Soot Combustion over Cu–Co Spinel Catalysts: The Intrinsic Effects of Precursors on Catalytic Activity

In this work, a series of CuCo₂O₄-x (x = N, A and C) catalysts were synthesized using different metal salt precursors by urea hydrothermal method for catalytic soot combustion. The effect of CuCo₂O₄-x catalysts on soot conversion and CO₂ selectivity in both loose and tight contact mode was investigated. The CuCo₂O₄-N catalyst exhibited outstanding catalytic activity with the characteristic temperatures (T₁₀, T₅₀ and T₉₀) of 451 °C, 520 °C and 558 °C, respectively, while the CO₂ selectivity reached 98.8% during the reaction. With the addition of NO, the soot combustion was further accelerated over all catalysts. Compared with the loose contact mode, the soot conversion was improved in the tight contact mode. The CuCo₂O₄-N catalysts showed better textural properties compared to the CuCo₂O₄-A and CuCo₂O₄-C, such as higher specific surface areas and pore volumes. The XRD results confirmed that the formation of a CuCo₂O₄ crystal phase in all catalysts. However, the CuO crystal phase only presented in CuCo₂O₄-N and CuCo₂O₄-A. The relative contents of Cu²⁺, Co³⁺ and O_ads on the surface of CuCo₂O₄-x (x = N, A and C) catalysts were analyzed by XPS. The CuCo₂O₄-N catalyst displayed the highest relative content of Cu²⁺, Co³⁺ and O_ads. The activity of catalytic soot combustion showed a good correlation with the order of the relative contents of Cu²⁺, Co³⁺ and O_ads. Additionally, the CuCo₂O₄-N catalyst exhibited lower reduction temperature compared to the CuCo₂O₄-A and CuCo₂O₄-C. The cycle tests clarified that the copper–cobalt spinel catalyst obtained good stability. In addition, based on the Mars–van Krevelen mechanism, the process of catalytic soot combustion was described combined with the electron transfer process and the role of oxygen species over CuCo₂O₄ spinel catalysts.