A molecular picture of surface interactions of organic compounds on prevalent indoor surfaces: limonene adsorption on SiO2

Chem Sci. 2019 Jan 9;10(10):2906-2914. doi: 10.1039/c8sc05560b. eCollection 2019 Mar 14.

Abstract

Indoor surfaces are often coated with organic compounds yet a molecular understanding of what drives these interactions is poorly understood. Herein, the adsorption and desorption of limonene, an organic compound found in indoor environments, on hydroxylated silica (SiO2) surfaces, used to mimic indoor glass surfaces, is investigated by combining vibrational spectroscopy, atomistic computer simulations and kinetic modeling. Infrared spectroscopy shows the interaction involves hydrogen-bonding between limonene and surface O-H groups. Atomistic molecular dynamics (MD) simulations confirm the existence of π-hydrogen bonding interactions, with one or two hydrogen bonds between the silica O-H groups and the carbon-carbon double bonds, roughly one third of the time. The concentration and temperature dependent adsorption/desorption kinetics as measured by infrared spectroscopy were reproduced with a kinetic model, yielding the adsorption enthalpy of ∼55 kJ mol-1, which is consistent with the value derived from the MD simulations. Importantly, this integrated experimental, theoretical and kinetic modeling study constitutes a conceptual framework for understanding the interaction of organic compounds with indoor relevant surfaces and thus provides important insights into our understanding of indoor air chemistry and indoor air quality.