Metal Exchange Boosts the CO2 Selectivity of Metal Organic Frameworks Having Zn-Oxide Nodes

Correction for ‘Introduction of a mediator for enhancing photocatalytic performance via post-synthetic metal exchange in metal–organic frameworks (MOFs)’ by Dengrong Sun et al., Chem. Commun., 2015, 51, 2056–2059.

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Upgrading the Hydrogen Storage of MOF-5 by Post-Synthetic Exchange with Divalent Metal Ions

Applied Sciences ◽

10.3390/app112411687 ◽

2021 ◽

Vol 11 (24) ◽

pp. 11687

Author(s):

Abdul Malik P. Peedikakkal ◽

Isam H. Aljundi

Keyword(s):

Metal Ions ◽

Adsorption Isotherms ◽

Metal Organic Frameworks ◽

Hydrogen Uptake ◽

Metal Exchange ◽

Mixed Metal ◽

H2 Adsorption ◽

Hydrogen Molecules ◽

Metal Metal ◽

Metal Organic

In metal-organic frameworks (MOFs), mixed-metal clusters have the opportunity to adsorb hydrogen molecules due to a greater charge density of the metal. Such interactions may subsequently enhance the gravimetric uptake of hydrogen. However, only a few papers have explored the ability of mixed-metal MOFs to increase hydrogen uptake. The present work reveals the preparation of mixed metal metal-organic frameworks M-MOF-5 (where M = Ni2+, Co2+, and Fe2+) (where MOF-5 designates MOFs such as Zn2+ and 1,4-benzenedicarboxylic acid ligand) using the post-synthetic exchange (PSE) technique. Powder X-ray diffraction patterns and scanning electron microscopy images indicate the presence of crystalline phases after metal exchange, and the inductively coupled plasma–mass spectroscopy analysis confirmed the exchange of metals by means of the PSE technique. The nitrogen adsorption isotherms established the production of microporous M-MOF-5. Although the additional metal ions decreased the surface area, the exchanged materials displayed unique features in the gravimetric uptake of hydrogen. The parent MOF-5 and the metal exchanged materials (Ni-MOF-5, Co-MOF-5, and Fe-MOF-5) demonstrated hydrogen capacities of 1.46, 1.53, 1.53, and 0.99 wt.%, respectively. The metal-exchanged Ni-MOF-5 and Co-MOF-5 revealed slightly higher H2 uptake in comparison with MOF-5; however, the Fe-MOF-5 showed a decrease in uptake due to partial discrete complex formation (discrete complexes with one or more metal ions) with less crystalline nature. The Sips model was found to be excellent in describing the H2 adsorption isotherms with a correlation coefficient ≅ 1. The unique hydrogen uptakes of Ni− and Co-MOF-5 shown in this study pave the way for further improvement in hydrogen uptake.

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Remodelling a Shp: Transmetallation in a Rare-Earth Cluster-Based Metal–Organic Framework

10.26434/chemrxiv.14498208.v1 ◽

2021 ◽

Author(s):

Hudson de Aguiar Bicalho ◽

P. Rafael Donnarumma ◽

Victor Quezada-Novoa ◽

Hatem M. Titi ◽

Ashlee J Howarth

Keyword(s):

Rare Earth ◽

Single Crystal ◽

Surface Area ◽

De Novo ◽

Metal Organic Framework ◽

Metal Organic Frameworks ◽

Metal Exchange ◽

X Ray Diffraction ◽

X Ray ◽

Metal Organic

<div> <p>Post-synthetic modification (PSM) of metal–organic frameworks (MOFs) is an important strategy for accessing MOF analogues that cannot be easily synthesized <i>de novo</i>. In this work, the rare-earth (RE) cluster-based MOF, Y-CU-10, with <b>shp</b> topology was modified through transmetallation using a series of RE ions, including: La(III), Nd(III), Eu(III), Tb(III), Er(III), Tm(III), and Yb(III). In all cases, metal-exchange higher than 70 % was observed, with reproducible results. All transmetallated materials were fully characterized and compared to the parent MOF, Y-CU-10, in regards to crystallinity, surface area, and morphology. Additionally, single-crystal X-ray diffraction (SCXRD) measurements were performed to provide further evidence of transmetallation occurring in the nonanuclear cluster nodes of the MOF. </p> </div>

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Integration of Fluorescent Functionality into Pressure Amplifying Metal-Organic Frameworks

10.26434/chemrxiv.14680335.v1 ◽

2021 ◽

Author(s):

Francesco Walenszus ◽

Jack D. Evans ◽

Volodymyr Bon ◽

Friedrich Schwotzer ◽

Irena Senkovska ◽

...

Keyword(s):

Structural Changes ◽

Gas Adsorption ◽

Metal Organic Frameworks ◽

Metal Exchange ◽

Limited Information ◽

X Ray Diffraction ◽

Metal Organic ◽

Synthetic Metal ◽

External Stimuli ◽

Highly Porous

The flexibility of soft porous crystals, i.e., their ability to respond to external stimuli with structural changes, is one of the most fascinating features of metal-organic frameworks. In addition to breathing and swelling phenomena of flexible MOFs, negative gas adsorption and pressure amplification is one of the more recent discoveries in this field, initially observed in the cubic DUT-49 framework. In recent years the structural contraction was monitored by physisorption, X‑ray diffraction, NMR and EPR techniques, providing only limited information about the electronic structure of the ligand. In this work we designed a new ligand with a fluorescent core in the linker backbone and synthesized three new MOFs, isoreticular to DUT-49, denoted as DUT‑140(M) (M - Cu, Co, Zn) crystalizing in space group. DUT‑140(Cu) can be desolvated and is highly porous with an accessible apparent surface area of 4870 m2g-1 and a pore volume of 2.59 cm3g-1. Furthermore, it shows flexibility and NGA upon adsorption of subcritical gases. DUT-140(Zn), synthesized using post-synthetic metal exchange, could only be studied with guests in the pores. In addition to the investigation of the adsorption behavior of DUT-140(Cu) spectroscopic and computational methods were used to study the light absorption properties.

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Introduction of a mediator for enhancing photocatalytic performance via post-synthetic metal exchange in metal–organic frameworks (MOFs)

Chemical Communications ◽

10.1039/c4cc09407g ◽

2015 ◽

Vol 51 (11) ◽

pp. 2056-2059 ◽

Cited By ~ 180

Author(s):

Dengrong Sun ◽

Wenjun Liu ◽

Mei Qiu ◽

Yongfan Zhang ◽

Zhaohui Li

Keyword(s):

Photocatalytic Performance ◽

Metal Organic Frameworks ◽

Metal Exchange ◽

Metal Organic ◽

Synthetic Metal

Introduction of Ti as a mediator in Ti substituted NH2-Uio-66(Zr) is an effective way to improve its photocatalytic performance.

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Revisiting the Incorporation of Ti(IV) in UiO-type Metal–Organic Frameworks: Metal Exchange versus Grafting and Their Implications on Photocatalysis

Chemistry of Materials ◽

10.1021/acs.chemmater.7b03320 ◽

2017 ◽

Vol 29 (21) ◽

pp. 8963-8967 ◽

Cited By ~ 37

Author(s):

Jara G. Santaclara ◽

Alma I. Olivos-Suarez ◽

Adrian Gonzalez-Nelson ◽

Dmitrii Osadchii ◽

Maxim A. Nasalevich ◽

...

Keyword(s):

Metal Organic Frameworks ◽

Metal Exchange ◽

Metal Organic

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Transmetalation: routes to metal exchange within metal–organic frameworks

Journal of Materials Chemistry A ◽

10.1039/c3ta10784a ◽

2013 ◽

Vol 1 (18) ◽

pp. 5453 ◽

Cited By ~ 197

Author(s):

Marianne Lalonde ◽

Wojciech Bury ◽

Olga Karagiaridi ◽

Zachary Brown ◽

Joseph T. Hupp ◽

...

Keyword(s):

Metal Organic Frameworks ◽

Metal Exchange ◽

Metal Organic

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Remodelling a Shp: Transmetallation in a Rare-Earth Cluster-Based Metal–Organic Framework

10.26434/chemrxiv.14498208 ◽

2021 ◽

Author(s):

Hudson de Aguiar Bicalho ◽

P. Rafael Donnarumma ◽

Victor Quezada-Novoa ◽

Hatem M. Titi ◽

Ashlee J Howarth

Keyword(s):

Rare Earth ◽

Single Crystal ◽

Surface Area ◽

De Novo ◽

Metal Organic Framework ◽

Metal Organic Frameworks ◽

Metal Exchange ◽

X Ray Diffraction ◽

X Ray ◽

Metal Organic

<div> <p>Post-synthetic modification (PSM) of metal–organic frameworks (MOFs) is an important strategy for accessing MOF analogues that cannot be easily synthesized <i>de novo</i>. In this work, the rare-earth (RE) cluster-based MOF, Y-CU-10, with <b>shp</b> topology was modified through transmetallation using a series of RE ions, including: La(III), Nd(III), Eu(III), Tb(III), Er(III), Tm(III), and Yb(III). In all cases, metal-exchange higher than 70 % was observed, with reproducible results. All transmetallated materials were fully characterized and compared to the parent MOF, Y-CU-10, in regards to crystallinity, surface area, and morphology. Additionally, single-crystal X-ray diffraction (SCXRD) measurements were performed to provide further evidence of transmetallation occurring in the nonanuclear cluster nodes of the MOF. </p> </div>

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Integration of Fluorescent Functionality into Pressure Amplifying Metal-Organic Frameworks

10.26434/chemrxiv.14680335 ◽

2021 ◽

Author(s):

Francesco Walenszus ◽

Jack D. Evans ◽

Volodymyr Bon ◽

Friedrich Schwotzer ◽

Irena Senkovska ◽

...

Keyword(s):

Structural Changes ◽

Gas Adsorption ◽

Metal Organic Frameworks ◽

Metal Exchange ◽

Limited Information ◽

X Ray Diffraction ◽

Metal Organic ◽

Synthetic Metal ◽

External Stimuli ◽

Highly Porous

The flexibility of soft porous crystals, i.e., their ability to respond to external stimuli with structural changes, is one of the most fascinating features of metal-organic frameworks. In addition to breathing and swelling phenomena of flexible MOFs, negative gas adsorption and pressure amplification is one of the more recent discoveries in this field, initially observed in the cubic DUT-49 framework. In recent years the structural contraction was monitored by physisorption, X‑ray diffraction, NMR and EPR techniques, providing only limited information about the electronic structure of the ligand. In this work we designed a new ligand with a fluorescent core in the linker backbone and synthesized three new MOFs, isoreticular to DUT-49, denoted as DUT‑140(M) (M - Cu, Co, Zn) crystalizing in space group. DUT‑140(Cu) can be desolvated and is highly porous with an accessible apparent surface area of 4870 m2g-1 and a pore volume of 2.59 cm3g-1. Furthermore, it shows flexibility and NGA upon adsorption of subcritical gases. DUT-140(Zn), synthesized using post-synthetic metal exchange, could only be studied with guests in the pores. In addition to the investigation of the adsorption behavior of DUT-140(Cu) spectroscopic and computational methods were used to study the light absorption properties.

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