Frustrated Lewis
Pair Meets Polyhedral Oligomeric
Silsesquioxane: Water-Tolerant Hybrid Porous Networks for Robust,
Efficient, and Recyclable CO2 Catalysis
posted on 2025-01-25, 14:05authored byNan Yang, Yixin Wang, Shiqing Huang, Xiaoyu Yan, Qiang Yan
Frustrated Lewis pair chemistry (FLP) occupy a crucial
position
in nonmetal-mediated catalysis, especially toward activation of inert
gas molecules. Yet, one formidable issue of homogeneous FLP catalysts
is their instability on preservation and recycling. Here we contribute
a general solution that marries the polyhedral oligomeric silsesquioxane
(POSS) with a structurally specific frustrated Lewis acid to fabricate
porous polymer networks, which can form in situ water-insensitive
heterogeneous FLP catalysts upon employing Lewis base substrates.
The excellent resistance to water derives from the synergy of superhydrophobicity
of silsesquioxane cage and the multiscale micro/nano-structural effect
of formed porous networks. Using CO2 as a C1 feedstock,
the FLP-POSS hybrid materials allow for the catalytically conversion
of a variety of diamine substrates into the medicinal benzimidazole
derivatives. Not only can the FLP units be immobilized on the networks
meeting the needs of recyclable utilization but, more importantly,
the materials are also of high catalytic efficiency and capable of
working at near ambient CO2 condition owing to their favorable
CO2 selectivity. Given that this organic/inorganic hybrid
FLP catalyst features low cost, ease of synthesis, and little requirements
on internal structural ordering, it will pave the way for large-scale
preparation of amorphous heterogeneous FLP materials toward low-cost,
robust, and sustainable C1 conversion.