The invention discloses a molten Al—Si alloy corrosion resistant composite coating and a preparation method and application thereof. The composite coating layer comprises an aluminized layer and a TiO2 thin film layer from the surface of a basal body to the external in sequence. The preparation method of the coating layer comprises the following steps: (S1) the surface of a Fe-based alloy is treated; and then, a solid powder permeating agent is adopted to permeate aluminum; (S2) sand-blasting the aluminized Fe-based alloy; (S3) the Fe-based alloy is washed and dried after sand blasting; and (S4) a TiO2 thin film layer is deposited on the surface of the dried aluminized Fe-based alloy by adopting an atomic layer vapor deposition method.
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