Direct assessment of the acidity of individual surface hydroxyls

M. Wagner, B. Meyer, M. Setvin, M. Schmid, U. Diebold

Institut für Angewandte Physik, TU Wien, 1040 Wien, Austria
Central European Institute of Technology (CEITEC), Brno University of Technology, Brno, Czech Republic
Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany
Computer Chemistry Center, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany
Department of Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University, Prague, Czech Republic

Nature 592 (2021) 722-725

The state of deprotonation/protonation of surfaces has far-ranging implications in chemistry, from acid-base catalysis and the electrocatalytic and photocatalytic splitting of water, to the behaviour of minerals and biochemistry. An entity's acidity is described by its proton affinity and its acid dissociation constant pKa (the negative logarithm of the equilibrium constant of the proton transfer reaction in solution). The acidity of individual sites is difficult to assess for solids, compared with molecules. For mineral surfaces, the acidity is estimated by semi-empirical concepts, such as bond-order valence sums, and increasingly modelled with first-principles molecular dynamics simulations. At present, such predictions cannot be tested—experimental measures, such as the point of zero charge, integrate over the whole surface or, in some cases, individual crystal facets. Here we assess the acidity of individual hydroxyl groups on In2O3(111)—a model oxide with four different types of surface oxygen atom. We probe the strength of their hydrogen bonds with the tip of a non-contact atomic force microscope and find quantitative agreement with density functional theory calculations. By relating the results to known proton affinities of gas-phase molecules, we determine the proton affinity of the different surface sites of In2O3 with atomic precision. Measurements on hydroxylated titanium dioxide and zirconium oxide extend our method to other oxides.

Corresponding author: Ulrike Diebold (diebold at iap_tuwien_ac_at).

This work was featured in the article "A microscope for measuring surface acidity" by Johanna L. Miller in Physics Today.

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