Rationally FabricatedCe–Mn@ZrO₂–SO₄^2– Catalyst Boosts the EfficientDestruction of Chlorobenzene with SO₂ Impurity: Synergyof Surface SO₄^2– and Acidic Sites

The catalytic deactivation caused by SO₂ impurity remains a great challenge in the efficient destruction of industrial chlorinated volatile organic compounds (CVOCs). Herein, a Ce–Mn@ZrO₂–SO₄^2– catalyst with a Ce–O–Mn active system and ZrO₂–SO₄^2– protective layer was rationally engineered, which exhibits superior activity for chlorobenzene (CB) and SO₂ cotreatment at 228 °C, achieving 90% CB mineralizationover 80% higher than that of the CeO₂ catalyst. In situ characterization and theoretical calculation results reveal that the SO₄^2– groups not only inhibit the adsorption of SO₂ molecules through steric hindrance and electrostatic repulsion but also act as the Brønsted acid sites (BAS) to promote C–Cl cleavage of chlorobenzene (CB) and accelerate the desorption of Cl radicals as inorganic chlorine (HCl and Cl₂). Additionally, the Ce–O–Mn structure accelerates electron transfer between active sites, enhances the strength of Lewis acid sites (LAS), and weakens the lattice oxygen stability to generate oxygen vacancies (O_v). These features collectively result in the excellent chlorine and sulfur resistance of the Ce–Mn@ZrO₂–SO₄^2– catalyst. Compared to CeO₂ and Ce–Mn@ZrO₂, chlorinated and sulfated byproducts respectively decrease by 7.9 and 2.7 times in the presence of 100 ppm SO₂. This study provides a feasible and promising strategy for engineering efficacious non-noble metal catalysts toward CVOCs’ deep purification with SO₂ impurity, showcasing substantial economic and environmental benefits.