Iron-Based 2D Conductive Metal–Organic Framework Nanostructure with Enhanced Pseudocapacitance

Stodolka, Michael; Choi, Ji Yong; Flood, J.; Pham, Hoai T. B.; Park, Jihye

doi:10.1021/acsanm.1c03862

Cited by 19 publications

(12 citation statements)

References 43 publications

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“…Triphenylene-based linkers with ortho-disubstituted donor atoms (N, O, and S) feature prominently in redox-active 2D MOFs . Triphenylenehexathiol (THT) specifically features dithiolene units that are known to be redox-active, offering the possibility of multiple discrete redox states.…”

Section: Introductionmentioning

confidence: 99%

Broad Electronic Modulation of Two-Dimensional Metal–Organic Frameworks over Four Distinct Redox States

et al. 2023

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Two-dimensional (2D) inorganic materials have emerged as exciting platforms for (opto)electronic, thermoelectric, magnetic, and energy storage applications. However, electronic redox tuning of these materials can be difficult. Instead, 2D metal−organic frameworks (MOFs) offer the possibility of electronic tuning through stoichiometric redox changes, with several examples featuring one to two redox events per formula unit. Here, we demonstrate that this principle can be extended over a far greater span with the isolation of four discrete redox states in the 2D MOFs Li x Fe 3 (THT) 2 (x = 0−3, THT = triphenylenehexathiol). This redox modulation results in 10,000-fold greater conductivity, p-to n-type carrier switching, and modulation of antiferromagnetic coupling. Physical characterization suggests that changes in carrier density drive these trends with relatively constant charge transport activation energies and mobilities. This series illustrates that 2D MOFs are uniquely redox flexible, making them an ideal materials platform for tunable and switchable applications.

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Section: Introductionmentioning

confidence: 99%

Broad Electronic Modulation of Two-Dimensional Metal–Organic Frameworks over Four Distinct Redox States

et al. 2023

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“…To this end, we synthesized Fe−HHTP (HHTP: 2,3,6,7,10,11-hexahydroxytriphenylene). 39 Unlike the previously reported 3D structure of Fe−HHTP, 40 our MOF consists of 2D layers distorted by the presence of N,Ndimethylformamide (DMF) molecules at the axial metal positions, leading to the expansion of the 2D interlayer distance (∼12.9 Å versus the common stacking distance of ∼3.4 Å) (Figure 6a,b). Consequently, the N 2 sorption of Fe− HHTP indicates a significant BET surface area of 675 m 2 /g, surpassing other common 2D HHTP-based EC-MOFs in the literature by nearly 200 m 2 /g (Figure 6c).…”

Section: Coordination Geometrymentioning

confidence: 54%

“…Introducing axial ligands can increase the interlayer stacking distance of 2D sheets, thereby enhancing the accessibility of the 2D sheets. To this end, we synthesized Fe–HHTP (HHTP: 2,3,6,7,10,11-hexahydroxytriphenylene) . Unlike the previously reported 3D structure of Fe–HHTP, our MOF consists of 2D layers distorted by the presence of N , N -dimethylformamide (DMF) molecules at the axial metal positions, leading to the expansion of the 2D interlayer distance (∼12.9 Å versus the common stacking distance of ∼3.4 Å) (Figure a,b).…”

Section: Enhancing Molecular Accessibility Within Ec-mofsmentioning

confidence: 98%

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Maximizing the Potential of Electrically Conductive MOFs

Pham,

Choi,

Stodolka

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Electrically conductive metal−organic frameworks (EC-MOFs) have emerged as a compelling class of materials, drawing increasing attention due to their unique properties facilitating charge transport within porous structures.The synergy between electrical conductivity and porosity has opened a wide range of applications, including electrocatalysis, energy storage, chemiresistive sensing, and electronic devices that have been underexplored for their insulating counterparts. Despite these promising prospects, a prevalent challenge arises from the predominant adoption of two-dimensional (2D) structures by most EC-MOFs. These 2D frameworks often show modest surface areas and short interlayer distances, hindering molecular accessibility, which deviates from the inherent characteristics of conventional MOFs. Furthermore, the quest for efficient charge transport imposes design constraints, leading to a restricted selection of functional building blocks. Additionally, there is a lack of established functionalization methods within EC-MOFs, limiting their functional diversity. Thus, these challenges have impeded EC-MOFs from reaching their full potential.In this Account, we summarize and discuss our group's efforts aimed at enhancing molecular accessibility and deploying the functional diversity of EC-MOFs. Our focus on enhancing molecular accessibility involves several strategies. First, we employed macrocyclic ligands with intrinsic pockets as the building blocks for EC-MOFs. The integrated intrinsic pockets in the frameworks supplement surface areas and additional pores to enhance molecular accessibility. The resulting macrocyclic ligand-based EC-MOFs exhibit exceptionally high surface areas and confer advantages in electrochemical performances. Second, our efforts extend to addressing the structural limitations, frequently associated with EC-MOFs' 2D structures. Through the pillar insertion strategy, we transformed a 2D EC-MOF platform into a three-dimensional (3D) structure, thereby achieving higher porosity and enhanced molecular accessibility. In pursuing functional diversity, we have delved into molecular-level tuning of EC-MOF building blocks. We demonstrated that electron-rich alkyne-based pockets in the macrocyclic ligands can host transition metals and alkali ions, enabling ion selectivity and showcasing diverse use of EC-MOFs. We utilized a postsynthetic approach to further functionalize metal nodes on the molecular level within an EC-MOF framework, introducing a proton-conducting pathway while preserving its electrical conductivity.We aspire for this Account to provide practical insights and strategies to surmount structural and functional diversity limitations in the realm of EC-MOFs. By integrating enhanced molecular accessibility and diverse functionality, our endeavor to propel the utility of these materials will inspire further rational development for future EC-MOFs and unlock their full potential.

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“…The CVs of blank NF, bulk Ni-HHTP, Ni-HHTP-Disc, and Ni-HHTP-Flower show a stark contrast in capacitance (Figure ). The performance of bulk Ni-HHTP prepared as a traditional ink exhibited a gravimetric capacitance in agreement with previous reports with a value of 3.73 F g –1 , when measured at a scan rate of 100 mV s –1 . , However, the capacitance of Ni-HHTP-Disc approximately doubled to 8.02 F g –1 while the capacitance of Ni-HHTP-Flower increased to 39.7 F g –1 , nearly a 10-fold increase compared to the bulk ink.…”

mentioning

confidence: 99%

Electrosynthesis of a Nickel-Based Conductive Metal–Organic Framework with Controlled Morphology for Enhanced Capacitance

Stodolka,

Choi,

Fang

et al. 2023

ACS Materials Lett.

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Electrically conductive metal−organic frameworks (EC-MOFs) are highly sought-after materials for electrocatalysis and energy storage because of their unique combination of intrinsic porosity and electrical conductivity. However, it is challenging to incorporate these exciting materials into functional devices because of the difficulty in synthesizing the frameworks directly on desired substrates and at a scale suitable for mass distribution with a controlled morphology. Electrosynthesis can provide a means that is both scalable and synthetically controllable by which metal−organic frameworks can be grown directly on targeted substrates for use in electronic devices. In this work, we demonstrate the electrosynthesis of an EC-MOF constructed with nickel and 2,3,6,7,10,11-hexahydroxytriphenylene, namely Ni-HHTP, with distinct disc and flower-like morphologies (Ni-HHTP-Disc and Ni-HHTP-Flower) by varying the ligand concentrations. The electrochemical performance of Ni-HHTP-Flower greatly exceeds that of bulk Ni-HHTP, boasting gravimetric capacitances and electrochemically active surface areas up to 10 times that of the bulk material because of mesoporous features absent in the bulk, showcasing electrosynthesis as a promising method for preparing future EC-MOFbased devices.

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Iron-Based 2D Conductive Metal–Organic Framework Nanostructure with Enhanced Pseudocapacitance

Cited by 19 publications

References 43 publications

Broad Electronic Modulation of Two-Dimensional Metal–Organic Frameworks over Four Distinct Redox States

Broad Electronic Modulation of Two-Dimensional Metal–Organic Frameworks over Four Distinct Redox States

Maximizing the Potential of Electrically Conductive MOFs

Electrosynthesis of a Nickel-Based Conductive Metal–Organic Framework with Controlled Morphology for Enhanced Capacitance

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