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Precise modulation of the electronic structure of the catalyst is critical for generating highly active sites in targeted catalytic transformations. We report a strategy to regulate the electronic properties of metal–organic frameworks (MOFs) by constructing functional-group-modified MOF-on-MOF heterojunctions for selective nitroarene hydrogenation. As a representative heterostructure, the ZIF-67-on-NH 2 -UiO-66 heterostructure is fabricated by epitaxially growing Co-based ZIF-67 on NH 2 -UiO-66. Combining experimental studies and first-principles calculations demonstrates that the electron-donating substituent (−NH 2 ) group elevates the d-band center of the heterojunction, facilitating electron transfer compared to the unfunctionalized ZIF-67-on-UiO-66 analog. Consequently, ZIF-67-on-NH 2 -UiO-66 exhibits exceptional reactivity and chemoselectivity for hydrogenating diverse functionalized nitroarenes under mild conditions, surpassing most reported catalysts under comparable settings. This work establishes ZIF-on-MOF functionalization as an effective strategy to engineer electronic structures at catalytic interfaces for advanced selective hydrogenations.
Cai et al. (Thu,) studied this question.