Novel Core–Shell (ε-MnO₂/CeO₂)@CeO₂ Composite Catalyst with a Synergistic Effect for Efficient Formaldehyde Oxidation

A novel core–shell (ε-MnO2/CeO2)@CeO2 composite catalyst with a synergistic effect was prepared by hydrothermal reaction and thermal decomposition and its application to high-efficiency oxidation removal of formaldehyde (HCHO) was systemically investigated. The (MnCO3/CeO2)@CeO2 precursor was prepared first by the one-pot hydrothermal reaction of Mn2+ and Ce3+ solutions with a CO2-storage material (CO2SM) without any external templates or surfactants required. The thermal decomposition of the precursor afforded the core–shell (ε-MnO2/CeO2)@CeO2 composite catalyst with excellent catalytic performance. HCHO in the feed gas (180 ppm HCHO, 21% O2, N2 balanced) at a gas hourly space velocity of 100 L/(gcat h) is 100% converted over the catalyst at 80 °C. The conversion rate remains above 95% in 72 h and above 73.8% in 140 h, suggesting the strong stability of the catalyst at high gas flow rates and relatively low temperatures. The synergistic mechanism of the catalyst was explored by X-ray diffraction, Raman, Brunauer–Emmett–Teller, transmission electron microscopy, and X-ray photoelectron spectroscopy. The number of defects in the catalyst and the strength of the Mn–O bond in ε-MnO2 can be tuned by adjusting the synthesis conditions. More oxygen vacancies on the surface of CeO2 can make the synergistic effect of the catalyst stronger, which significantly improves the lattice oxygen (Olatt) activity on the surface of ε-MnO2. Our work has provided new insights into the preparation of the desired composite catalysts with excellent performances.