Spectroelectrochemical study of perchloroethylene reduction at copper electrodes in neutral aqueous medium

Abstract

The potential-dependent chemical reaction of perchloroethylene (PCE) on copper in neutral noncomplexing aqueous media is explored by means of surface-enhanced Raman spectroscopy (SERS), linear sweep voltammetry and preparative electrolysis at controlled potential. Voltammetric peaks associated with copper oxide reduction in Na2SO4 solution in the presence and the absence of Cl- are correlated with simultaneously acquired SER spectra. Perchloroethylene undergoes a dechlorination process at potentials at E≤-0.3V vs. Ag/AgCl/KCl (3M), as shown by the emergence of an intense Cu-Cl stretching band at 290cm-1 and a C-H stretching band together with the presence of Cl- in the catholyte. In the potential region between 0 and -0.9 V vs. Ag/AgCl/KCl (3 M) a broad band assigned to -C≡C- structures is observed in the triple-bond region (∼1900cm-1 FWHM= 180 cm-1). In addition, dichloroethylene (DCE) is detected (but not trichloroethylene (TCE)) in this potential region during preparative electrolysis. At potentials lowerthan - 1 V vs. Ag/AgCl/KCl (3M) carbon residues are the main product, detected on the copper surface by SERS (and confirmed by XPS), whereas in solution higher levels of dichloroethylene and trichloroethylene are detected with a DCE/TCE ratio below 1.