Experimental evidence for a general model of modulated MOF nanoparticle growth

Nanoparticles of metal-organic frameworks (nanoMOFs) boast superior properties compared to their bulk analogs, yet little is known about how common synthetic parameters dictate particle sizes. Here, we provide experimental evidence for the “seesaw” model of nanoMOF growth. Solution acidity, ligand excess, and reactant concentrations are decoupled and shown to form the key independent determinants of nanoMOF sizes, thereby validating the proposal that nanoMOFs arise from coupled equilibria involving ligand deprotonation and metal-ligand complexation. By achieving the first demonstration of a seesaw relationship between nanoMOF sizes and ligand excess, these results provide further proof of the model, as they required deliberate manipulation of relationships outlined by the model. Exploring the relative impacts of these parameters reveals that ligand excess has the greatest ability to decrease sizes, although low acidity and high concentrations can exhibit similar effects. As a complement to existing models of polymer formation and crystal growth, the seesaw model therefore offers a powerful tool for reliable control over nanoMOF sizes.

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Experimental Evidence for a General Model of Modulated MOF Nanoparticle Growth

10.26434/chemrxiv.12401708 ◽

2020 ◽

Author(s):

Checkers R. Marshall ◽

Sara Staudhammer ◽

Carl Brozek

Keyword(s):

Experimental Evidence ◽

Reliable Control ◽

Particle Sizes ◽

Nanoparticle Growth ◽

Seesaw Model ◽

Polymer Formation ◽

Metal Organic ◽

High Concentrations ◽

Solution Acidity ◽

Metal Ligand

Nanoparticles of metal-organic frameworks (nanoMOFs) boast superior properties compared to their bulk analogs, yet little is known about how common synthetic parameters dictate particle sizes. Here, we provide experimental evidence for the “seesaw” model of nanoMOF growth. Solution acidity, ligand excess, and reactant concentrations are decoupled and shown to form the key independent determinants of nanoMOF sizes, thereby validating the proposal that nanoMOFs arise from coupled equilibria involving ligand deprotonation and metal-ligand complexation. By achieving the first demonstration of a seesaw relationship between nanoMOF sizes and ligand excess, these results provide further proof of the model, as they required deliberate manipulation of relationships outlined by the model. Exploring the relative impacts of these parameters reveals that ligand excess has the greatest ability to decrease sizes, although low acidity and high concentrations can exhibit similar effects. As a complement to existing models of polymer formation and crystal growth, the seesaw model therefore offers a powerful tool for reliable control over nanoMOF sizes.

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Experimental Evidence for a General Model of Modulated MOF Nanoparticle Growth

10.26434/chemrxiv.12401708.v1 ◽

2020 ◽

Author(s):

Checkers R. Marshall ◽

Sara Staudhammer ◽

Carl Brozek

Keyword(s):

Experimental Evidence ◽

Reliable Control ◽

Particle Sizes ◽

Nanoparticle Growth ◽

Seesaw Model ◽

Polymer Formation ◽

Metal Organic ◽

High Concentrations ◽

Solution Acidity ◽

Metal Ligand

Nanoparticles of metal-organic frameworks (nanoMOFs) boast superior properties compared to their bulk analogs, yet little is known about how common synthetic parameters dictate particle sizes. Here, we provide experimental evidence for the “seesaw” model of nanoMOF growth. Solution acidity, ligand excess, and reactant concentrations are decoupled and shown to form the key independent determinants of nanoMOF sizes, thereby validating the proposal that nanoMOFs arise from coupled equilibria involving ligand deprotonation and metal-ligand complexation. By achieving the first demonstration of a seesaw relationship between nanoMOF sizes and ligand excess, these results provide further proof of the model, as they required deliberate manipulation of relationships outlined by the model. Exploring the relative impacts of these parameters reveals that ligand excess has the greatest ability to decrease sizes, although low acidity and high concentrations can exhibit similar effects. As a complement to existing models of polymer formation and crystal growth, the seesaw model therefore offers a powerful tool for reliable control over nanoMOF sizes.

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Probing the dynamics of Cu nanoparticle growth inside metal-organic frameworks upon electron beam irradiation

Photonics and Nanostructures - Fundamentals and Applications ◽

10.1016/j.photonics.2020.100832 ◽

2020 ◽

Vol 41 ◽

pp. 100832 ◽

Cited By ~ 1

Author(s):

Yuri A. Mezenov ◽

Stéphanie Bruyere ◽

Nikita K. Kulachenkov ◽

Andrei N. Yankin ◽

Sergey S. Rzhevskiy ◽

...

Keyword(s):

Electron Beam ◽

Electron Beam Irradiation ◽

Metal Organic Frameworks ◽

Beam Irradiation ◽

Nanoparticle Growth ◽

Metal Organic ◽

Cu Nanoparticle

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Electron beam induced nanoparticle growth in metal-organic frameworks

10.1063/5.0031914 ◽

2020 ◽

Author(s):

Yuri A. Mezenov ◽

Nikita K. Kulachenkov ◽

Stéphanie Bruyere ◽

Valentin A. Milichko

Keyword(s):

Electron Beam ◽

Metal Organic Frameworks ◽

Nanoparticle Growth ◽

Metal Organic

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Cu(I/II) Metal–Organic Frameworks Incorporated Nanofiltration Membranes for Organic Solvent Separation

Membranes ◽

10.3390/membranes10110313 ◽

2020 ◽

Vol 10 (11) ◽

pp. 313

Author(s):

Lakshmeesha Upadhyaya ◽

Yu-Hsuan Chiao ◽

S. Ranil Wickramasinghe ◽

Xianghong Qian

Keyword(s):

Separation Factor ◽

Phase Inversion ◽

Room Temperature ◽

Metal Organic Frameworks ◽

Oxidation States ◽

Particle Sizes ◽

Mixed Matrix ◽

Barrier Layer Thickness ◽

Preferential Adsorption ◽

Metal Organic

Copper-based metal–organic frameworks (MOFs) with different oxidation states and near-uniform particle sizes have been successfully synthesized. Mixed-matrix polyimide membranes incorporating 0.1–7 wt% of Cu(II) benzene-1,2,5-tricarboxylic acid (Cu(II)BTC), Cu(I/II)BTC and Cu(I) 1,2-ethanedisulfonic acid (EDS) (Cu(I)EDS) MOFs were fabricated via non-solvent-induced phase inversion process. These membranes are found to be solvent resistant and mechanically stable. Liquid phase nanofiltration experiments were performed to separate toluene from n-heptane at room temperature. These membranes demonstrate preferential adsorption and permeation of the aromatic toluene over aliphatic n-heptane. The amount of MOF particles incorporated, the oxidation state of the Cu ion and membrane, and barrier layer thickness have a significant impact on the separation factor. Toluene/heptane separation factor at 1.47, 1.67 and 1.79 can be obtained for membranes incorporating 7 wt% Cu(II)BTC, Cu(I/II)BTC and Cu(I)EDS respectively at room temperature.

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Controllable Synthesis of Metal-Organic Framework/Polyethersulfone Composites

Crystals ◽

10.3390/cryst10010039 ◽

2020 ◽

Vol 10 (1) ◽

pp. 39

Author(s):

Xiaomin Guo ◽

Bin Zheng ◽

Jinlei Wang

Keyword(s):

Composite Materials ◽

Structural Integrity ◽

Metal Organic Framework ◽

Metal Organic Frameworks ◽

Vital Role ◽

Particle Sizes ◽

High Porosity ◽

Controllable Synthesis ◽

Wide Range ◽

Metal Organic

Composite materials that contain metal-organic frameworks (MOFs) as a filler and a polymer matrix have attracted attention because they present a combination of high porosity and structural integrity. Phase compatibilities of the MOF and polymer play a vital role in the formation of the composites. In particular, the stiff polymer cannot easily adapt to penetrate into the surface pore of MOF and mainly depends on chemical attractions to form the MOF/polymer composites. We report the synthesis of MOF/polyethersulfone (Young’s modulus = ~2.6 GPa) via different fabrication methods, different MOF types and particle sizes, and different solvents. The formed network structures are robust, monolithic composites with 60% MOF loadings; also, the MOF surface area and porosity were fully preserved. The study explored the formation of the composite between MOF and a stiff polymer and encourages the design of more MOF/polymer composite materials across a wide range of applications.

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Defect engineering of highly stable lanthanide metal–organic frameworks by particle modulation for coating catalysis

Journal of Materials Chemistry A ◽

10.1039/c7ta09036f ◽

2018 ◽

Vol 6 (2) ◽

pp. 342-348 ◽

Cited By ~ 20

Author(s):

Yifa Chen ◽

Shenghan Zhang ◽

Fan Chen ◽

Sijia Cao ◽

Ya Cai ◽

...

Keyword(s):

Metal Organic Frameworks ◽

Particle Sizes ◽

Defect Engineering ◽

Structure Control ◽

Metal Organic ◽

Lanthanide Metal ◽

Powerful Strategy

A powerful strategy to design the structure, control the particle sizes and fabricate catalytic devices is developed for lanthanide MOFs.

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Experimental Evidence for the Incorporation of Two Metals at Equivalent Lattice Positions in Mixed‐Metal Metal–Organic Frameworks

Chemistry - A European Journal ◽

10.1002/chem.201905596 ◽

2020 ◽

Vol 26 (25) ◽

pp. 5667-5675

Author(s):

Johannes Bitzer ◽

Steffen Otterbach ◽

Kavipriya Thangavel ◽

Anastasia Kultaeva ◽

Rochus Schmid ◽

...

Keyword(s):

Experimental Evidence ◽

Metal Organic Frameworks ◽

Mixed Metal ◽

Metal Metal ◽

Metal Organic

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Facile synthesis of metal/metal oxide nanoparticles inside a nanoporous carbon matrix (M/MO@C) through the morphology-preserved transformation of metal–organic framework

Chemical Communications ◽

10.1039/c5cc01701g ◽

2015 ◽

Vol 51 (33) ◽

pp. 7238-7241 ◽

Cited By ~ 39

Author(s):

Woojeong Bak ◽

Hee Soo Kim ◽

Hyungphil Chun ◽

Won Cheol Yoo

Keyword(s):

Metal Oxide ◽

Metal Organic Framework ◽

Metal Oxide Nanoparticles ◽

Metal Organic Frameworks ◽

Carbon Matrix ◽

Carbon Composites ◽

Particle Sizes ◽

Facile Synthesis ◽

Metal Metal ◽

Metal Organic

Metal–organic frameworks (MOFs) undergo a simple, two-step process to form morphology-preserved metal/metal oxide@carbon composites with tunable porosity and particle sizes.

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