Nickel-Mediated Formation of Stable Frustrated Lewis Pairs in Rare Earth MOFs for Dicyclopentadiene Hydrogenation
Rare earth metal-organic frameworks (RE-MOFs) exhibit limited active site density and insufficient thermal stability, constraining their catalytic utility. This study employs heteroatom doping and defect engineering to synthesize RE-Ni-BTC materials. Nickel incorporation into RE-MOFs alters charge distribution and crystal structure stability, generating atomic-scale defects that induce RE–O frustrated Lewis pairs (FLPs) and a distinct Ni–O4 coordination motif. Nd-Ni-BTC surpasses Ce-Ni-BTC due to enhanced Lewis acid-base properties and superior substrate adsorption/desorption, achieving complete dicyclopentadiene (DCPD) conversion and at least seven recycling cycles under 100 °C, 2 MPa H2, and 10 h. The approach balances catalytic activity and stability without structural degradation, offering a route for defective MOFs in hydrogenation catalysis and catalyst design.