Structure Effects Induced by High Mechanical Compaction of STAM‐17‐OEt MOF Powders

Abstract

Metal-organic frameworks (MOFs) are promising materials for many potential applications, spacing from gas storage to catalysis. However, the powder form they are generally made of is not suitable, mainly because of the low packing density. Powder compaction is therefore necessary, but also challenging because of its typical mechanical fragility. Indeed, generally, MOF powders undergo irreversibly damages upon densification processes, for example partially or totally loosing microporosity and catalytic activity. In this work, we have deeply studied the compaction effects on the flexible Cu(II)-based MOF STAM-17-OEt (Cu(C 10 O 5 H 8 ) • 1.6 H 2 O), whose chemical composition is close to that of HKUST-1, obtaining that, by contrast, STAM-17-OEt is extremely suitable for mechanical compaction processes with pressures up to 200 MPa, which increase its packing density and its catalytic activity, and then also preserve the characteristic porosity, flexibility and water stability of STAM-17-OEt. The results are supported by many experimental techniques including EPR spectroscopy, PXRD diffraction, CO 2 isotherms studies and catalytic tests.

Ab Initio Study of Hydrostable Metal–Organic Frameworks for Postsynthetic Modification and Tuning toward Practical Applications

“…The calculated Δ H ads are presented in Table . The predicted Δ H ads for CO 2 on a STAM-17-OEt of −19.3 kJ/mol is in reasonable agreement with an experimental isosteric heat of adsorption of −16.2 kJ/mol and at a higher pressure of −27.6 kJ/mol . In the absence of additional experimental data, a definitive conclusion could not be reached for the other gases.…”

“…The predicted ΔH ads for CO 2 on a STAM-17-OEt of −19.3 kJ/mol is in reasonable agreement with an experimental isosteric heat of adsorption of −16.2 kJ/mol and at a higher pressure of −27.6 kJ/mol. 55 In the absence of additional experimental data, a definitive conclusion could not be reached for the other gases. However, the calculated ΔH ads still gives us a sense of how STAM-17-OEt will perform under experimental conditions at 298 K.…”

Engineering Catalysis within a Saturated In(III)-Based MOF Possessing Dynamic Ligand–Metal Bonding

“…In particular, the local dynamic metal–carboxylate interactions that underpin whole-framework processes such as ligand/cation exchange have only been reported and rationalized in the MOF literature in recent years. − In 2021, we demonstrated that dynamic metal–carboxylate interactions (Figure e) could be exploited to facilitate ammonium uptake in a saturated scandium-based MOF (MFM-300­(Sc)) . This investigation demonstrated an unusual route via which the framework interacts with guest molecules due to the labile Sc­(III)–carboxylate bond interaction present in the MOF architecture.…”

Switchable Metal Sites in Metal–Organic Framework MFM‐300(Sc): Lewis Acid Catalysis Driven by Metal–Hemilabile Linker Bond Dynamics

“…The concept of hemilability in MOFs and different consequences on the hydrolytic stability and many other properties of this family of porous materials, it has been intensively developed by Morris et al [18][19][20] The associated reversible metal-ligand bond dynamics can explain key phenomena in MOFs from their crystal growth to their phase transitions. [21] For example, Bennett and Horike, elegantly proposed, the different melting mechanisms for ZIFs.…”