Modular O2 electroreduction activity in triphenylene-based metal–organic frameworks

Miner, Elise M.; Wang, Lu; Dincă, Mircea

doi:10.1039/c8sc02049c

Cited by 141 publications

(135 citation statements)

References 28 publications

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“…Lastly, the bimetallic Co x Ni y ‐CAT prepared from the ball‐milling reaction also displayed an excellent ORR activity ( E = 0.46 V; j l @0.0 V = –5.79 mA cm −2 ), similar to that of the sample prepared via the normal hydrothermal reaction (Figure f). Even though there are several reports regarding on the material preparation related to the monometallic M‐CATs and their electrochemical utilization, the strategy demonstrated here for the property enhancement by mixing the metal components and the method for the mass production of high‐quality M‐CATs should be beneficial for the advancement on this research area.…”

Section: Resultsmentioning

confidence: 99%

“…Conductive 2D hexagonal MOF layers (named M‐CAT; M = Co, Ni, or Cu) have been constructed from the hydrothermal reaction between 2,3,6,7,10,11‐hexahydroxytriphenylene (HHTP) and a divalent metal ion such as Co 2+ , Ni 2+ , or Cu 2+ , and have been utilized in chemiresistive sensors, supercapacitors, and ORR catalysts . For example, Xu and coworkers utilized a Cu‐CAT nanowire array as a high‐performance solid‐state supercapacitor .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (Co_xNi_y‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity

Yoon

Lee

et al. 2019

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The development of new electrocatalysts for electrochemical oxygen reduction to replace expensive and rare platinum‐based catalysts is an important issue in energy storage and conversion research. In this context, conductive and porous metal–organic frameworks (MOFs) are considered promising materials for the oxygen reduction reaction (ORR) due to not only their high surface area and well‐developed pores but also versatile structural features and chemical compositions. Herein, the preparation of bimetallic conductive 2D MOFs (CoxNiy‐CATs) are reported for use as catalysts in the ORR. The ratio of the two metal ions (Co2+ and Ni2+) in the bimetallic CoxNiy‐CATs is rationally controlled to determine the optimal composition of CoxNiy‐CAT for efficient performance in the ORR. Indeed, bimetallic MOFs display enhanced ORR activity compared to their monometallic counterparts (Co‐CAT or Ni‐CAT). During the ORR, bimetallic CoxNiy‐CATs retain an advantageous characteristic of Co‐CAT in relation to its high diffusion‐limiting current density, as well as a key advantage of Ni‐CAT in relation to its high onset potential. Moreover, the ORR‐active bimetallic CoxNiy‐CAT with excellent ORR activity is prepared at a large scale via a convenient method using a ball‐mill reactor.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (Co_xNi_y‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity

Yoon

Lee

et al. 2019

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118

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“…Electrically conductive metal-organic frameworks (MOFs) have recently attracted attention as potential materials for supercapacitors, 1,2 batteries, 3 thermoelectric devices, 4 chemiresistive sensors, 5,6 and electrocatalysts. [7][8][9][10] Significant effort is devoted towards the development of MOFs with increasingly higher conductivities. 11,12 Current record values of 2500 S/cm at room temperature for non-porous coordination polymers 13 and 40 S/cm for porous MOFs, 14 with many others approaching them, [15][16][17] were reported in hexagonal layered frameworks based on hexa-substituted triphenylenes and benzenes connected by first-row divalent transition metal ions such as Ni 2+ and Cu 2+ .…”

Section: Main Textmentioning

confidence: 99%

Efficient and Tunable One-Dimensional Charge Transport in Layered Lanthanide Metal-Organic Frameworks

Skorupskii¹,

Trump²,

Kasel³

et al. 2018

Preprint

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The most conductive MOFs are those made from organic ligands and square-planar transition metal ions connected into two-dimensional (2D) sheets that stack in a similar manner to the graphene sheets in graphite. Their electrical properties are thought to depend critically on the covalency of the metal-ligand bond. Much less importance is given to charge transport normal to the 2D sheets, not least because there is little synthetic opportunity to control their stacking sequence or distance. Here, we report exquisite control over the stacking sequence and distance in a series of materials made from 2D sheets of organic ligands connected in the third dimension by infinite lanthanide-oxygen chains. Contrary to transition metal MOFs, efficient charge transport leading to conductivity values of up to 0.5 S/cm in the lanthanide materials occurs primarily normal to the 2D sheets. We further show that the smaller lanthanides Yb3+ and Ho3+ enforce a shorter stacking distance of only 3.002(6) Å and afford consistently higher conductivity than the larger lanthanides Nd3+ and La3+, which distend the sheets up to 3.068(2) Å. This first systematic study of structure-function relationships in layered conductive MOFs is enabled by the high degree of crystallinity afforded by the relatively ionic lanthanide-ligand bonds. These results demonstrate that increasing the covalency of the metal-ligand bond is not the only viable path to achieve record conductivity in 2D MOFs, and that the interactions of the organic ligands alone can produce efficient charge transport pathways.

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“…Electrically conductive MOFs are of considerable interest from many perspectives. They are relevant as active materials for many applications, including electrocatalysis, 16 − 20 chemiresistive sensing, 21 − 26 and energy storage technologies. 27 − 30 Their fundamental transport properties merit further study, as certain conductive MOFs have been predicted to host topologically nontrivial electronic structures.…”

Section: Introductionmentioning

confidence: 99%

Electrically Conductive Metal–Organic Frameworks

2020

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Metal–organic frameworks (MOFs) are intrinsically porous extended solids formed by coordination bonding between organic ligands and metal ions or clusters. High electrical conductivity is rare in MOFs, yet it allows for diverse applications in electrocatalysis, charge storage, and chemiresistive sensing, among others. In this Review, we discuss the efforts undertaken so far to achieve efficient charge transport in MOFs. We focus on four common strategies that have been harnessed toward high conductivities. In the “through-bond” approach, continuous chains of coordination bonds between the metal centers and ligands’ functional groups create charge transport pathways. In the “extended conjugation” approach, the metals and entire ligands form large delocalized systems. The “through-space” approach harnesses the π–π stacking interactions between organic moieties. The “guest-promoted” approach utilizes the inherent porosity of MOFs and host–guest interactions. Studies utilizing less defined transport pathways are also evaluated. For each approach, we give a systematic overview of the structures and transport properties of relevant materials. We consider the benefits and limitations of strategies developed thus far and provide an overview of outstanding challenges in conductive MOFs.

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Modular O₂ electroreduction activity in triphenylene-based metal–organic frameworks

Abstract: Electrically conductive layered metal–organic frameworks, regardless of the metal or chelating atom identity, exhibit phase-dependent catalytic activity for O2 electroreduction.

Cited by 141 publications

References 28 publications

Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (Co_xNi_y‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity

Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (Co_xNi_y‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity

Efficient and Tunable One-Dimensional Charge Transport in Layered Lanthanide Metal-Organic Frameworks

Electrically Conductive Metal–Organic Frameworks

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Modular O2 electroreduction activity in triphenylene-based metal–organic frameworks

Abstract: Electrically conductive layered metal–organic frameworks, regardless of the metal or chelating atom identity, exhibit phase-dependent catalytic activity for O2 electroreduction.

Cited by 141 publications

References 28 publications

Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (CoxNiy‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity

Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (CoxNiy‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity

Efficient and Tunable One-Dimensional Charge Transport in Layered Lanthanide Metal-Organic Frameworks

Electrically Conductive Metal–Organic Frameworks

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Product

Resources

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Modular O₂ electroreduction activity in triphenylene-based metal–organic frameworks

Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (Co_xNi_y‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity

Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (Co_xNi_y‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity