Atomic-scale modelling of organic matter in soil: adsorption of organic molecules and biopolymers on the hydroxylated α-Al 2 O 3 (0001) surface.

Binding of organic molecules on oxide mineral surfaces is a key process which impacts the fertility and stability of soils. Aluminium oxide and hydroxide minerals are known to strongly bind organic matter. To understand the nature and strength of sorption of organic carbon in soil, we investigated the binding of small organic molecules and larger polysaccharide biomolecules on α-Al 2 O 3 (corundum). We modelled the hydroxylated α-Al 2 O 3 (0001) surface, since these minerals' surfaces are hydroxylated in the natural soil environment. Adsorption was modelled using density functional theory (DFT) with empirical dispersion correction. Small organic molecules (alcohol, amine, amide, ester and carboxylic acid) were found to adsorb on the hydroxylated surface by forming multiple hydrogen bonds with the surface, with carboxylic acid as the most favourable adsorbate. A possible route from hydrogen-bonded to covalently bonded adsorbates was demonstrated, through co-adsorption of the acid adsorbate and a hydroxyl group to a surface aluminium atom. Then we modelled the adsorption of biopolymers, fragments of polysaccharides which naturally occur in soil: cellulose, chitin, chitosan and pectin. These biopolymers were able to adopt a large variety of hydrogen-bonded adsorption configurations. Cellulose, pectin and chitosan could adsorb particularly strongly, and therefore are likely to be stable in soil. This article is part of a discussion meeting issue 'Supercomputing simulations of advanced materials'.