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CuCeOx/CuO Catalyst Derived from the Layered Double Hydroxide Precursor: Catalytic Performance in NO Reduction with CO in the Presence of Water and Oxygen
journal contributionposted on 2023-05-10, 14:36 authored by Zhiwen Li, Yifei Zhang, Qike Jiang, Liangliang Xu, Zhong-Kang Han, Alfons Baiker, Gao Li
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 CuCeOx catalysts (CuCeOx/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 CuCeOx 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 CuCeOx/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.
promising synthetic strategymesoporous catalyst consistingmain reaction intermediateslayered double hydroxide8 – 3reduced copper speciesadsorbed hyponitrite speciesray photoelectron spectroscopyhigh surface population6 sub2 + sup2 subhigh populationmetal species2 nmraman spectroscopysub ><> subx thermal pretreatmenttheoretical simulationsterm stabilityredox equilibriareconstitution processespreparing cuopivotal rolen metal oxidelattice defectsdispersed cuochemical propertiescatalyzed reactionscatalytic performancealso corroborated