Developing non-noble metal oxides, replacing platinum group catalysts for auto-exhaust purification, where their usage amount exceeds 40 % of global demand, remains a challenge. Herein, we presented a combined approach on the synthesis and application of robust CuOx/TiO2 catalysts with ultra-fine CuOx clusters (ca. 1 nm). The strong interaction between CuOx and TiOx induces favorable interfacial charge accumulation, facilitating the extraction of the interfacial oxygen atoms in Cu2-x-O-Ti4-y chains and the surface lattice oxygen on CuOx clusters. Isotope 18O2 experiments and DFT calculations jointly confirmed that these oxygen atoms preferentially participate in the oxidation through the Mars-van Krevelen mechanism below 250 °C. The resulted oxygen vacancies facilitate the adsorption and activation of O2 molecules, which will participate the oxidation above 250 °C through Eley-Rideal mechanism. The increase in the temperature also drives the synergy of active oxygen species in the interfacial Cu2-x-O-Ti4-y bond chains and on CuOx clusters, cooperatively promoting the conversion of NO to NO2. As a result, the CuOx/TiO2 catalyst exhibits exceptional catalytic performance in soot oxidation, with a four-fold higher reaction rate (4.17 μmol g−1 min−1) than that of single-atom Cu₁-TiO2 catalyst. Such findings provide a novel strategy for the advancement of Cu-based cluster catalysts in environmental applications.
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