03587h

Title: Interfacial acidity on the strontium titanate surface: a scaling paradigm and the role of the hydrogen bond

Journal Article · 16 September 2021 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/d1cp03587h · OSTI ID:1823374

^[1]; Chowdhury, Azhad U. ^[2]; Mason, Kyle R. ^[3];

^[2];

^[3]

Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)

A fundamental understanding of acidity at an interface, as mediated by structure and molecule–surface interactions, is essential to elucidate the mechanisms of a range of chemical transformations. While the strength of an acid in homogeneous gas and solution phases is conceptually well understood, acid–base chemistry at heterogeneous interfaces is notoriously more complicated. Using density functional theory and nonlinear vibrational spectroscopy, we present a method to determine the interfacial Brønsted–Lowry acidity of aliphatic alcohols adsorbed on the (100) surface of the model perovskite, strontium titanate. Here, while shorter and less branched alkanols are known to be less acidic in the gas phase and more acidic in solution, here we show that shorter alcohols are less acidic whereas less substituted alkanols are more acidic at the gas–oxide interface. Hydrogen bonding plays a critical role in defining acidity, whereas structure–acidity relationships are dominated by van der Waals interactions between the alcohol and the surface.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC05-00OR22725; SC0012704

OSTI ID:: 1823374

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 0 Vol. 1; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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