The Chemistry of Metal Organic Framework Materials

Abstract

The journal started its 35th year by celebrating 35 recent manuscripts in a virtual issue that highlighted diverse materialsbased research: battery materials, MXenes and layered dichalcogenides, covalent organic frameworks and porous materials, hydrogels, catalysts, photovoltaics and thermoelectrics, luminescent and optical materials, and materials discovery. The subsequent virtual issue on π-Conjugated Materials accentuated how chemical structure and conjugation can shape materials for various applications. Continuing with the theme of designable crystalline materials, we now look at Metal Organic Frameworks (MOFs), whose structure− property investigations have consistently embellished the pages of Chemistry of Materials and advanced their applications. In the last three decades, MOFs have been established as excellent candidates for interlacing complementary functions to realize high surface area materials for molecular separations and gas storage, stimuli-responsive and dynamic crystalline frameworks, and conductive crystalline porous structures. More recently, MOF glasses, a disordered form of MOFs, are finding niche applications. This virtual collection catalogues recent MOF advances featured in Chemistry of Materials from 2022 to 2023, 1−37 with an accompanying editorial by Laura Gagliardi and Omar Yaghi that outlines three critical future directions for MOFs. 38

Exploration of Charge Storage in an Anion-Exchanged Synthesized Sn–Co–Se Nanorod-Based Flexible Symmetric Supercapacitor

“…Metal–organic frameworks (MOFs) are often used as sacrificial templates to synthesize porous electrode materials such as metal hydroxides, oxides, chalcogenides, and others. − Among the MOF-derived electrode materials, metal-selenides (M-Se) are promising candidates for supercapacitors due to their higher conductivity than M-oxides/hydroxides/phosphides/sulfides and layered double hydroxides (LDHs). , The electron density of the transition metal’s bonding d-orbital is higher in M-Se than in M-oxides and M-phosphides due to the less electronegative anion (Se n – ), which facilitates the favorable reversible redox reaction of M-Se with OH – ions in the KOH electrolyte. , The advantages of M-Se as a supercapacitor material have led to the development of some interesting MOF-derived nanostructured metal-selenides in recent literature studies. − Cobalt-based materials are known for their electrochemical activity for water splitting and energy storage applications. − The activity of cobalt can be further enhanced by the synergistic effect of other metals by synthesizing bimetallic advanced materials. Cobalt-based bimetallic electrode materials have been synthesized by combining cobalt with more electronegative metals, such as nickel (1.91) and copper (1.90), which have higher electronegativities than cobalt (1.88). , These Ni–Co and Cu–Co electrodes have shown the best synergistic effect of the metals. − On the other hand, the combination of cobalt with less electronegative metals (≤1.88), such as vanadium, chromium, iron, and zinc, does not offer higher electrochemical activity. , In a nutshell, when cobalt is combined with a more electronegative metal, such as Sn (1.96), the more electronegative metal will pull electrons toward itself from the cobalt, creating a partial positive charge on the cobalt.…”

Design, synthesis and characterization of hierarchical porous stacked thin films based on MOFs and ordered mesoporous oxides

“…Since the appearance of pioneering studies reporting their interesting adsorption properties, 21,22 MOFs have raised an ever-increasing interest due to a myriad of possible applications in diverse fields such as separation, catalysis, sensing, energy, or drug delivery, just to mention some of the most relevant examples. 23–29,77 The potential of MOFs as building blocks for optical sensors and PCs has not gone unnoticed. 30 Following the seminal contribution by Hupp et al of a Fabry-Pèrot MOF-based vapour sensor, 31 research efforts along this line have increased substantially; interesting reports include direct nanoparticle self-assembly for RI contrast, 32–35 and filling or imprinting strategies for the nanofabrication of patterned surfaces acting as 2D-PCs.…”

Expanding the Reticular Chemistry Building Block Library toward Highly Connected Nets: Ultraporous MOFs Based on 18-Connected Ternary, Trigonal Prismatic Superpolyhedra

“…Metal–organic frameworks (MOFs) represent an important class of functional porous materials made of the combination of inorganic and organic building blocks, linked together by coordination bonds. , The use of diverse inorganic and organic components has led to the discovery of crystalline MOFs with exceptional porosity in terms of surface area and pore volume, as well as framework functionalities mainly originating from ligand modifications. For these reasons, MOFs are highly suitable for important applications including gas storage/separation and catalysis, among others. − …”