Acid-base equilibria: not exactly like you remember in chemistry class

Work published in the Royal Society of Chemistry with the support of the Helmholtz Association through the Center for Free-Electron Laser Science at DESY, MAX IV Laboratory, Lund University, Sweden,  European Research Council (ERC) under the European Union’s Horizon 2020 and the Academy of Finland.

Remember doing titrations in chemistry class? Adding acid drop-by-drop to the beaker and the moment you took your eye off it the solution completely changed colour.
We learned in chemistry that by doing this titration, we were actually affecting an important equilibrium in the beaker between acids and bases. This equilibrium was first described at the turn of the 20th century by American biochemist Lawrence Henderson and modified by Karl Hasselbalch giving us the Henderson-Hasselbalch equation. The discovery and subsequent study of acids and bases using this equation has led to the discovery of many important phenomena in the natural world from as how cells function to how materials are formed.

However, after years of study, an idea arose that questioned the validity of the Henderson-Hasselbalch equation, what happens at the surface? If you have a beaker filled with a dilute acid, what happens at the very top atomic layer? The top layer of a liquid in a beaker is special for many reasons, but if you’re a dissolved molecule, it means that you’re no longer surrounded by water on all sides. For hydrophobic molecules, this means that it is favourable to be at the surface. With this in mind, the scientists took another look at the Henderson-Hasselbalch equilibrium equation and thought that it couldn’t work at the surface. Many studies have measured indicator chemical species, and determined that the Henderson-Hasselbalch equation does not seem to apply at the surface, and concluded that the concentration of hydronium or hydroxide ions, which determines the acidity/basicity, is different at the air-liquid interface than in the bulk.

>Read more on the MAXIV Laboratory website

 

 

Tailoring the surface chemical reactivity of transition‐metal dichalcogenide PtTe2 crystals

Recently, the PtX2 (X=S, Se, Te) class of transition-metal dichalcogenides has emerged as one of the most promising among layered materials “beyond graphene” for the presence of high room-temperature electron mobility and, moreover, bulk type-II Dirac fermions, arising from a tilted Dirac cone.
Information on the ambient stability of PtTe2 is a crucial step in order to evaluate the feasibility of its exploitation in technology. Moreover, the possibility to tune surface chemical reactivity by appropriate surface modification is an essential step for its employment for diverse applications, especially in catalysis.
By means of experiments with several surface-science spectroscopies and density functional theory, an international team of researchers from Italy, Republic of Korea, and Taiwan (coordinated by Graphene Labs of Istituto Italiano di Tecnologia) has investigated the reactivity of the PtTe2 surface toward most common ambient gases (oxygen and water), under the framework of the European Graphene Flagship-Core1 project.
To assess the surface chemical reactivity of PtTe2, X-ray photoelectron spectroscopy (XPS) carried out at the APE-HE beamline has been combined with high-resolution electron energy loss (HREELS) experiments and with density functional theory.
From the analysis of Te 3d core-level spectra in XPS and from the featureless vibrational spectrum in HREELS, it has been demonstrated that as-cleaved defect-free PtTe2 surface is inert toward most common ambient gases (oxygen and water).
In the evaluation of the ambient stability of PtTe2, the possible influence of Te vacancies on surface chemical reactivity deserves particular attention. As a matter of fact, Te vacancies may appear on non-stoichiometric samples during the growth process. To check the influence of Te vacancies on ambient stability of PtTe2, Te vacancies have been intentionally introduced in stoichiometric PtTe2 samples by Ar-ion sputtering. After exposing to O2 the PtTe2 surface defected by ion sputtering, with a Pt:Te ratio of 39:61, spectral features related to Te(IV) species appear, arising from the formation of Te=O bonds in a tellurium-oxide phase. The Te(IV) components are the most intense lines in the Te 3d XPS spectra for the case of air-exposed defected samples (see Figure 1). Concerning reactivity to water, it adsorbs molecularly even at room temperature on defected PtTe2. These findings also imply that the presence of Te vacancies is able to jeopardize the ambient stability of uncapped PtTe2-based devices, with a subsequent necessity to reduce the amount of Te vacancies for a successful technological exploitation of PtTe2.

>Read more on the Elettra website

Figure: XPS spectra of Te-3d core levels acquired for: defected PtTe2 (green curve), the same surface exposed to 106 L of O2 (black curve) and air-exposed defected PtTe2 (yellow curve). The photon energy is 745 eV.