The effect of acid treatment on the surface chemistry and topography of graphite

Highly oriented pyrolytic graphite (HOPG) samples were investigated as model catalyst supports. The surfaces were treated with dilute HCl and HNO3 under ambient conditions and examined with atomic force microscopy and scanning tunnelling microscopy (STM) and Xray photoelectron spectroscopy (XPS). Raised features were formed on the HOPG surface after acid treatment. These protrusions were typically 4-6 nm in height and between 10 and 100 nm in width, covering 5-20% of the substrate for acid concentrations between 0.01 and 0.2 M. Both width and surface density of the features increases with acid concentration but the heights are not affected. STM images show that the graphite lattice extends over the protrusions indicating that the features are "blisters" on the surface rather than deposited material, a view that is supported by the XPS which shows no other significant adsorbates except for oxygen in the case of the nitric acid. We propose that penetration of the acid at defective sites leads to a decrease in the interplanar van der Waals forces and a local delamination similar to the "bubbles" reported between exfoliated graphene sheets and a substrate. These findings are important in the context of understanding how carbon supports stabilise active components in heterogeneous catalysts. (C) 2013 Elsevier Ltd. All rights reserved.