1. Northeast Normal Univ, Key Lab Polyoxometalate & Reticular Mat Chem, Minist Educ, Changchun 130024, Peoples R China
2. Tianjin Univ Technol, Sch Mat Sci & Engn, Inst New Energy Mat & Low Carbon Technol, Tianjin 300384, Peoples R China
折叠
Abstract
It is extremely desirable to explore molecular catalysts with precise structure for in-depth exploring structureactivity relationship of CO2 photoreduction. Herein, we demonstrate the precise encapsulation of dual-nuclear clusters {Fe2(H2O)6(triazole)3} into metal-organic frameworks (MOFs) via ligand substitution strategy, resulting in two Fe2@Fe3-MOF composites (Fe3-Fe2 and NH2-Fe3-Fe2). The fixed distance between two adjacent Fe3(mu 3O)Cl(H2O)2 nodes in the MOF matrix allows the Fe2-Tri clusters to be fixed at a predetermined distance to unveil the critical role in improving the activity and selectivity for CO2 reduction. The performance of Fe3-Fe2 and NH2Fe3-Fe2 can reach to 309.3 and 395.5 mu mol g-1 h-1 respectively, much superior to most of the state-of-the-art MOF catalysts. Such high activity and selectivity for formate generation can be attributed to the inter-clusters synergy mediated via in situ formed H-bonds and the cluster-framework cooperativity, supported by the results of DFT calculations and systemic experimental characterizations.
NSTL
Elsevier