Synthesis, Characterization, and Catalytic Performance of a New Heterobimetallic Y/Tb Metal−Organic Framework with High Catalytic Activity

Abstract

A three-dimensional heterobimetallic porous structure with the formula {[Y3.5Tb1.5L6(OH)3(H2O)1.5 (DMF)1.5]n· 1.5H2O·DMF}n (L = 3-amino-4-hydroxybenzoate) (Y/Tb-MOF) has been synthesized and characterized by single crystal and powder X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), inductively coupled plasma mass spectrometry (ICP-MS), electrophoretic mobility, and Fourier transform infrared (FTIR) spectroscopy. The structure presents two metal environments: a bioaugmented isosceles wedge (mm2) MO8 and a tricapped trigonal prism (−6m2) MN3O6. These configurations facilitate the creation of channels with a diameter of 10.7 Å, enabling its utilization as an active catalyst where the heterobimetallic nature of the assembly will be explored. This mixed-metal metal−organic framework has been tested in the cycloaddition of epoxides with carbon dioxide as well as in the cyanosilylation and hydroboration reactions of carbonylic substrates. Additionally, a monometallic Tb-MOF analogue has been synthesized for comparative evaluation of their catalytic performances. Both the mixed metal and monometallic variants exhibit outstanding activity in the cyanosilylation and hydroboration of carbonyls and in the synthesis of carbonates under CO2 pressure. However, only the latter exhibits high recyclability.