Synthesis of Quasi-MOFs featuring special hub-and-spoke channels and surface NiO species for enhanced total hydrogenation of furfural

Abstract

The design of Ni-based catalysts with high activity for the conversion of furfural (FFR) into tetrahydrofurfuryl alcohol (THFA) holds great promise for the upgrading of renewable resources. However, the weak affinity between the furan ring and Ni⁰ limits the hydrogenation reaction under moderate conditions. In this work, we propose a new strategy for the design of highly efficient hydrogenation catalysts. Quasi-MOFs with unique hub-and-spoke channels, and abundant Ni⁰ and surface NiO species were successfully prepared through controlled deligandation of Ni-MOF-74 by partial thermal transformation. The spokewise channels facilitate the delivery of the reactants and expose more catalytic active sites. The obtained Quasi-MOF exhibits strong interaction between Ni metal nanoparticles and the partially decomposed ligand. The presence of surface NiO species can strengthen the affinity between the catalyst and FFR/H₂ molecules and enhance the H-donation capacity, leading to dramatically enhanced hydrogenation activity. The synthesized Quasi-MOF-9h exhibited excellent activity in the total hydrogenation of FFR, achieving 98% yield of THFA within 4 h at 70 °C and 3 MPa H₂.