Browse
Submit Data
Databases
API
Help

Dataset Information

41 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Switchable electrical conductivity in a three-dimensional metal-organic framework via reversible ligand n-doping.

ABSTRACT: Redox-active metal-organic frameworks (MOFs) are promising materials for a number of next-generation technologies, and recent work has shown that redox manipulation can dramatically enhance electrical conductivity in MOFs. However, ligand-based strategies for controlling conductivity remain under-developed, particularly those that make use of reversible redox processes. Here we report the first use of ligand n-doping to engender electrical conductivity in a porous 3D MOF, leading to tunable conductivity values that span over six orders of magnitude. Moreover, this work represents the first example of redox switching leading to reversible conductivity changes in a 3D MOF.

SUBMITTER: Wentz HC

PROVIDER: S-EPMC8148085 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Switchable electrical conductivity in a three-dimensional metal-organic framework <i>via</i> reversible ligand n-doping.

Wentz Hanna C HC Skorupskii Grigorii G Bonfim Ana B AB Mancuso Jenna L JL Hendon Christopher H CH Oriel Evan H EH Sazama Graham T GT Campbell Michael G MG

Chemical science 20191218 5

Redox-active metal-organic frameworks (MOFs) are promising materials for a number of next-generation technologies, and recent work has shown that redox manipulation can dramatically enhance electrical conductivity in MOFs. However, ligand-based strategies for controlling conductivity remain under-developed, particularly those that make use of reversible redox processes. Here we report the first use of ligand n-doping to engender electrical conductivity in a porous 3D MOF, leading to tunable cond ...[more]

PMID: 34123257

Similar Datasets

Electrical conductivity through π-π stacking in a two-dimensional porous gallium catecholate metal-organic framework.

Project description:Metal-organic frameworks (MOFs) are hybrid materials known for their nanoscale pores, which give them high surface areas but generally lead to poor electrical conductivity. Recently, MOFs with high electrical conductivity were established as promising materials for a variety of applications in energy storage and catalysis. Many recent reports investigating the fundamentals of charge transport in these materials focus on the role of the organic ligands. Less consideration, however, is given to the metal ion forming the MOF, which is almost exclusively a late first-row transition metal. Here, we report a moderately conductive porous MOF based on trivalent gallium and 2,3,6,7,10,11-hexahydroxytriphenylene. Gallium, a metal that has not been featured in electrically conductive MOFs so far, has a closed-shell electronic configuration and is present in its trivalent state-in contrast to most conductive MOFs, which are formed by open-shell, divalent transition metals. Our material, made without using any harmful solvents, displays conductivities on the level of 3 mS/cm and a surface area of 196 m2 /g, comparable to transition metal analogs.

| S-EPMC10092259 | biostudies-literature

An electrically switchable metal-organic framework.

Project description:Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

| S-EPMC4137262 | biostudies-other

Valence-Dependent Electrical Conductivity in a 3D Tetrahydroxyquinone-Based Metal-Organic Framework.

Project description:Electrically conductive metal-organic frameworks (cMOFs) have become a topic of intense interest in recent years because of their great potential in electrochemical energy storage, electrocatalysis, and sensing applications. Most of the cMOFs reported hitherto are 2D structures, and 3D cMOFs remain rare. Herein we report FeTHQ, a 3D cMOF synthesized from tetrahydroxy-1,4-quinone (THQ) and iron(II) sulfate salt. FeTHQ exhibited a conductivity of 3.3 ± 0.55 mS cm-1 at 300 K, which is high for 3D cMOFs. The conductivity of FeTHQ is valence-dependent. A higher conductivity was measured with the as-prepared FeTHQ than with the air-oxidized and sodium naphthalenide-reduced samples.

| S-EPMC7888195 | biostudies-literature

Reversible Thermal Conductivity Switching Using Flexible Metal-Organic Frameworks.

Project description:The ability to control thermal transport is critical for the design of thermal rectifiers, logic gates, and transistors, although it remains a challenge to design materials that exhibit large changes in thermal conductivity with switching ratios suitable for practical applications. Here, we propose the use of flexible metal-organic frameworks, which can undergo significant structural changes in response to various stimuli, to achieve tunable switchable thermal conductivity. In particular, we use molecular dynamics simulations to show that the thermal conductivity of the flexible framework Fe(bdp) (bdp2- = 1,4-benzenedipyrazolate) becomes highly anisotropic upon transitioning from the expanded to the collapsed phase, with the conductivity decreasing by nearly an order of magnitude along the direction of compression. Our results add to a small but growing number of studies investigating metal-organic frameworks for thermal transport.

| S-EPMC10449012 | biostudies-literature

Intrinsic electrical conductivity of nanostructured metal-organic polymer chains.

Project description:One-dimensional conductive polymers are attractive materials because of their potential in flexible and transparent electronics. Despite years of research, on the macro- and nano-scale, structural disorder represents the major hurdle in achieving high conductivities. Here we report measurements of highly ordered metal-organic nanoribbons, whose intrinsic (defect-free) conductivity is found to be 10(4) S m(-1), three orders of magnitude higher than that of our macroscopic crystals. This magnitude is preserved for distances as large as 300 nm. Above this length, the presence of structural defects (~ 0.5%) gives rise to an inter-fibre-mediated charge transport similar to that of macroscopic crystals. We provide the first direct experimental evidence of the gapless electronic structure predicted for these compounds. Our results postulate metal-organic molecular wires as good metallic interconnectors in nanodevices.

| S-EPMC3644075 | biostudies-literature

Alkali Doping Leads to Charge-Transfer Salt Formation in a Two-Dimensional Metal-Organic Framework.

Project description:Efficient charge transfer across metal-organic interfaces is a key physical process in modern organic electronics devices, and characterization of the energy level alignment at the interface is crucial to enable a rational device design. We show that the insertion of alkali atoms can significantly change the structure and electronic properties of a metal-organic interface. Coadsorption of tetracyanoquinodimethane (TCNQ) and potassium on a Ag(111) surface leads to the formation of a two-dimensional charge transfer salt, with properties quite different from those of the two-dimensional Ag adatom TCNQ metal-organic framework formed in the absence of K doping. We establish a highly accurate structural model by combination of quantitative X-ray standing wave measurements, scanning tunnelling microscopy, and density-functional theory (DFT) calculations. Full agreement between the experimental data and the computational prediction of the structure is only achieved by inclusion of a charge-transfer-scaled dispersion correction in the DFT, which correctly accounts for the effects of strong charge transfer on the atomic polarizability of potassium. The commensurate surface layer formed by TCNQ and K is dominated by strong charge transfer and ionic bonding and is accompanied by a structural and electronic decoupling from the underlying metal substrate. The consequence is a significant change in energy level alignment and work function compared to TCNQ on Ag(111). Possible implications of charge-transfer salt formation at metal-organic interfaces for organic thin-film devices are discussed.

| S-EPMC7315632 | biostudies-literature

Iodine Adsorption in a Redox-Active Metal-Organic Framework: Electrical Conductivity Induced by Host-Guest Charge-Transfer.

Project description:We report a comparative study of the binding of I2 (iodine) in a pair of redox-active metal-organic framework (MOF) materials, MFM-300(VIII) and its oxidized, deprotonated analogue, MFM-300(VIV). Adsorption of I2 in MFM-300(VIII) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the VIII centers in the host framework and formation of I3- species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δσ = 700000) of I2@MFM-300(VIII/IV) in comparison to MFM-300(VIII). In contrast, no host-guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I2 in MFM-300(VIV). High-resolution synchrotron X-ray diffraction of I2@MFM-300(VIII/IV) confirms the first example of self-aggregation of adsorbed iodine species (I2 and I3-) into infinite helical chains within a MOF.

| S-EPMC6806328 | biostudies-literature

Continuous porous aromatic framework membranes with acid-/base-induced reversible isomerization for switchable ion conductivity.

Project description:Stimuli-responsive ion conductor materials are highly sought after in the fields of biological systems, clean energy, and smart devices. However, it remains a huge challenge to achieve acid/base switchable ion conductors owing to their stringent requirements of structural responsive behaviors, high stability and porosity. In this study, porous aromatic frameworks (PAFs) are utilized as a favorable platform to successfully design and prepare ion conductive powders and its continuous membranes based on a commercially available pH indicator. Interestingly, these PAFs possessed structural reversibility in response to acidic and alkaline environments, followed by an apparent ion-conducting switch of about 4 orders of magnitude (from 3.36 × 10-7 S cm-1 to 4.59 × 10-3 S cm-1) under the conditions of 25 °C and 98% RH. Moreover, the continuous PAF membrane exhibited an ultrahigh ion conductivity of 7.29 × 10-1 S cm-1 after 1 mol per L NaOH treatment and good acid/base switchable cycle stability. To our knowledge, this is the first report on exploring ion-conductive porous frameworks and continuous membranes that dynamically respond to acid/base chemical stimuli. This work provides a new research strategy for the application of ion conductors as so-called "smart materials" even in extremely harsh chemical environments.

| S-EPMC11905450 | biostudies-literature

Highly mesoporous metal-organic framework assembled in a switchable solvent.

Project description:The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

| S-EPMC4109014 | biostudies-literature

Integration of a (-Cu-S-)<sub>n</sub> plane in a metal-organic framework affords high electrical conductivity.

Project description:Designing highly conducting metal-organic frameworks (MOFs) is currently a subject of great interest for their potential applications in diverse areas encompassing energy storage and generation. Herein, a strategic design in which a metal-sulfur plane is integrated within a MOF to achieve high electrical conductivity, is successfully demonstrated. The MOF {[Cu2(6-Hmna)(6-mn)]·NH4}n (1, 6-Hmna = 6-mercaptonicotinic acid, 6-mn = 6-mercaptonicotinate), consisting of a two dimensional (-Cu-S-)n plane, is synthesized from the reaction of Cu(NO3)2, and 6,6'-dithiodinicotinic acid via the in situ cleavage of an S-S bond under hydrothermal conditions. A single crystal of the MOF is found to have a low activation energy (6 meV), small bandgap (1.34 eV) and a highest electrical conductivity (10.96 S cm-1) among MOFs for single crystal measurements. This approach provides an ideal roadmap for producing highly conductive MOFs with great potential for applications in batteries, thermoelectric, supercapacitors and related areas.

| S-EPMC6461620 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data