Surface science of environmental interfaces

The research described here falls into the broad area of environmental molecular surface science. The chemistry of single crystal surfaces of CaCO₃, MgO and BaO with several pollutant molecules including NO₂, HNO₃ and SO₂ at the gas-solid interface as a function of relative humidity is being investigated. Nitrogen and sulfur oxides represent major components of air pollution and there is a great deal of interest in these gases from several perspectives including the heterogeneous chemistry of these gases with aerosol particles in the atmosphere (e.g. mineral dust aerosol) and the environmental remediation of these gases from automotive exhaust and power plants. Our goal is to determine fundamental molecular-level aspects of the chemistry of nitrogen and sulfur oxides on the surface of oxides and carbonates under ambient conditions. It is well documented from a number of studies using a wide range of surface sensitive techniques that single crystal oxide and carbonate surfaces cleaved in air undergo facile reaction with atmospheric H₂O to yield hydroxyl and bicarbonate, in the case of carbonates, groups on the surface. Water readily adsorb to these surfaces, most likely through hydrogen bonding to the surface OH and CO₃H groups. It is our goal to understand the molecular level details of these reactions by using a combination of spectroscopy and Atomic Force Microscopy to study these “wet” complex interfaces. This combined approach will give us important information about the molecular-level mechanistic aspects of these reactions including surface speciation, surface segregation and phase transitions. We are also collaborating with Professor Jan Jensen in quantum chemical calculations to further our understanding of environmental interfaces.

A combined approach of spectroscopy and microscopy to study surface reactions under ambient conditions and pressure will provide a detail understanding of these reactions. Schematic cartoon (below) of the complexities of an environmental interface. Oxide and carbonate surfaces under ambient conditions of temperature and relative humidity. Surfaces of oxides and carbonates are usually terminated with hydroxyl groups and bicarbonate that can readily adsorb water.