Defect‐driven electronic coupling and oxygen vacancy engineering in supported high‐entropy oxides for desulfurization

Abstract High‐entropy oxides (HEOs) are promising heterogeneous catalysts due to their multiple active sites and structural stability, but their application is limited by complex synthesis and nanoparticle sintering. Here, we present a defect‐induced strategy to construct strong metal‐support interactions (SMSI) between MnCeNiCuCo HEO nanoparticles and defect‐rich hexagonal boron nitride nanosheets (h‐BNNS), forming HEO/h‐BNNS. Contrary to classical H 2 ‐induced SMSI, the inherent N/B vacancies in h‐BNNS anchor the HEO and induce spontaneous B‐atom migration over the HEO surface under N 2 , forming a permeable B–O encapsulation. This encapsulation not only inhibits sintering but also induces electronic coupling with the HEO lattice, modulating local charge density and generating abundant oxygen vacancies. Using aerobic oxidative desulfurization as a model reaction, HEO/h‐BNNS achieves a 99.9% desulfurization efficiency. This work demonstrates a defect‐driven pathway to engineer supported high‐entropy catalysts and provides a rational framework for designing efficient, durable, and scalable catalytic systems for energy and environmental applications.