Versatile rare earth hexanuclear clusters for the design and synthesis of highly-connected<b>ftw</b>-MOFs

Luebke, Ryan; Belmabkhout, Youssef; Weseliński, Łukasz J.; Cairns, Amy; Alkordi, Mohamed H.; Norton, George K; Wojtas, Łukasz; Adil, Karim; Eddaoudi, Mohamed

doi:10.1039/c5sc00614g

Cited by 139 publications

(125 citation statements)

References 28 publications

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“…Accordingly, we designed and synthesized the tetratopic ligand 3,3″,5,5″-tetrakis(4-carboxyphenyl)- p -terphenyl (H 4 TCPT) ( H 4 L1 ) 19 that can act as a rectangular MBB. Successfully, reactions between H 4 L1 and AlCl 3 ·6H 2 O in acidic solution containing a mixture of N , N ′-dimethylformamide (DMF) and acetonitrile (CH 3 CN) afforded colorless homogeneous crystals with a cube-shaped morphology, characterized and formulated by SCXRD as [Al 3 O(TCPT) 1.5 (H 2 O) 3 ]·|Cl – | ( 1 ).…”

Section: Results and Discussionmentioning

confidence: 99%

“…19 As anticipated, under reaction conditions similar to those used to isolate the Al- soc -MOF-1, cube-shaped crystals were obtained and characterized using SCXRD and powder X-ray diffraction (PXRD) studies (Figure 2b), revealing the construction of two isoreticular Al- soc -MOF compounds, naphthalene Al- soc -MOF-2 ( 2 ) and anthracene Al- soc -MOF-3 ( 3 ) with the formula [Al 3 O(Ligand) 1.5 (H 2 O) 3 ]·|Cl – |.…”

Section: Results and Discussionmentioning

confidence: 99%

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MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc-MOF for CH₄, O₂, and CO₂ Storage

Alezi¹,

Belmabkhout²,

Suyetin³

et al. 2015

J. Am. Chem. Soc.

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714

361

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The molecular building block approach was employed effectively to construct a series of novel isoreticular, highly porous and stable, aluminum-based metal–organic frameworks with soc topology. From this platform, three compounds were experimentally isolated and fully characterized: namely, the parent Al-soc-MOF-1 and its naphthalene and anthracene analogues. Al-soc-MOF-1 exhibits outstanding gravimetric methane uptake (total and working capacity). It is shown experimentally, for the first time, that the Al-soc-MOF platform can address the challenging Department of Energy dual target of 0.5 g/g (gravimetric) and 264 cm3 (STP)/cm3 (volumetric) methane storage. Furthermore, Al-soc-MOF exhibited the highest total gravimetric and volumetric uptake for carbon dioxide and the utmost total and deliverable uptake for oxygen at relatively high pressures among all microporous MOFs. In order to correlate the MOF pore structure and functionality to the gas storage properties, to better understand the structure–property relationship, we performed a molecular simulation study and evaluated the methane storage performance of the Al-soc-MOF platform using diverse organic linkers. It was found that shortening the parent Al-soc-MOF-1 linker resulted in a noticeable enhancement in the working volumetric capacity at specific temperatures and pressures with amply conserved gravimetric uptake/working capacity. In contrast, further expansion of the organic linker (branches and/or core) led to isostructural Al-soc-MOFs with enhanced gravimetric uptake but noticeably lower volumetric capacity. The collective experimental and simulation studies indicated that the parent Al-soc-MOF-1 exhibits the best compromise between the volumetric and gravimetric total and working uptakes under a wide range of pressure and temperature conditions.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc-MOF for CH₄, O₂, and CO₂ Storage

Alezi¹,

Belmabkhout²,

Suyetin³

et al. 2015

J. Am. Chem. Soc.

Self Cite

714

361

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show abstract

“…Microporous solids appear to allow access to optimal heterogeneous catalyst design, with tailorable pore systems . Commonly described aspects of microporous molecular solids include par excellence control and predictability of their pore size, window dimensions controlling access to the pores, and pore chemistry . This is largely due to their modular nature, where in many examples deliberate exchange of the molecular building units resulted in varied overall dimensions or chemistry of the pore systems but with maintained overall blueprint topology of the parent scaffold …”

Section: Introductionmentioning

confidence: 99%

Microporous Solids En Route to Heterogeneous Electrocatalysis: The Oxygen Reduction Reaction

2019

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The recent progress and challenges in developing highly active microporous materials as heterogeneous electrocatalysts for oxygen reduction reaction (ORR) are discussed. Due to the slow kinetics of ORR, the search for novel highly stable catalysts that can outperform Pt‐based ones is a growing demand. Functional microporous materials and exceptional chemical stability are of great interest due to their unique catalytic properties. The crucial rule of porosity and catalyst design strategies are thoroughly discussed with emphasis on the influence of the degree of microporosity on the material's intrinsic catalytic activity and the current best practice for catalyst testing and activity reporting. This Review focuses on microporous materials, which are classified into crystalline as metal–organic frameworks (MOFs), covalent–organic frameworks (COFs), or amorphous porous–organic polymers (POPs) as to their recent utilization in constructing efficient ORR electrocatalysts. The fundamental challenges in obtaining stable catalysts with appreciable kinetics from non‐noble metal ions, and ways to form them utilizing microporous solids as catalyst matrices, are reviewed. The fundamental criteria for future generation ORR catalysts based on microporous solids, including stability in acidic medium, high electrical conductivity, and accessibility of the active sites within the matrix are highlighted for guidance to future works.

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“…This is because polynuclearm etal clusters are usually prone to accept more organic ligandsa round themselves as the nuclearity and positive charge increase, and this leads to the formation of high-connected dense topologies. [52][53][54][55][56] In this context,t he search for suitable polynuclear metal clusters as 4-connected nodes to make ZCOFs is an attractive but challengingt ask. Given the continuous enthusiasm of researchers to pursue ZCOFs and the fact that some important advances have been made in the last few years, acomprehensiver eview on the design and synthesis of ZCOFsw ill undoubtedly promote furtherd evelopment and research in this area.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Zeolite‐like Cluster Organic Frameworks

Lin

Zhao

et al. 2018

Chemistry A European J

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During the past decade, research on the design and synthesis of zeolite-like metal-organic frameworks (ZMOFs) has developed greatly. As an important subclass of ZMOFs, zeolite-like cluster organic frameworks (ZCOFs) built from 4-connected metal-cluster secondary building units (SBUs) and appropriate linear organic ligand bridges have attracted sustained interest, because such materials not only integrate the merits of inorganic zeolites, ZMOFs, and metal clusters, including interesting topologies, high surface areas, extra-large cavities and channels, structural tunability, and unique physicochemical properties from various metal clusters, but also open up a new avenue to design and fabricate hybrid zeolite-like materials that have many potential applications in material sciences. In this review, recent developments in ZCOFs are summarized by classifying the ZCOFs into four categories according to the composition of the SBUs: 1) ZCOFs based on metal-halide cluster SBUs, 2) ZCOFs based on metal-oxygen cluster SBUs, 3) ZCOFs based on metal-chalcogen cluster SBUs, and 4) ZCOFs based on mixed types of metal-cluster SBUs. Besides, challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed.

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Versatile rare earth hexanuclear clusters for the design and synthesis of highly-connectedftw-MOFs

Abstract: A targeted rare earth ftw-MOF platform offers the potential to assess the effect of pore functionality and size on gas adsorption via ligand functionalization and/or expansion.

Cited by 139 publications

References 28 publications

MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc-MOF for CH₄, O₂, and CO₂ Storage

MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc-MOF for CH₄, O₂, and CO₂ Storage

Microporous Solids En Route to Heterogeneous Electrocatalysis: The Oxygen Reduction Reaction

Recent Advances in Zeolite‐like Cluster Organic Frameworks

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Versatile rare earth hexanuclear clusters for the design and synthesis of highly-connectedftw-MOFs

Abstract: A targeted rare earth ftw-MOF platform offers the potential to assess the effect of pore functionality and size on gas adsorption via ligand functionalization and/or expansion.

Cited by 139 publications

References 28 publications

MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc-MOF for CH4, O2, and CO2 Storage

MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc-MOF for CH4, O2, and CO2 Storage

Microporous Solids En Route to Heterogeneous Electrocatalysis: The Oxygen Reduction Reaction

Recent Advances in Zeolite‐like Cluster Organic Frameworks

Contact Info

Product

Resources

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MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc-MOF for CH₄, O₂, and CO₂ Storage

MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc-MOF for CH₄, O₂, and CO₂ Storage