Proton Transfers at a Dopamine-Functionalized TiO2 Interface

by C. Ronchi, D. Selli, W. Pipornpong and C. Di Valentin
J. Phys. Chem. C, 2019, 123, pp 7682-7695 View at Publisher
DOI: 10.1021/acs.jpcc.8b04921

Despite the many successful syntheses and applications of dopamine-functionalized TiO2 nanohybrids, there has not yet been an atomistic understanding of the interaction of this 1,2-dihydroxybenzene derivative ligand with the titanium dioxide surfaces. In this work, on the basis of a wide set of dispersion-corrected hybrid density functional theory (DFT) calculations and density functional tight binding (DFTB) molecular dynamics simulations, we present a detailed study of the adsorption modes, patterns of growth, and configurations of dopamine on the anatase (101) TiO2 surface, with reference to the archetype of 1,2-dihydroxybenzene ligands, i.e., catechol. At low coverage, the isolated dopamine molecule prefers to bend toward the surface, coordinating the NH2 group to a Ti5c ion. At high coverage, the packed molecules succeed in bending toward the surface only in some monolayer configurations. When they do, we observe a proton transfer from the surface to the ethyl-amino group, forming terminal NH3+ species, which highly interact with the O atoms of a neighboring dopamine molecule. This strong Coulombic interaction largely stabilizes the self-assembled monolayer. On the basis of these results, we predict that improving the probability of dopamine molecules being free to bend toward the surface through thermodynamic versus kinetic growth conditions will lead to a monolayer of fully protonated dopamine molecules.