Catalysis Today, Vol.359, 124-132, 2021
Dual-functionalized ZIF-8 as an efficient acid-base bifunctional catalyst for the one-pot tandem reaction
An acid-base bifunctional zeolitic imidazolate framework catalyst (ZIF8-A61-SO3H) with amine and sulfonic acid groups was successfully prepared through simple two step post-synthetic modification: preparation of aminefunctionalized ZIF-8 with amine contents of 61% (ZIF8-A61) by the ligand exchange of 2-mIM with 3-amino1,2,4-triazole (Atz), followed by the sulfonic acid functionalization by the ring-opening reaction of 1,3-propanesultone with -NH2 groups in ZIF8-A61. Amine-functionalized ZIF8-A materials with difference amine contents (15%, 34%, and 61%, respectively) were also prepared by controlling the synthesis time. All obtained ZIF catalysts evaluated as a heterogeneous catalyst for one-pot deacetalization-Knoevenagel condensation tandem reaction. Compared with ZIF-8 and amine-functionalized ZIF-8 catalysts, ZIF8-A61-SO3H catalyst showed good catalytic performance with 100% conversion of the reactant and 98% selectivity of the final Knoevenagel product. An enhanced catalytic activity can be attributed to the co-existence of site-isolated acid-base groups on the ZIF8-A61-SO3H catalyst in close proximity. The heterogeneous nature of the catalytic system was confirmed by a hot-filtering test and the catalyst also exhibited reusable in the five repeated cycles. A plausible catalytic mechanism of deacetalization-Knoevenagel condensation reaction over ZIF8-A61-SO3H was also proposed.
Keywords:Zeolitic imidazolate frameworks (ZIFs);Amine-functionalization;Post-synthetic modification;Acid-base reaction;One-pot tandem reaction