Inverse Kinetic Solvent Isotope Effect in TiO2 Photocatalytic Dehalogenation of Non‐adsorbable Aromatic Halides: A Proton‐Induced Pathway

An efficient redox reaction between organic substrates in solution and photoinduced h+vb/e−cb on the surface of photocatalysts requires the substrates or solvent to be adsorbed onto the surface, and is consequentially marked by a normal kinetic solvent isotope effect (KSIE≥1). Reported herein is a universal inverse KSIE (0.6–0.8 at 298 K) for the reductive dehalogenation of aromatic halides which cannot adsorb onto TiO2 in a [D0]methanol/[D4]methanol solution. Combined with in situ ATR‐FTIR spectroscopy investigations, a previously unknown pathway for the transformation of these aromatic halides in TiO2 photocatalysis was identified: a proton adduct intermediate, induced by released H+/D+ from solvent oxidation, accompanies a change in hybridization from sp2 to sp3 at a carbon atom of the aromatic halides. The protonation event leads these aromatic halides to adsorb onto the TiO2 surface and an ET reaction to form dehalogenated products follows.