CuCeO_x/CuO Catalyst Derived from the Layered Double Hydroxide Precursor: Catalytic Performance in NO Reduction with CO in the Presence of Water and Oxygen

Valencies of metal species and lattice defects, such as oxygen vacancies, play a pivotal role in metal oxide-catalyzed reactions. Herein, we report a promising synthetic strategy for preparing CuO-supported CuCeO_x catalysts (CuCeO_x/CuO) by calcination of a hydrotalcite precursor [Cu₆Ce₂(OH)₁₆]CO₃·nH₂O. The structural and chemical properties of catalysts were characterized by XRD, ICP-AES, TEM, TPR, NH₃-TPD, XPS, Raman spectroscopy, and N₂ adsorption, which revealed that the thermal pretreatment in an oxidative atmosphere caused segregation and reconstitution processes of the precursor, resulting in a mesoporous catalyst consisting of well-dispersed CuO-supported CuCeO_x clusters of 1.8–3.2 nm in size with a high population of oxygen vacancies. The as-prepared catalyst shows excellent catalytic performance in the reduction of NO by CO in the absence as well as in the presence of water and oxygen. This behavior is attributed to its high oxygen defect concentration facilitating the interplay of the redox equilibria between Cu²⁺ and reduced copper species (Cu⁺/Cu⁰) and (Ce⁴⁺/Ce³⁺). The high surface population of oxygen vacancies and in situ-generated metallic copper species have been evidenced by Raman spectroscopy and X-ray photoelectron spectroscopy. The layered double hydroxide-derived CuCeO_x/CuO also showed good water tolerance and long-term stability. In situ infrared spectroscopy investigations indicated that adsorbed hyponitrite species are the main reaction intermediates of the NO conversion as also corroborated by theoretical simulations.