In situ Raman monitoring of electroreductive dehalogenation of aryl halides at an Ag/aqueous solution interface

Electroreductive dehalogenation as an efficient and green approach has attracted much attention in pollution remediation. Herein, we have employed a shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) technique to in situ probe the electroreductive dehalogenation process of aryl halides with thiol groups at Ag/aqueous solution interfaces. It is found that 4-bromothiophenol (BTP) and 4-chlorothiophenol (CTP) can turn into mixed products of 4,4′-biphenyldithiol (BPDT) and thiophenol (TP) as the electrode potential decreases. The conversion ratios estimated from the Raman intensity variations of C–Cl and C–Br vibrations are 44% and 58% for CTP and BTP in neutral solution, respectively. Furthermore, the quantitative analysis of benzene ring vibrations reveals a C–C cross coupling between the benzene free radical intermediate and adjacent TP product, which results in increased selectivity for biphenyl products at negative potentials.