Methylene bromide chemistry and photochemistry on rutile TiO2(110)

The chemistry and photochemistry of methylene bromide (CD2Br2) on the rutile TiO2(110) surface was probed using temperature programmed desorption (TPD). CD2Br2 desorbed in three desorption states at 145, 160 and 250 K tentatively assigned to desorption from the multilayer, from an η1-CD2Br2 species and a bridging η2-CD2Br2 species, respectively. The latter two TPD states presumably involve binding of CD2Br2 molecules to the surface through Br coordination at five-coordinate Ti4+ surface sites. The 160 and 250 K TPD states saturated at coverages of 1.0 and 0.33 ML, respectively, where 1 ML is equivalent to the surface Ti4+ site density (5.2 × 1014 cm− 2). No thermal decomposition of CD2Br2 was observed on either the clean surface or with preadsorbed O2. UV irradiation of CD2Br2 on TiO2(110) resulted in predominately photodesorption, with trace amounts of photodecomposition evidenced in TPD. The rate of CD2Br2 photodesorption from TiO2(110) occurred with a low cross section (~ 2 × 10− 21 cm2) similar to that expected from direct optical excitation of CD2Br2. This observation suggests that charge carriers generated in TiO2(110) were no more effective in activating adsorbed CD2Br2 molecules than would be expected through direct molecular excitation. These findings suggest that photocatalytic destruction of halocarbons such as CD2Br2 on TiO2 may preferentially occur though indirect processes (such as OH radical attack) as opposed to direct electron transfer processes involving charge carriers generated in TiO2 by bandgap excitation.