A three-dimensional ordered macroporous oxygen-deficient cerium dioxide catalyst, and a preparation method and a use therefor. The catalyst is prepared using polymethyl methacrylate (PMMA) colloidal crystal templating, and subjection to reducing/oxydizing atmosphere calcination and steam treatment. The prepared catalyst exhibits excellent activity and stability in photothermal catalytic purification of styrene, n-hexane, cyclohexane, and other classic atmospheric pollutants. The method features cheap and easily obtainable ingredients and a simple preparation process, controllable oxygen vacancy and amount and strength of surface acid in the resulting material, and excellent photothermal catalytic performance in said material.
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