Growth Mechanism of Metal–Organic Frameworks: Insights into the Nucleation by Employing a Step‐by‐Step Route

Abstract

One step at a time: The in situ monitoring of the step-by-step formation of metal-organic frameworks (MOFs) by using surface plasmon resonance (SPR), allows the nucleation process and the formation of the secondary building units to be investigated. Growth rates on functionalized organic surfaces with different crystallographic orientations can also be studied.

Stability and Hydrolyzation of Metal Organic Frameworks with Paddle-Wheel SBUs upon Hydration

“…The X-ray diffraction pattern clearly points to a structural change after hydration. All peaks shift to a higher 2θ value except for the [001], indicating that the distance between the 2D Cu 2 (COO) 4 layers remains unchanged, which is consistent with the Raman observation that ted still coordinates to the metal sites after hydration. The twotheta position of the phases (i.e.…”

“…We also find that the initial decomposition pathways sensitively depend on the central metal ions: For Cu(bdc)(ted) 0.5 , a hydrolysis reaction of water molecules with Cu-O-C group induces the paddle wheel structural decomposition. For Zn(bdc)(ted) 0.5 and Co(bdc)(ted) 0.5 , the water molecules replace ted pillars and bond to the apical sites of paddle wheel Zn 2 (COO) 4 and Co 2 (COO) 4. Finally, we find that the overall stability of isostructural MOFs M(bdc)(ted) 0.5 follows the order of Cu-MOF<Ni-MOF>Zn-MOF> Co-MOF and this order can be correlated with bond dissociation energy of diatomic molecules metal-oxygen and overall formation(stability) constants of metal amine complexes.…”

“…However, unlike the D 2 O molecules in hydrated Zn(bdc)(ted) 0.5 that have a bifurcated-deuterium bonding with Zn 2 (bdc) 2 layers, the D 2 O molecules in hydrated Co(bdc)(ted) 0.5 are coordinated to Co(II) ions via one oxygen atom only. As a result, the paddle wheel Co 2 (COO) 4 is distorted and the Co-Co interaction is removed. This is why the doublet involving Co-Co in Raman spectra of Fig.…”

“…S1). M(bdc)(ted) 0.5 has been shown to be an excellent absorbent for a variety of gases (H 2 , CO 2 , CH 4 and other hydrocarbons). [29][30][31] The paddle wheel binuclear metal clusters within M(bdc)(ted) 0.5 can be found in a large number of reported nanoframeworks materials with high microporosity, thermal stability, good sorption properties and other advanced functional properties such as magnetic property.…”

Langmuir–Blodgett Films of the Metal–Organic Framework MIL-101(Cr): Preparation, Characterization, and CO2 Adsorption Study Using a QCM-Based Setup

“…In this method, gold supports functionalized with self-assembled monolayers (SAMs) of organic molecules are typically used. 13 In this context, different SURMOFs have been directly grown on SAM-modified quartz crystal microbalance (QCM) gold substrates and the adsorption and desorption of different substances onto the films have been monitored. 14 QCM substrates coated with SURMOFs are very interesting systems for the development of chemical sensors and also for studying and characterizing fundamental properties of MOFs such as mass transfer processes.…”