Chlorination of perforated graphite via interaction with thionylchloride

A heating of graphite oxide in concentrated sulfuric acid results in partial removal of oxygen and formation of polyatomic vacancy defects in graphene layers. The boundaries of the defects are decorated by oxygen‐containing groups, the number of which can be significantly reduced with the sample annealing in an inert atmosphere. It is shown that initial and annealed perforated graphite (PG) samples interact with gaseous thionylchloride at room temperature. X‐ray photoelectron and near‐edge X‐ray absorption fine structure spectroscopy find negatively charged chlorine and covalently bonded chlorine in the initial PG and only the latter chlorine form in the annealed PG. According to the reference data and our quantum‐chemical calculations, graphene donates charge to the adsorbed chlorine atoms, while covalent chlorine bonding occurs at vacancy edges. Two chemical states of chlorine detected by XPS in perforated graphene after exposure to SOCl2.