scholarly journals Metal Centers and Organic Ligands Determine Electrochemistry of Metal–Organic Frameworks

Small ◽  
2022 ◽  
pp. 2106607
Author(s):  
Caoling Li ◽  
Jian Shen ◽  
Kangbing Wu ◽  
Nianjun Yang
Keyword(s):  
Metal Organic Frameworks ◽  
Organic Ligands ◽  
Metal Centers ◽  
Metal Organic

Organically-functionalised supertetrahedra as building blocks for hybrid materials

2008 ◽  
Vol 1148 ◽  
Author(s):  
Paz Vaqueiro ◽  
M Lucia Romero
Keyword(s):  
Crystal Structures ◽  
Hybrid Materials ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Organic Ligands ◽  
Reaction Conditions ◽  
Metal Centers ◽  
Covalently Bonded ◽  
Metal Organic ◽  
Solvothermal Conditions

AbstractThe crystal structures of gallium sulfides prepared under solvothermal conditions, using 4-picoline as a solvent, are described. These materials contain [Ga10S16(NC6H7)4]2− clusters, in which the terminal S2− anions have been replaced by covalently bonded 4-picoline molecules. Whilst these phases contain isolated supertetrahedral clusters separated by organic moieties, linkage of such clusters via organic ligands is possible under suitable reaction conditions. These organically-functionalised supertetrahedra could therefore be used to design novel Metal-Organic frameworks (MOFs) in which the normally-encountered metal centers are replaced by supertetrahedral clusters.

Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

2019 ◽  
Author(s):  
Andrew Rosen ◽  
M. Rasel Mian ◽  
Timur Islamoglu ◽  
Haoyuan Chen ◽  
Omar Farha ◽  
...  
Keyword(s):  
Density Functional ◽  
Metal Organic Frameworks ◽  
Redox Activity ◽  
Screening Methods ◽  
Bridging Ligands ◽  
Metal Centers ◽  
Computational Screening ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Unsaturated Metal Sites

<p>Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O<sub>2</sub> and N<sub>2</sub> adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br<sup>-</sup>, μ-Cl<sup>-</sup>, μ-F<sup>-</sup>, μ-SH<sup>-</sup>, or μ-OH<sup>-</sup> groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O<sub>2</sub> affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O<sub>2</sub>. In contrast with O<sub>2</sub> adsorption, N<sub>2</sub> adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V<sup>2+</sup> open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl<sup>-</sup> ligands of M<sub>2</sub>Cl<sub>2</sub>(BBTA) (H<sub>2</sub>BBTA = 1<i>H</i>,5<i>H</i>-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH<sup>-</sup> groups would significantly enhance the strength of O<sub>2</sub> adsorption at the open metal sites without a corresponding increase in the N<sub>2</sub> affinity. Experimental investigation of Co<sub>2</sub>Cl<sub>2</sub>(BBTA) and Co<sub>2</sub>(OH)<sub>2</sub>(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O<sub>2</sub> at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH<sup>-</sup><sub> </sub>ligands and the presence of H-bonding interactions between the μ-OH<sup>-</sup> bridging ligands and the O<sub>2</sub> adsorbate.</p>

Metal-organic frameworks for electrochemical reduction of carbon dioxide: The role of metal centers

2020 ◽  
Vol 40 ◽  
pp. 156-170 ◽  
Author(s):  
Ping Shao ◽  
Luocai Yi ◽  
Shumei Chen ◽  
Tianhua Zhou ◽  
Jian Zhang
Keyword(s):  
Carbon Dioxide ◽  
Electrochemical Reduction ◽  
Metal Organic Frameworks ◽  
Metal Centers ◽  
Metal Organic

Vapor-assisted self-conversion of basic carbonates in metal–organic frameworks

Nanoscale ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 5069-5076
Author(s):  
Miaomiao Jia ◽  
Jingyi Su ◽  
Pengcheng Su ◽  
Wanbin Li
Keyword(s):  
Carbon Capture ◽  
Metal Organic Frameworks ◽  
Solvent Vapor ◽  
Metal Centers ◽  
Metal Organic ◽  
High Alkalinity

Basic carbonates with high alkalinity are incorporated into metal–organic frameworks by solvent vapor-assisted self-conversion of partial metal centers to improve carbon capture performance.

Dimensional selective syntheses of metal–organic frameworks using mixed organic ligands

2020 ◽  
Vol 513 ◽  
pp. 119739
Author(s):  
Giseong Lee ◽  
Jung Heum Yoon ◽  
Kangin Kwon ◽  
Hogyu Han ◽  
Jeong Hwa Song ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Organic Ligands ◽  
Metal Organic

scholarly journals Increasing the Stability of Metal-Organic Frameworks

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Mathieu Bosch ◽  
Muwei Zhang ◽  
Hong-Cai Zhou
Keyword(s):  
Metal Organic Frameworks ◽  
Luminescent Properties ◽  
Vacuum Treatment ◽  
Donor Ligands ◽  
Gas Sorption ◽  
Nitrogen Donor Ligands ◽  
Metal Centers ◽  
Ligand Interactions ◽  
Metal Organic ◽  
The Stability

Metal-organic frameworks (MOFs) are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapse upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.

scholarly journals Screening for high-spin metal organic frameworks (MOFs): density functional theory study on DUT-8(M1,M2) (with Mi = V,…,Cu)

2016 ◽  
Vol 18 (11) ◽  
pp. 8075-8080 ◽  
Author(s):  
Sebastian Schwalbe ◽  
Kai Trepte ◽  
Gotthard Seifert ◽  
Jens Kortus
Keyword(s):  
Density Functional Theory ◽  
High Spin ◽  
First Principles ◽  
Density Functional ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Metal Centers ◽  
Metal Organic

We present a first principles study of low-spin (LS)/high-spin (HS) screening for 3d metal centers in the metal organic framework (MOF) DUT-8(Ni).

Facile room temperature synthesis of metal–organic frameworks from newly synthesized copper/zinc hydroxide and their application in adsorptive desulfurization

RSC Advances ◽  
2016 ◽  
Vol 6 (44) ◽  
pp. 37530-37534 ◽  
Author(s):  
Wencong Xu ◽  
Gang Li ◽  
Weigang Li ◽  
Haojie Zhang
Keyword(s):  
Room Temperature ◽  
Metal Organic Frameworks ◽  
Organic Ligands ◽  
Zinc Hydroxide ◽  
Facile Synthesis ◽  
Adsorptive Desulfurization ◽  
Temperature Synthesis ◽  
Room Temperature Synthesis ◽  
Metal Organic ◽  
Copper Zinc

Facile synthesis of metal–organic frameworks was demonstrated via directly adding organic ligands solution into the newly synthesized copper/zinc hydroxide solution.

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