Silicates, i.e., minerals containing Si and O as well as other ions, are ubiquitous on our planet. They largely compose the rocks we stand on, and are active in sequestrating atmospheric CO2. Through weathering processes, they transform into clays and create soils, providing essential nutrients for plant growth. Furthermore, they exist as airborne dust particles in the atmosphere, where they influence ice nucleation and cloud formation, profoundly impacting global weather patterns.

Most of these phenomena are regulated by reactions at silicate surfaces: small molecules thereby adsorb and react to form new molecules or minerals or both. The atomic details of silicate surfaces – e.g., their composition, crystallographic orientation, atomic structure, active/defect sites, and charge distribution – will determine the precise reaction paths and rates.

To date, knowledge about silicate surfaces is limited due to technical reasons – the strong insulating nature of these minerals makes it challenging for scanning probe techniques. However, recent developments in atomic force microscopy (AFM) allow us to overcome the hurdles and tap into the surface chemistry of silicates and its relevance for many important natural processes. In our labs, we employ constant-height non-contact AFM with a qPlus sensor in UHV to investigate the surfaces of different silicates at the atomic level. We complement these studies by area-averaging spectroscopic techniques such as X-ray photoelectron spectroscopy and ab-initio theoretical modeling.

Mica

Muscovite mica: structure and AFM images

© CC BY 4.0 Giada Franceschi/IAP

Muscovite mica: structure and AFM images

Muscovite mica, a common 2D aluminosilicate, offers a nice example. Facile cleaving occurs between planes of K ions. In our labs, we have resolved the distribution of these K ions – neither disordered nor fully ordered – and investigated its relation to the underlying Al ions.

  • G. Franceschi, P. Kocán, A. Conti, S. Brandstetter, J. Balajka, I. Sokolović, M. Valtiner, F. Mittendorfer, M. Schmid, M. Setvín, U. Diebold
    Resolving the intrinsic short-range ordering of K+ ions on cleaved muscovite mica
    Nature Communications 14, 208 (2023); doi: 10.1038/s41467-023-35872-y

Feldspars

Feldspar crystal (microcline); at the bottom right the surface structure with OH groups

© Giada Franceschi

Feldspar crystal

Feldspar crystal (microcline); at the bottom right the surface structure with OH groups

Feldspars are a group of minerals that form more than 50% of the rocks in the Earth’s crust. They are also found as fine dust in the atmosphere, where they have a vital role for atmospheric ice nucleation. To date, very little is known about them and the role of their surface chemistry for atmospheric ice nucleation.

We have investigated the UHV-cleaved surface of microcline feldspar (KAlSi3O8) and its interaction with water at the atomic scale. The results suggest that the surface chemistry of microcline, specifically the ordering of its surface hydroxyl (OH) groups, is essential for condensing water in an ordered manner, which leads to the nucleation of ice.

G. Franceschi, A. Conti, L. Lezuo, R. Abart, F. Mittendorfer, M. Schmid, U. Diebold
How water binds to microcline feldspar (001)
The Journal of Physical Chemistry Letters 15, 15 (2024); doi: 10.1021/acs.jpclett.3c03235, opens an external URL in a new window