Fast and scalable synthesis of uniform zirconium-, hafnium-based metal–organic framework nanocrystals

Abstract

Metal–organic frameworks based on zirconium or hafnium possess tantalizing commercial prospects due to their high stability but require a long reaction time to form crystals. The fast synthesis of uniform Zr-, Hf-MOF nanocrystals at scale is of key importance in the potential commercial application of MOFs. In this work, we have developed a versatile strategy through controlling the hydrolysis and nucleation of metal salts in the presence of acetic acid and water; up to 24 grams of UiO-66-NH₂ nanocrystals with a uniform octahedron could be synthesized within 15 minutes using a one step method. The current synthetic strategy could be extended to other Zr-, Hf-MOF nanocrystals [UiO-66-Fast, UiO-66-(OH)₂-Fast, UiO-66-2,6-NDC-Fast, UiO-67-Fast, BUT-12-Fast, PCN-222-Ni-Fast, PCN-222-Co-Fast, Hf-UiO-66-Fast, Hf-UiO-66-NH₂-Fast, Hf-UiO-66-(OH)₂-Fast, Hf-UiO-66-2,6-NDC-Fast and Hf-BUT-12-Fast]. Significantly, when noble metal nanoparticles (NPs) are introduced into MOF precursors, NPs encapsulated in MOFs with excellent dispersion have also been obtained and show outstanding performance in catalysis. This facile procedure is expected to pave the way to expand the commercial applications of MOFs.