Enhanced oxidative ability, recyclability, water tolerance and aromatic resistance of α-MnO2 catalyst for room-temperature formaldehyde oxidation via simple oxalic acid treatment

To obtain a versatile formaldehyde oxidation material, simultaneously increasing the oxidative ability, recyclability and deactivation repellence (e.g., enduring the interference from moisture and aromatic compound omnipresent in indoor air) is of great significance. Herein, the above properties of α-MnO2 were synchronously updated via one step treatment in oxalic acid (H2C2O4), and an in-depth understanding of the surface properties-performance relationship was provided by systematic characterizations and designed experiments. Compared with the pristine sample, XPS, ESR, O2-TPD, CO-TPR and pyridine-IR reveal that H2C2O4 created substantial Mn3+ species on surface, exposing a higher coverage of oxygen vacancies that actively participated in the dissociative activation of gas-phase O2 into reactive chemically adsorbed oxygen (OC), and the abundant Lewis acid sites further enabled the effective O2 activation process. The large amount of oxygen OC promoted the HCHO-to-CO2 conversion and inhibited the accumulation of formate that required a high temperature of 170 °C to be eliminated, thus conspicuously improving the α-MnO2's thermal recovery. The combined H2O-TPD, H2O-preadsorbed CO-TPR, C6H6-TPD and C6H6-preadsorbed CO-TPR investigations shed light on the H2C2O4-induced water and benzene resistance. The notably weakened water and benzene binding strength with the H2C2O4-modified surface together with the unrestrained oxygen OC accounted for the outstanding anti-deactivation performance.