Do observations on surface coverage-reactivity correlations always describe the true catalytic process? A case study on ceria

In situ (operando) investigations aim at establishing structure-function and/or coverage-reactivity correlations. Herein, we investigated the gas-phase HCl oxidation (4HCl + O2 → 2Cl2 + 2H2O) over ceria. Despite its remarkable performance, under low oxygen over-stoichiometry, this oxide is prone to a certain extent to subsurface/bulk chlorination, which leads to deactivation. In situ Prompt Gamma Activation Analysis (PGAA) studies evidenced that the chlorination rate is independent of the pre-chlorination degree but increases at lower oxygen over-stoichiometry, while dechlorination is effective in oxygen-rich feeds, and its rate is higher for a more extensively pre-chlorinated ceria. Even bulk CeCl3 could be transformed into CeO2 under oxygen excess. Electron Paramagnetic Resonance experiments strongly suggested that oxygen activation is inhibited by a high surface chlorination degree. The coverages of most abundant surface intermediates, OH and Cl, were monitored by in situ infrared spectroscopy and PGAA under various conditions. Higher temperature and p(O2) led to enhanced OH coverage, reduced Cl coverage, and increased reactivity. Variation of p(HCl) gave rise to opposite correlations, while raising p(Cl2) did not induce any measurable increase in the Cl coverage, despite the strong inhibition of the reaction rate. The results indicate that only a small fraction of surface sites is actively involved in the reaction, and most of the surface species probed in the in situ observation are spectators. Therefore, when performing in situ steady-state experiments, a large set of variables should be considered to obtain accurate conclusions.