Thorium–Organic Framework Constructed with a Semirigid Triazine Hexacarboxylic Acid Ligand: Unique Structure with Thorium Oxide Wheel Clusters and Iodine Adsorption Behavior

Zhang, Na; Sun, Lixian; Xing, Yong Heng

doi:10.1021/acs.inorgchem.9b03639

Cited by 57 publications

(43 citation statements)

References 65 publications

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“…[ 78 ] For uranyl‐organic framework (U‐TATAB) developed by Zhang et al., the reported iodine adsorption is 14.6 wt% (146 mg g −1 ). [ 79 ] It should be noted that the Cd‐MOF crystals described herein are nonporous and exhibit no iodine adsorption. In contrast, the MONs generated after exfoliation using mechanical grinding display notable iodine adsorption, demonstrating a new dimension to the properties of 2D MONs.…”

Section: Resultsmentioning

confidence: 99%

Metal–Organic Nanosheets (MONs): Exfoliation by Mechanical Grinding and Iodine Capture

Tamuly

Sama

Moorthy

2022

Adv Materials Inter

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in terms of the number of MOFs synthesized over the past two decades for a variety of applications, MOFs with high iodine uptake capacity remain conspicuously sparse. [7] 129 I is one of the most hazardous radioisotopes in nuclear waste with a long radioactive half-life of 1.57 × 10 7 years. Several adsorbents that include chalcogenides, aerogels, functionalized clays, silver-based porous zeolitic materials, etc. with loading amounts ranging from 8 to 175 wt% have been reported. [8][9][10] However, their application is precluded by one or the other of the disadvantages such as high cost, limited adsorption ability, and serious environmental effects. The materials with better high-iodine trapping ability are a need of the hour. In general, adsorption capacity for iodine by porous materials is related not only to the pore size but also to other important factors such as effective availability of sorption sites, I 2 -framework interactions, composition/ratio of I 2 and polyiodide anions. One of the important ways to develop materials with high iodine capture is to introduce π-conjugated organic ligands, pyridines with readily available electron pairs and electron-rich functional groups such as OH, NH 2 , NR 2 , and COOH, which permit either formation of stable charge-transfer complexes or stronger halogen bonds with iodine; electron-rich moieties are expected to enhance charge-transfer interactions and hence the efficiency of adsorption of iodine. [11][12][13][14][15][16][17] The properties of any porous material are determined by constituent building blocks, pore attributes, and characteristics of the exposed surface area. As compared to 3D MOFs, the analogous lower dimensional 2D metal-organic nanosheets (MONs) have garnered much attention in the last few years [18][19][20][21][22][23][24][25] since the discovery of graphene and its burgeoning applications in diverse domains. [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] An important feature of MONs is the high surface area, which allows better interaction with guest molecules. Due to the ultrathin nature of the sheets, [42] large surface area, high ratio of surface area-to-volume, [43] and readily accessible active sites, MONs have been tremendously explored for gas separations, [30][31][32][33][34][35] energy storage and conversion, [38] catalysis, [28] sensing, [34,39] etc. The synthesis of 2D MONs is a challenge, as the growth of the crystals is a limiting factor. Several synthetic strategies have now been developed for MONs, which include bottom-up and top-down approaches. [19][20][21][22][23] The former is a straightforward direct synthesis of nanosheets from An electron-rich π-conjugated organic linker H 4 BPDP (BPDP = biphenyl dipyrrole tetracarboxylic acid) is designed and subjected to metal-assisted self-assembly to afford a layered metal-organic framework (MOF), i.e., Cd-BPDP. Single crystal X-ray structure determination and analysis show that two corrugated layers of the MOF are intertwined to yield thick strands of porous 2D metal-o...

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Section: Resultsmentioning

confidence: 99%

Metal–Organic Nanosheets (MONs): Exfoliation by Mechanical Grinding and Iodine Capture

Tamuly

Sama

Moorthy

2022

Adv Materials Inter

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“…The ability of the CPs to accommodate iodine molecules in the interchain/interlayer space perhaps governs the iodine adsorption capacity [ 16 , 17 , 18 ]. The solvent accessible volumes calculated by using the PLATON program [ 19 ] for 7 – 9 were 6.9, 9.3 and 13.7%, respectively, of the unit cell volume, indicating that the 2D 9 may accommodate more iodine than the 1D 7 and 8 .…”

Section: Resultsmentioning

confidence: 99%

Nickel(II) Coordination Polymers Supported by Bis-pyridyl-bis-amide and Angular Dicarboxylate Ligands: Role of Ligand Flexibility in Iodine Adsorption

Lee

Liao

Chen

2022

IJMS

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Reactions of N‚N’-bis(3-pyridylmethyl)oxalamide (L1), N‚N’-bis(4-pyridylmethyl)oxalamide (L2), or N,N’-bis(3-pyridylmethyl)adipoamide) (L3) with angular dicarboxylic acids and Ni(II) salts under hydro(solvo)thermal conditions afforded a series of coordination polymers: {[Ni(L1)(OBA)(H2O)]·H2O}n (H2OBA = 4,4-oxydibenzoic acid), 1, {[Ni(L1)(SDA)(H2O)2]·H2O·CH3OH}n (H2SDA = 4,4-sulfonyldibenzoic acid), 2, {[Ni(L2)(OBA)]·C2H5OH}n, 3, {[Ni(L2)(OBA)]·CH3OH}n, 4, {[Ni2(L2)(SDA)2(H2O)3]·5H2O}n, 5, {[Ni2(L2)(SDA)2(H2O)3]·H2O·2C2H5OH}n, 6, {[Ni(L3)(OBA)(H2O)2]·2H2O}n, 7, {[Ni(L3)(SDA)(H2O)2]·2H2O}n, 8, and {[Ni(L3)0.5(SDA)(H2O)2]·0.5C2H5OH}n, 9, which have been structurally characterized by using single-crystal X-ray crystallography. Complex 1 exhibits an interdigitated 2D layer with the 2,4L2 topology and 2 is a 2D layer with the sql topology, while 3 and 4 are 3D frameworks resulting from polycatenated 2D nets with the sql topology and 5 and 6 are 2-fold interpenetrated 3D frameworks with the dia topology. Complexes 7 and 8 are 1D looped chains and 9 is a 2D layer with the 3,4L13 topology. The various structural types in 1–9 indicate that the structural diversity is subject to the flexibility and donor atom position of the neutral spacer ligands and the identity of the angular dicarboxylate ligands, while the role of the solvent is uncertain. The iodine adsorption of 1–9 was also investigated, demonstrating that that the flexibility of the spacer L1–L3 ligands can be an important factor that governs the feasibility of the iodine adsorption. Moreover, complex 9 shows a better iodine adsorption and encapsulates 166.55 mg g−1 iodine in the vapor phase at 60 °C, which corresponded to 0.38 molecules of iodine per formula unit.

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“…Later, they reported another thorium‐based MOF (Th‐TTHA) with the same thorium oxide wheel clusters by utilizing a semirigid triazine hexacarboxylic acid linker (H 6 TTHA = 1,3,5‐triazine‐2,4,6‐triamine hexaacetic acid). [ 129 ] The thermogravimetric analysis of Th‐TTHA reveals that the framework is thermally stable until 200 °C under nitrogen. Th‐TTHA exhibits excellent adsorption capacity for iodine, which can be attributed to its abundant adsorption sites such as the triazine ring that is nitrogen‐rich and carboxyl oxygen atoms without coordination with a central metal.…”

Section: Mofs Based On Ans (Group 3 Metals)mentioning

confidence: 99%

“…In addition, adsorption properties of thorium‐based MOFs toward I 2 and dyes with different charges were explored owing to their pore character. [ 128,129,132 ] Th‐TATAB displays excellent adsorption properties toward iodine in cyclohexane solution. [ 128 ] Additionally, Th‐TATAB shows excellent adsorption performance for anionic, neutral, and cationic dyes individually and simultaneously from aqueous solutions, although the simultaneous removal of molecules with different charges is challenging.…”

Section: Mofs Based On Ans (Group 3 Metals)mentioning

confidence: 99%

“…Th‐TTHA also displays an excellent adsorption capacity for iodine because Th‐TTHA has abundant adsorption sites including the N‐rich triazine ring and carboxyl oxygen atoms without coordination with a central metal. [ 129 ] The exploration of adsorption performance of Th‐MOF for iodine in cyclohexane solutions and dye contaminants in aqueous solutions is of great significance for environmental aspects, which offers a new strategy for opening up potential applications of thorium‐based MOFs and understanding actinides chemistry.…”

Section: Mofs Based On Ans (Group 3 Metals)mentioning

confidence: 99%

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Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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Metal-organic frameworks (MOFs), a class of porous crystalline framework materials, are linked by strong bonds between inorganic and organic building blocks. [1-3] In the past two decades, MOFs have rapidly grown as a star material due to their exceptional performance in areas such as storage, separation and catalysis. [4] The outstanding performance of MOFs in applications benefits from their intrinsically porous structures and highly tunable pore environment. [5-7] The creation and modification of pore space with optimized size, functionality and diversity can be precisely tuned at the molecular level by rationally designing building blocks and synthetic procedures. [8,9] The diversity of MOFs can be enriched by expanding the library of organic linkers with varying lengths, geometries, and functional groups. [10] Additionally, very diverse metal cations are applied to MOF synthesis, ranging from monovalent (Ag + , Cu + , etc.), divalent (Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ , etc.), trivalent (Al 3+ , Sc 3+ , V 3+ , Cr 3+ , etc.), to tetravalent (Ti 4+ , Zr 4+ , Hf 4+ , etc.) cations. [11] In this review, we mainly focus on MOFs with group 3 and 4 metals, including Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr (Figure 1). Group 3 metal cations are generally found in the oxidation state of +3 in the MOF structures, while group 4 metal cations mainly exist in the oxidation state of +4, leading to the formation of much stronger coordination bonds with carboxylates. [12] Therefore, group 4 metal-based MOFs (M IV-MOFs) generally have enhanced stability compared with MOFs constructed from metals of group 3 and other groups. This series of MOFs stands out because the involved metals can generally coordinate with carboxylates to form frameworks with strong coordination bonds, according to the Pearson's hard/soft acid/base principle, where group 3 and 4 metal cations are regarded as hard acids while carboxylate ligands are hard bases. [11] One remarkable feature of MOFs with group 3 and 4 metals is that they generally can form phases containing M 6 O 8 (M = Y, Ln, An, Zr and Hf) clusters, regardless of their atomic numbers, charges and radius. This series of M 6-based MOFs is best represented by UiO series such as UiO-66 with fcu topology. [13] Under different synthetic conditions, UiO-66(M, M = An, Zr and Hf) constructed from [M 6 (μ 3-O) 4 (μ 3-OH) 4 ] clusters and linear carboxylates can be obtained, while UiO-66(M, M = Y, Ln) is assembled from Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status an...

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Thorium–Organic Framework Constructed with a Semirigid Triazine Hexacarboxylic Acid Ligand: Unique Structure with Thorium Oxide Wheel Clusters and Iodine Adsorption Behavior

Cited by 57 publications

References 65 publications

Metal–Organic Nanosheets (MONs): Exfoliation by Mechanical Grinding and Iodine Capture

Metal–Organic Nanosheets (MONs): Exfoliation by Mechanical Grinding and Iodine Capture

Nickel(II) Coordination Polymers Supported by Bis-pyridyl-bis-amide and Angular Dicarboxylate Ligands: Role of Ligand Flexibility in Iodine Adsorption

Metal–Organic Frameworks Based on Group 3 and 4 Metals

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