H₂-Induced In Situ Formation of Magnetic Nickel-Based Metal–Organic Frameworks for Catalytic Hydrogenation of Dicyclopentadiene

The development of low-cost and durable nickel-based catalysts presents a significant challenge in the hydrogenation of dicyclopentadiene (DCPD). In this study, we synthesized a nickel-based metal–organic framework (MOF), Ni-PET, utilizing waste poly(ethylene terephthalate) (PET) as a ligand, which undergoes an in situ transformation into magnetic MOFs (Ni-PET-M) under a pressurized hydrogen atmosphere at 100 °C. This transformation enhances spin polarization at the nickel active centers, significantly increasing unpaired electron density and lowering the electron transfer barrier for hydrogen dissociation. Remarkably, Ni-PET-M achieves complete DCPD conversion (100%) and a near-perfect selectivity of 99.9% for trans-hydrodicyclopentadiene (THDCPD) at 100 °C, demonstrating excellent structural stability and reusability. This performance represents the best results to date for pure MOF materials in DCPD hydrogenation. Furthermore, the reconfiguration of the electronic structure within the nickel-based catalytic system not only facilitates Ni–H bond formation by reducing the activation energy barrier but also optimizes charge redistribution on the adsorbed C═C bonds. This optimization significantly decreases the π-bond activation energy, thereby enhancing the hydrogenation performance. This work provides a novel strategy linking the spintronic structure of magnetic catalytic systems to the hydrogenation reaction, offering new insights for the design of advanced catalytic materials.