CVD-induced corrosion reconstruction of defective metal–organic frameworks boosted advanced catalytic oxidation

Abstract

Metal–organic frameworks (MOFs) are promising candidates for many applications, particularly catalysis. However, the development of highly active MOFs with controlled defective structures and components still remains a significant challenge. Herein, we report a new and versatile CVD-induced corrosion strategy for the reconstruction of defective Fe-MOFs through persulfate gasification. Strong confined interactions between guests and Fe nodes realized the reconstruction of the crystal structure and allowed the introduction of a heteroatom. With this novel approach, a uniform dispersion of defects and a perfect metallic/heteroatom interface were obtained. This simultaneous structural engineering method that could utilize SO₂ emissions successfully led MIL-53(Fe) to exhibit superior activity for photocatalytic oxidation (TOFs as high as 2.287 h⁻¹). DFT calculations coupled with experimental evidence revealed that the performance was triggered by the synergistic catalysis of abundant sulfur and oxygen vacancies on the defective (100) crystal face. This unique “waste-to-treasure” approach significantly boosts catalytic efficiency while harnessing valuable resource from waste gas, offering a practical pathway for advanced oxidation.