Mineralization of CCl4 with copper oxide

Experimentally, CCl4 was effectively mineralized by CuO to yield stable inorganic species of CO2 and CuCl2 (CCl4 + 2CuO --> 2CuCl2 + CO2). High CCl4 conversions (63-83%) were found in the mineralization process performed at 513-603 K for 10-30 min. Using X-ray-absorption near edge structure (XANES) and X-ray photoelectron spectroscopies, we found that most CuCl2 was encapsulated in the CCl4-mineralized product solid (mineralization at 513 K for 30 min). At higher mineralization temperatures (563-603 K), CuCl2 was found to be predominant on the surfaces of the mineralization product. Speciation of copper in the mineralization product solid was also studied by extended X-ray absorption fine structure (EXAFS) spectroscopy. Bond distances of Cu-O and Cu-Cl in the CCl4-mineralized product solid were 1.93-1.94 and 2.10-2.12 , respectively, which were greater than those of normal CuO and CuCl2 by 0.03-0.07 A. The increase of the bond distances for Cu-O and Cu-Cl might be due to Cl insertion and concomitant structural perturbation of unreacted CuO in the mineralization process. Forthe second shell around copper atom, bond distances of Cu-(O)-Cu also increased by 0.03-0.05 A, and the coordination numbers of Cu-O and Cu-(O)-Cu decreased, as expected, in the mineralization process. In addition, stoichiometrically excess oxygen atoms were found on the solid surfaces, and they might play an important role in the mineralization of CCl4, leading to the formation of CO2 and Cl. Chloride atoms might be further captured by CuO, yielding CuCl2 in the mineralization process. This work exemplifies the utilization of X-ray spectroscopies (XANES, EXAFS, and XPS) to reveal the speciation and possible reaction pathway in a very complex mineralization process in detail.