Direct assessment of the acidity of individual surface hydroxyls

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26620%2F21%3APU140822" target="_blank" >RIV/00216305:26620/21:PU140822 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11320/21:10439686

Výsledek na webu

<a href="https://www.nature.com/articles/s41586-021-03432-3" target="_blank" >https://www.nature.com/articles/s41586-021-03432-3</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1038/s41586-021-03432-3" target="_blank" >10.1038/s41586-021-03432-3</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Direct assessment of the acidity of individual surface hydroxyls

Popis výsledku v původním jazyce

The state of deprotonation/protonation of surfaces has far-ranging implications in chemistry, from acid-base catalysis(1) and the electrocatalytic and photocatalytic splitting of water(2), to the behaviour of minerals(3) and biochemistry(4). An entity's acidity is described by its proton affinity and its acid dissociation constant pK(a) (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(5), and increasingly modelled with first-principles molecular dynamics simulations(6,7). At present, such predictions cannot be tested-experimental measures, such as the point of zero charge(8), integrate over the whole surface or, in some cases, individual crystal facets(9). 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. Non-contact atomic force microscopy measurements are used to probe the hydrogen bond strength of individual surface hydroxyl groups and determine their acidity with atomic precision.

Název v anglickém jazyce

Direct assessment of the acidity of individual surface hydroxyls

Popis výsledku anglicky

The state of deprotonation/protonation of surfaces has far-ranging implications in chemistry, from acid-base catalysis(1) and the electrocatalytic and photocatalytic splitting of water(2), to the behaviour of minerals(3) and biochemistry(4). An entity's acidity is described by its proton affinity and its acid dissociation constant pK(a) (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(5), and increasingly modelled with first-principles molecular dynamics simulations(6,7). At present, such predictions cannot be tested-experimental measures, such as the point of zero charge(8), integrate over the whole surface or, in some cases, individual crystal facets(9). 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. Non-contact atomic force microscopy measurements are used to probe the hydrogen bond strength of individual surface hydroxyl groups and determine their acidity with atomic precision.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10302 - Condensed matter physics (including formerly solid state physics, supercond.)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

NATURE

ISSN

0028-0836

e-ISSN

1476-4687

Svazek periodika

592

Číslo periodika v rámci svazku

7856

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

4

Strana od-do

722-725

Kód UT WoS článku

000645368900013

EID výsledku v databázi Scopus

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