Concentration effect of copper loading on the reductive dechlorination of tetrachloroethylene by zerovalent silicon

The dechlorination of tetrachloroethylene (PCE) by zerovalent silicon (Si(0)) in the presence of low concentration of Cu(II) ion was investigated under anaerobic conditions. The mass loadings of Cu(II) in the Si(0)-H(2)O system were in the range 0.06-3 wt% (0.02-1 mM). In addition, the X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA) were used to characterize the change in chemical species and distribution patterns of metals, respectively. Results showed that the pre-incubation time of 3 d was needed to activate the reactive sites of Si(0) before the dechlorination of PCE. Addition of low concentration of Cu(II) at 0.06 wt% significantly enhanced the dechlorination of PCE, while high concentration of Cu(II) would occupy the reactive sites of Si(0), and subsequently decreased the dechlorination efficiency and rate of PCE. The pseudo first-order rate constant (k(obs)) for PCE dechlorination by 0.06 wt% Cu/Si was 0.028 h(-1), which was 2.8 times higher than that by Si(0) alone. However, the k(obs) for PCE dechlorination decreased to 0.0016 h(-1) when the loading of Cu(II) increased to 3 wt%. The EPMA results showed that the distribution of 0.06 wt% Cu on the Si(0) surface was homogeneous without any aggregation, which means that the maximum rate constant was observed before the total coverage of the active sites on the reductive metal by the catalytic metal layer. The surface coverage of Cu to Si(0) can theoretically calculate by estimation of the lowest energy fcc(111) crystallographic orientation. The calculated surface coverage of 0.06 wt% Cu onto Si(0) was approximately 43%, which is consistent with the experimental results obtained in this study.