BACKGROUND: Catalytic hydrodechlorination (HDC) is a progressive approach to treating chlorinated waste streams. While carbon is widely used as a catalyst support, the influence of carbon surface functionality on HDC performance has not been established. This work sets out to assess the impact of surface acid groups associated with activated carbon (AC), graphite and graphitic nanofibers (GNF) on Pd promoted gas phase HDC of chlorobenzene (CB) and 1,3-dichlorobenzene (DCB). RESULTS: The acid groups were introduced by HNO3 washing and the HDC reaction performed over bulk Pd and Pd physically mixed with each carbon. The carbon was subjected to a thermal treatment to remove the surface acidity. Characterization was by temperature programmed decomposition (TPD), temperature programmed hydrogen treatment (TPH), BET area, acid-base titration, scanning and transmission electron microscopy. TPD, TPH and titration analyses served to establish the presence of surface oxygen groups after acid washing and facilitated an evaluation of the effectiveness of the thermal treatment to remove these groups. CONCLUSIONS: The surface acid groups inhibited HDC activity, a response most pronounced for Pd+AC, less so for Pd+graphite, while the effect was slight for Pd+GNF. HDC inhibition is attributed to chloroarene interaction with the surface functional (notably carboxylic) groups that impedes HDC. Fractional dechlorination of DCB was equivalent to or lower than CB HDC; there is some evidence of DCB interactions with heat treated graphite and GNF that served to raise HDC activity. Effective HDC over carbon based catalysts requires removal of surface acid groups. (c) 2008 Society of Chemical Industry.