Weakened Mn-O bond in Mn-Ce catalysts through K doping induced oxygen activation for boosting benzene oxidation at low temperatures.

K-doped Mn-Ce solid solution catalysts were synthesized using a combination of coprecipitation and hydrothermal methods, demonstrating excellent performance in benzene oxidation. The catalyst K1Ce5Mn5 exhibited comparable activity to noble metal catalysts, achieving a 90 % benzene conversion at approximately 194 ℃. Durable tests under dry and moist conditions revealed that the catalyst could maintain its activity for 50 h at 218 ℃ and 236 ℃, respectively. Characterization results indicated that the catalyst's enhanced activity resulted from the weakened Mn-O bonding caused by the introduction of K+, facilitating the activation of oxygen and its involvement in the reaction. CeOx, the main crystalline phase of Mn-Ce solid solutions, provided abundant oxygen vacancies for capturing and activating oxygen molecules for the weakened Mn-O structures. This conclusion was further supported by partial density of state analysis from density functional theory computations, revealing that the introduction of K+ weakened the orbital hybridization of Mn3d and O2p. Finally, in situ diffuse reflectance infrared Fourier-transform spectroscopy (in situ DRIFTS) studies on Ce5Mn5 and K1Ce5Mn5 catalysts suggested that the introduction of K+ promoted the conversion of adsorbed benzene. Furthermore, intermediate products were transformed more rapidly for K1Ce5Mn5 compared to Ce5Mn5.