The
amorphous silica (SiO2) shell on diatom frustules
is a highly attractive biomaterial for removing pollutants from aquatic
ecosystems. The surface activity of silica can be enhanced by modification
with organosilanes. In this work, we present an atomic-level theoretical
study based on molecular dynamics and dispersion-corrected density
functional theory calculations on the surface stability and adsorption
of heavy metal (HM) compounds on silane- and 3-aminopropyltriethoxysilane
(APTES)-covered SiO2 surfaces. Our simulations show that
at low APTES coverage, the molecular adsorption of Cd(OH)2 and HgCl2 is more favorable near the modifier, compared
to As(OH)3 that binds at the hydroxylated region on silica.
At higher coverages, the metallic compounds are preferentially adsorbed
by the terminating amino group on the surface, whereas the adsorption
in the region between APTES and the oxide surface is also spontaneous.
The adsorption is strongly driven by van der Waals interactions at
the highly covered surface, where the consideration of dispersion
corrections reduces the modifier–adsorbate interatomic distances
and increases the adsorption energy by ca. 0.4–0.7 eV. The
adsorption of water is favorable, although it is generally weaker
than for the HM compounds. Based on our results, we conclude that
the addition of APTES modifiers on silica increases the adsorption
strength and provides extra binding sites for the adsorption of HM
pollutants. These outcomes can be used for the design of more efficient
structures of biomaterials for depollution of HMs.