One‐Step Room‐Temperature Synthesis of Metal(IV) Carboxylate Metal—Organic Frameworks

Abstract

Room‐temperature syntheses of metal–organic frameworks (MOFs) are of interest to meet the demand of the sustainable chemistry and are a pre‐requisite for the incorporation of functional compounds in water‐stable MOFs. However, only few routes under ambient conditions have been reported to produce metal(IV)‐based MOFs. Reported here is a new versatile one‐step synthesis of a series of highly porous M6‐oxocluster‐based MOFs (M=Zr, Hf, Ce) at room temperature, including 8‐ or 12‐connected micro/mesoporous solids with different functionalized organic ligands. The compounds show varying degrees of defects, particularly for 12‐connected phases, while maintaining the chemical stability of the parent MOFs. Proposed here are first insights into in situ kinetics observations for efficient MOF preparation. Remarkably, the synthesis has a high space‐time yield and also provides the possibility to tune the particle size, therefore paving the way for their practical use.

Recent Progresses in Metal–Organic Frameworks Based Core–shell Composites

“…Tang et al reported a series of sandwich structures based on MIL-101 and Pt NPs in 2016, which represent a proof of concept to design highly efficient and selective catalysts. [58] Recently, this group synthesized a series of sandwich structures UiO-67@Pd NPs@UiO-X (X=66, 67(N) (N = 2,2'-bipyridine-5,5'dicarboxylic acid), 67,68) to study the contribution of organic linkers in catalytic efficiency via a similar epitaxial growth method (Figure 5 (A)). Micron-scale UiO-67 was chosen as the core and pre-synthesized in DMF through a conventional method (Figure 5 (B, C)).…”

A Showcase of Green Chemistry: Sustainable Synthetic Approach of Zirconium‐Based MOF Materials

“…[29a] Cohen firstly prepared UiO-66-F 4 by the same approach, [61] and then through postsynthetic exchange, obtained several derivatives in neutral aqueous solution under room temperature within hours. Noteworthily, S. Dai et al [50] provided a simple, green and scalable route to produce more species of ZrÀ MOFs, including benchmark MOF-801, and other metal(IV) MOFs(Ce and Hf) under ambient temperature and pressure, together with good STY (168 kg • m À 3 • day À 1 for MOF-801). The successful synthesis can ascribe the rapid formation of Zr 6 oxoclusters in a highly acidic solution hydrolyzed by the zirconium salts.…”

Advances in Functional Metal‐Organic Frameworks Based On‐Demand Drug Delivery Systems for Tumor Therapeutics

“…Most recently, Dai et al ( Figure 6 ) reported a one‐step, room temperature synthesis of highly porous metal(IV) carboxylate MOF systems containing five 12‐connected and two 8‐connected M 6 oxo‐clusters with different functionalized organic ligands. [ 83 ] Furthermore, scale‐up of the synthesis involved the use of a 5 L pilot‐scale system, giving evidence of a high yield for room temperature syntheses of Zr‐based MOFs.…”