Abstract:
The utilization of CO2 as a C1 feedstock for the synthesis of high-value chemicals and fuels is an important step towards mitigating the increasing concentration of atmospheric carbon dioxide as well as the
production of value-added chemicals. Herein, we demonstrate the development of an efficient recyclable
catalyst for the conversion of CO2 into oxazolidinones, which are important commodity chemicals for
antibiotics, by utilizing an N-heterocyclic carbene (NHC)-based metal–organic framework (MOF). The
NHC-centers lined in the pore walls of the MOF were utilized to anchor catalytically active Cu(I) ions by
post-synthetic modification (PSM). The Cu(I)-embedded MOF showed highly recyclable and selective CO2
uptake properties with a high heat of interaction energy of 43 kJ mol−1
. The presence of a high density of
CO2-philic NHC and catalytic Cu(I) sites in the 1D channels of the MOF render highly efficient catalytic
activity for fixation of CO2 into α-alkylidene cyclic carbonates and oxazolidinones at RT and atmospheric
pressure conditions. Notably, Cu(I)@NHC–MOF showed excellent recyclability for up to 10 cycles of
regeneration with retention of catalytic activity as well as chemical stability. To the best of our knowledge,
Cu(I)@NHC–MOF is the first example of a noble metal-free MOF-based heterogeneous catalyst for the
utilization of CO2 to synthesize important value-added chemicals under mild conditions.
