The creation of smart catalytic materials whose active sites can be dynamically tuned represents a significant challenge in materials science. Herein, we demonstrate the rational design of a ZSM-5@NO2-MIL-53(Al) core–shell heterostructure that enables in situ switching between Brønsted and Lewis acid functionalities via postsynthetic AlCl3 modification. This engineered interface is pivotal to the material’s dynamic behavior. Density functional theory (DFT) calculations reveal that the acid-site switching dramatically simplifies the catalytic pathway for chlorosilane disproportionation, reducing the number of steps from six to four and increasing the energy difference between the main and side reaction pathways to 19.41 kJ·mol–1, which is projected to enhance the selectivity for dimethyldichlorosilane by over 25%. This work not only elucidates the electronic-level mechanism of the universal strategy “interface postmodification-induced dynamic acid switching” but also provides quantitative predictions for selective enhancement based on transition state theory. This offers a clear theoretical blueprint for designing next-generation intelligent catalytic materials that combine high activity, high selectivity, and high stability.
Xu et al. (2026) studied this question.