Ceria lattice oxygen ion substitution by Cl- during the reduction of Rh(Cl)/CeO2 catalysts. Formation and stability of CeOCl

Rh/CeO2 systems prepared by anionic exchange of anionic rhodium chloro comp lexes contain significant amounts of chloride. They are referred to as Rh(C l)/CeO2 catalysts. Reduction at 1173 K does not decrease the chloride conte nt of these catalysts but calcination in air at the same temperature leads to total elimination of Cl- ions. A temperature-programmed reduction (TPR) study evidenced the promoting effect of rhodium on the reducibility of CeO2 and showed that quasi-stoichiometric incorporation of chloride ions into c eria occurred at a relatively low reduction temperature (323-523 K), simult aneously with rhodium reduction to Rh(0). It is proposed that chloride inco rporation occurs through the migration of surface Cl- ions into oxygen vaca ncies of CeO2 resulting from the reduction of surface oxygen by dissociated hydrogen spilled over from Rh(0) to the CeO2 surface. The incorporation of chloride was found to inhibit progressively the process of hydrogen spillo ver below 773 K. No CeOCl phase could be detected at the corresponding low reduction temperatures. However, catalysts containing higher chloride loadi ngs were used to show that CeOCl was formed at higher reduction temperature s than that necessary for chloride incorporation into CeO2, supporting the hypothesis that Cl- ions are incorporated into the ceria lattice at low tem peratures. CeOCl was found to be unstable in air but the phase could be res tored upon additional reducing treatment, thus showing the reversibility of the Cl- ion migration into the oxygen vacancies of ceria.