Regulating electron transfer between valence-variable cuprum and cerium sites within bimetallic metal-organic...

Modulating the electron distribution between active sites in metal-organic frameworks (MOFs) offers a promising strategy for optimizing their catalytic performance. In this study, we employed a novel heterovalent substitution strategy to synthesize bimetallic organic frameworks (Cu_xCe_y-BTC) that feature dual active sites with copper (Cu) and cerium (Ce), Our objective was to achieve efficient hydrogenation of dicyclopentadiene (DCPD) by regulating the electron transfer between the valence-variable Cu and Ce species. The designed Cu_xCe_y-BTC were characterized using various spectroscopic and microscopic techniques, along with density functional theory (DFT) calculations, confirming the successful incorporation of bimetallic nodes within the framework structure and the electron transfer between them. The transfer of electrons from the less electronegative Ce to the Cu sites promotes the chemisorption of hydrogen gas (H₂) on the electron-rich Cu sites, thereby optimizing the activation of the CC bond in DCPD. The Cu₄Ce-BTC catalyst demonstrated exceptional performance, achieving complete conversion of DCPD and significantly surpassing monometallic MOFs. Moreover, we proposed a plausible pathway for the hydrogenation of DCPD. This work highlights the synergistic effects between bimetallic centers and offers a novel strategy to improve the MOFs' catalytic activity by modulating electron distribution between dual active sites.