Chemical and morphological heterogeneities of carbon sorbents play important roles in gas-phase adsorption. However, the specific chemical complexes and topological structures of carbon that favor or impede elemental mercury uptake are not well understood and are the subject of this study. Temperature programmed desorption (TPD) with a model carbonaceous material (highly oriented pyrolytic graphite, HOPG) under ultrahigh vacuum (UHV) conditions and fixed bed adsorption by activated carbon (BPL) at atmospheric pressure were combined to investigate the effects of chemical and morphological heterogeneities on mercury adsorption by carbonaceous surfaces. TPD results show that mercury adsorption at 100 K onto HOPG surfaces with and without chemical functional groups and topological heterogeneity created by plasma oxidation occurs through physisorption. The removal of chemical functionalities from the HOPG surface enhances mercury physisorption. Plasma-oxidation of HOPG provides additional surface area for mercury adsorption. However, the pits created by plasma oxidation are more than 10 nm in diameter and do not simulate microporosity that predominates in activated carbons. Mercury adsorption by activated carbon at atmospheric pressure occurs through two distinct mechanisms. Physisorption governs mercury adsorption at lower temperatures (i.e., below 348 K), while chemisorption predominates at high adsorption temperatures (i.e., above 348 K). Presence of water on activated carbon surface enhances mercury uptake by both physisorption and chemisorption. Oxygen containing functional groups reduce mercury uptake by physisorption by blocking access to the micropores. No significant impact of oxygen functionalities was observed in the chemisorption regime. The key findings of this study open the possibility to apply scientific information obtained from the studies with simple surfaces such as HOPG under ideal conditions (UHV) to industrial sorbents under realistic process conditions.
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