A Microporous Zirconium Metal‐Organic Framework Based on trans‐Aconitic Acid for Selective Carbon Dioxide Adsorption

Abstract

The discovery of naturally occurring linker-based zirconium MOFs with permanent porosity and accessible functional groups remains a challenge. Using trans-aconitic acid to assemble with Zr 6 oxoclusters under green and scalable conditions, a novel microporous Zr-aconitate framework has been prepared successfully with a high space-time yield. This MOF is isostructural to the previously reported Zr-fumarate, however with a smaller pore size and an abundant concentration of free IntroductionZirconium metal-organic frameworks (MOFs) have been intensively investigated and developed over the last decade, mainly due to their improved stability compared to most of the other metal cations-based MOFs. [1] Among diverse organic linkers used for Zr-MOFs, the majority are artificially synthetic ones, including most of the aromatic multi-carboxylic acids, [2] phenolates [3] and phosphonates. [4] In sharp contrast to artificial linkers, naturally occurring ones display numerous advantages, such as low toxicity and bio-compatibility, cost-effective, easy and abundant availability, which fulfil the sustainable development criteria. Nevertheless, there are very limited examples of Zr-MOFs constructed from naturally occurring linkers. Indeed only the three-dimensional (3D) Zr-Fumarate (also known as MOF-801) [5] and 2D Zr-formate, [6] have been reported so far. The 3D Zr-Fumarate is of particular interest due to its UiO-66 type rigid micropore system. [7] It was reported as a promising material in applications including water harvesting [8] and removal of fluoride contaminant. [9] The incorporation of functional groups into [a]

Engineering Structural Dynamics of Zirconium Metal–Organic Frameworks Based on Natural C4 Linkers

“…Pure formic acid was used as solvent in this case since it has been shown to be an efficient modulator for preparing group IV metal-based MOFs. 38,44 As expected, instead of forming the well-known Zr-Fumarate structure, MIP-203-F, a new phase with lower structural symmetry was obtained ( Fig.1b). When succinic acid was used under the same reaction conditions, a clear solution was observed without any solid product, possibly due to the much greater solubility of succinic acid in formic acid.…”

“…23,28 Among the reported flexible linkers, naturally occurring compounds are of particular interest since they are bio-compatible and thus efficiently reduce the toxicity of the resulting MOFs. In the limited cases of existing Zr-MOFs composed of natural acids, fumaric acid and its derivatives are dominant despite the fact that they all share the 12-fold connectivity, which highlights the controllable crystallization of Zr-fumarate type frameworks, [36][37][38][39] as well the rigid structural character of fumaric acid, which is the same as evidenced in other MOFs. [24][25]40 On the contrary, succinic acid, which behaves as a soft molecular spring as seen in Co-MOFs, [41][42] Fumaric acid ( Fig.…”

Toward Green Production of Water-Stable Metal–Organic Frameworks Based on High-Valence Metals with Low Toxicities

“…It is worthy to note that some recent examples of Zr-MOFs prepared at a laboratory gram-scale have shown an interesting effect of reactant concentration on the final production. In a sharp contrast to the conventional diluted solution for growing single crystalline products, those Zr-MOFs required considerably higher reactant concentrations to generate corresponding products. − , This possibly suggests distinct reaction mechanisms other than the conventional ones, which could be important and helpful for the green production of related MOFs. Furthermore, the final target is to finalize the green production of each useful MOF by carefully analyzing its formation mechanism, which likely requires a combination of chemistry, material, physics and engineering.…”

Metal–Organic Frameworks Based on Group 3 and 4 Metals

“…In addition, other groups have also reported some tritopic cluster based Zr-MOFs with 9 or 12 connected Zr clusters. [194][195][196]…”

“…[183] Additionally, the twofold interpenetrated Zr-IAM-4, the trans-aconitic acid based MIP-205, and the fcu Zr-TzTz are all show selective adsorption of CO 2 over N 2 . [176,196,210]…”