Zirconium metal–organic frameworks incorporating tetrathiafulvalene linkers: robust and redox-active matrices for <i>in situ</i> confinement of metal nanoparticles

Su, Jian; Yuan, Shuai; Wang, Tao; Lollar, Christina; Zuo, Jing‐Lin; Zhang, Jiangwei

doi:10.1039/c9sc06009j

Cited by 49 publications

(38 citation statements)

References 70 publications

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“…[56] MOFs:T unable electrical conductivity and redox-activity 1932 Ref. [79] 10 À3 Ref. [64] [47], [64]- [79] COFs:T unable electrical conductivity, photocatalysis 3000 Ref.…”

Section: Electroactive Building Blockmentioning

confidence: 99%

“…[79] 10 À3 Ref. [64] [47], [64]- [79] COFs:T unable electrical conductivity, photocatalysis 3000 Ref. [83] 10 À2 Ref.…”

Section: Electroactive Building Blockmentioning

confidence: 99%

“…[77] Very recently,z irconium MOFs using TTF linkersh ave also been presented as promising redox-active and highly stable frameworks for heterogeneous catalysis and photocatalysis. [78,79] The electroactive TTF has also been employeda sabuilding block for the constructiono fC OFs exhibitingh igh electrical conductivity.I n2 014, severalg roupsr eported the first 2D TTFbased COF (TTF-Ph-COF) [80][81][82] prepared by the solvothermalr eaction of TTF-tetrabenzaldehyde and 1,4-phenylenediamine. TTF-Ph-COF exhibits permanent porosity with aB ET surface area as high as 1014m 2 g À1 ,a nd electrical conductivity (10 À6 Scm À1 )t hat is enhanced by three orders of magnitude upon partial oxidation with iodine, generating the more conductive mixed-valence TTF species ( Figure 4).…”

Section: Tetrathiafulvalene(ttf)mentioning

confidence: 99%

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Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Souto

Strutyński

Melle‐Franco

et al. 2020

Chemistry A European J

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Electroactive organic molecules have received a lot of attention in the field of electronics because of their fascinating electronic properties, easy functionalization and potential low cost towards their implementation in electronic devices. In recent years, electroactive organic molecules have also emerged as promising building blocks for the design and construction of crystalline porous frameworks such as metal–organic frameworks (MOFs) and covalent‐organic frameworks (COFs) for applications in electronics. Such porous materials present certain additional advantages such as, for example, an immense structural and functional versatility, combination of porosity with multiple electronic properties and the possibility of tuning their physical properties by post‐synthetic modifications. In this Review, we summarize the main electroactive organic building blocks used in the past few years for the design and construction of functional porous materials (MOFs and COFs) for electronics with special emphasis on their electronic structure and function relationships. The different building blocks have been classified based on the electronic nature and main function of the resulting porous frameworks. The design and synthesis of novel electroactive organic molecules is encouraged towards the construction of functional porous frameworks exhibiting new functions and applications in electronics.

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“…[56] MOFs:T unable electrical conductivity and redox-activity 1932 Ref. [79] 10 À3 Ref. [64] [47], [64]- [79] COFs:T unable electrical conductivity, photocatalysis 3000 Ref.…”

Section: Electroactive Building Blockmentioning

confidence: 99%

“…[79] 10 À3 Ref. [64] [47], [64]- [79] COFs:T unable electrical conductivity, photocatalysis 3000 Ref. [83] 10 À2 Ref.…”

Section: Electroactive Building Blockmentioning

confidence: 99%

Section: Tetrathiafulvalene(ttf)mentioning

confidence: 99%

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Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Souto

Strutyński

Melle‐Franco

et al. 2020

Chemistry A European J

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“…Zhou and co-workers also reported a series of tetratopic ligands with different symmetries and Zr-MOFs with flu (PCN-605 or UMCM-312), scu (PCN-606), and csq (PCN-608) topologies were formed. [206][207][208] In past two years, lots of Zr-MOFs with the abovementioned topologies have been documented, including ftw (Zr-bptc, [209] Zr-IAM-4, [210] and Zr-PdX [211] ), csq (BUT-17, [212] MIP-200, [213] and NU-100x, x = 3, 4, 5, 6, 7, [214] 8 [215] ), scu (Zr-TTFTB, [216] PCN-901-SO 2 , [217,218] LIFM-114, [219] BUT-62, [220] BUT-63, [220] BUT-74, [221] Zr-abtc, [209] Zr-LMOF [222] and UU-100 [223] ), she (Zr-Me-TTFTB [216] ), sqc (MFM-601 [224] or BUT-15, [225] BUT-72, [221] and BUT-73 [221] ), and flu (PCN-902-O [217] ). The spirobifluorenelinkerbased ftw MOF Zr-IAM-4 is a twofold interpenetrated s tructure, which is different from PCN-221.…”

Section: Zr-mofs Based On Tetratopic Linkersmentioning

confidence: 99%

“…In past two years, lots of Zr‐MOFs with the abovementioned topologies have been documented, including ftw (Zr‐bptc, [ 209 ] Zr‐IAM‐4, [ 210 ] and Zr‐PdX [ 211 ] ), csq (BUT‐17, [ 212 ] MIP‐200, [ 213 ] and NU‐100 x , x = 3, 4, 5, 6, 7, [ 214 ] 8 [ 215 ] ), scu (Zr‐TTFTB, [ 216 ] PCN‐901‐SO 2 , [ 217,218 ] LIFM‐114, [ 219 ] BUT‐62, [ 220 ] BUT‐63, [ 220 ] BUT‐74, [ 221 ] Zr‐abtc, [ 209 ] Zr‐LMOF [ 222 ] and UU‐100 [ 223 ] ), she (Zr‐Me‐TTFTB [ 216 ] ), sqc (MFM‐601 [ 224 ] or BUT‐15, [ 225 ] BUT‐72, [ 221 ] and BUT‐73 [ 221 ] ), and flu (PCN‐902‐O [ 217 ] ). The spirobifluorenelinker‐based ftw MOF Zr‐IAM‐4 is a twofold interpenetrated structure, which is different from PCN‐221.…”

Section: Mofs Based On Zr (Group 4 Metal)mentioning

confidence: 99%

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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Spatially Confined Silver Nanoparticles in Mercapto Metal–Organic Frameworks to Compartmentalize Li Deposition Toward Anode‐Free Lithium Metal Batteries

Qin

et al. 2023

Advanced Materials

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As the promising next‐generation energy storage solution, lithium metal battery (LMB) has gained great attention but still suffers from troubles associated with the highly active metallic lithium. Herein, it is aimed to develop an anode‐free LMB engaging no Li disk or foil by modifying the Cu current collector with mercapto metal–organic frameworks (MOFs) impregnating Ag nanoparticles (NPs). While the polar mercapto groups facilitate and guide Li+ transport, the highly lithiophilic Ag NPs help to enhance the electric conductivity and lower the energy barrier of Li nucleation. Furthermore, the MOF pores allow compartmentalizing bulk Li into a 3D matrix Li storage so that not only the local current density is reduced, but also is the plating/stripping reversibility greatly enhanced. As a result, full cells pairing the prelithiated Ag@Zr‐DMBD/Cu anodes with LiFePO4 cathodes demonstrate a high initial specific capacity of 159.8 mAh g−1, first‐cycle Coulombic efficiency of 96.6%, and long‐term cycling stability over 1000 cycles with 99.3% capacity retention at 1 C. This study underlines the multi‐aspect functionalization of MOFs to impart lithiophilicity, polarity, and porosity to achieve reversible Li plating/stripping and paves the way for realizing high‐performance anode‐free LMBs through exquisite modification of the Cu current collector.

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Zirconium metal–organic frameworks incorporating tetrathiafulvalene linkers: robust and redox-active matrices for in situ confinement of metal nanoparticles

Abstract: Stable and redox active metal–organic frameworks were constructed by incorporating Zr6 clusters and redox-active TTF-based linkers, which allow in situ generation and stabilization of ultra-small noble metal nanoparticles for heterogenous catalysis.

Cited by 49 publications

References 70 publications

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Spatially Confined Silver Nanoparticles in Mercapto Metal–Organic Frameworks to Compartmentalize Li Deposition Toward Anode‐Free Lithium Metal Batteries

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