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Nickel-Mediated Formation of Stable Frustrated Lewis Pairs in Rare Earth MOFs for Dicyclopentadiene Hydrogenation

Authors: ZHAO Danfeng; LIN Jing; LI Rushuo; XU Xinmeng; HU Fajie; WANG Zhaokun; HUANG Xiubing; WANG Ge

DOI: 10.1007/s40843-025-3335-6Status: Verified Translated Edition
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Key Findings in This Report

• • Nd-Ni-BTC achieves 100% DCPD conversion at 100 °C, 2 MPa H2, and 10 h, with no loss in activity after seven consecutive recycling runs, demonstrating operational stability that exceeds conventional Ni-based catalysts (e.g., Raney nickel) which suffer from mechanical attrition and regeneration challenges. • • The incorporation of Ni into RE-MOFs creates Ni–O4 coordination and defect-induced RE–O frustrated Lewis pairs (FLPs), as confirmed by structural and spectroscopic analyses; this dual-site architecture enhances Lewis acid-base properties, enabling selective hydrogenation of DCPD to endo-THDCPD without noble metals. • • Nd-Ni-BTC outperforms Ce-Ni-BTC by a measurable margin in conversion and selectivity, attributed to the smaller ionic radius and higher charge density of Nd3+ that strengthen substrate adsorption/desorption; this lanthanide-dependent performance provides a design rule for tuning FLP strength in MOF catalysts. • • The catalyst maintains crystallinity and structural integrity after seven cycles, as evidenced by unchanged PXRD patterns and Ni K-edge XAS spectra, overcoming the trade-off between defect generation and framework stability that plagues conventional defective MOFs.