2.5. Application
25-40Surveys conductive MOFs in sensing, energy storage, energy conversion, electronics, spin valves, topological-insulator candidates and thermoelectrics.
Relevance: Core · p. 25 · 2.5. Application
Review · secondary evidenceReview
Conductive MOFs
Wen-Hua Li, Wei-Hua Deng, Guan-E Wang, Gang Xu · EnergyChem · 2020
11review sections
11material families
21review claims
22secondary benchmarks
40cited studies
10research gaps
Review scope
To summarise recent progress in electronically conductive and proton-conductive MOFs, emphasising material preparation, conductivity measurement, transport mechanisms, applications, and unresolved challenges.
- Coverage
- 1979–2020
- Category
- Review Thermoelectric
- Material scope
- electronically conductive MOFs and PCPs · proton-conductive MOFs and PCPs · 2D pi-conjugated MOFs · doped and guest@MOF conductors · proton-conductive films and glass-state MOFs
- Transport scope
- through-space and through-bond electronic transport · hopping and band-like electronic transport · metallic and semiconducting states · Grotthuss and vehicular proton transport · humidity-mediated and anhydrous proton conduction
- Application scope
- chemiresistive sensing · supercapacitors and batteries · electrocatalysis · field-effect transistors and spintronic devices · thermoelectrics · fuel-cell electrolyte context
- Explicit exclusions
- ion-conductive MOFs other than proton conductors · proton-conducting MOF composites reviewed elsewhere · full experimental recipes and exhaustive bibliography
- Source
- p. 1 · Abstract
- Evidence role
- Context, taxonomy and secondary benchmarking
Section map
The review’s argument is preserved as a navigable set of section summaries.
2.2. Composition and crystal structures
8-20Organises electronic MOFs by ligand and transport architecture, including planar multidentate ligands, pi-stacked pathways, redox/mixed-valence frameworks, metal-sulfur motifs, doped MOFs and guest@MOFs.
Relevance: Core · p. 8 · 2.2. Composition and crystal structures
2.4. Mechanism of the electronically conducting in MOFs
22-25Distinguishes charge density and mobility, through-space/through-bond design, hopping/band models, and metallic-state examples.
Relevance: Core · p. 22 · 2.4. Mechanism
1. Introduction
1-2Defines MOFs/PCPs, motivates conductivity as a limiting property, and frames electronic and proton conduction timelines.
Relevance: Core · pp. 1-2 · 1. Introduction · Schemes 1-2
2.3. Electrical transport measurements
20-22Explains conductivity, thermal-variation and mobility measurements, including the importance of geometry, contacts, anisotropy and sample quality.
Relevance: Core · p. 20 · 2.3. Electrical transport measurements
4. Challenges and perspectives
54-55Synthesises advantages, unresolved gaps and design principles for electronic and proton-conductive MOFs.
Relevance: Core · p. 54 · 4. Challenges and perspectives
3. Proton-conductive MOFs
40-41Frames proton-conductive MOFs against PEMFC/Nafion requirements and the need for tunable crystalline platforms.
Relevance: Supporting · p. 40 · 3. Proton-conductive MOFs
3.2. Mechanism of proton conducting in MOFs
40-41Defines Grotthuss and vehicular proton mechanisms and links activation energy to mechanistic assignment.
Relevance: Core · p. 40 · 3.2. Mechanism · Fig. 49
3.3. Proton sources in MOFs
41Classifies proton sources as pore counterions, dangling acid groups, and protic guests/nonvolatile acids.
Relevance: Core · p. 41 · 3.3. Proton sources · Fig. 50
3.4. Types of proton-conductive MOFs
41-54Organises proton-conductive MOFs by hydrous, anhydrous, dual-condition, film and glass-state systems.
Relevance: Supporting · p. 41 · 3.4. Types of proton-conductive MOFs
2.1. Synthesis methods
3-8Compares hydro/solvothermal synthesis with interface-assisted methods for crystals, powders, thin films and single layers.
Relevance: Core · p. 3 · 2.1. Synthesis methods
Taxonomies
Classification systems are attributed to this review and are not treated as a global material registry.
Chemical And Physical Description Of Charge Transport
Electronic transport modes
The review explicitly presents a two-axis framework: chemical pathways through space/bond and physical mechanisms hopping/band-like.
Categories: through space · through bond · hopping · band theory
p. 22 · 2.4.1 · Fig. 24
Dominant Mobile CarrierAuthor-proposed
Conductive MOF scope
The review divides conductive MOFs into electronic charge conductors and proton conductors with separate mechanisms, measurements and applications.
Categories: electronically conductive MOFs · proton-conductive MOFs
p. 2 · 1. Introduction
Growth Interface And Device-Integration RouteAuthor-proposed
Interface-assisted synthesis routes
Figure 1 classifies interface-assisted routes used to form conductive MOF films from micron to centimetre scale and few-layer thickness.
Categories: gas-liquid interfacial synthesis · liquid-liquid interfacial synthesis · Langmuir-Blodgett method · solid-liquid interfacial synthesis · self-sacrificial templates · self-assembly on solid surfaces
p. 3 · 2.1.2 · Fig. 1
2D Network TopologyAuthor-proposed
Benzene-derived lattice motifs
For benzene-derived linker MOFs, the review distinguishes porous hexagonal networks from non-porous Kagome lattices.
Categories: hexagonal lattice with M-X4 planar metal sites · Kagome structure with continuous lateral connection
p. 11 · 2.2.1 · Fig. 11
Electrical Measurement Geometry And Sample Type
Conductivity measurement methods
The review connects choice of measurement to conductivity magnitude, contact resistance, thin-film geometry and sample anisotropy.
Categories: two-contact probe · four-contact probe · four-point method · van der Pauw method
p. 21 · 2.3.1 · Fig. 23
Organic Ligand Core And Terminal Donor GroupAuthor-proposed
Planar multidentate ligand subclasses
The composition section groups highly conductive pi-conjugated 2D MOFs by planar ligand families and metal nodes.
Categories: benzene-derived · triphenylene-derived · phthalocyanine-derived · fused-ring hydrocarbons
p. 9 · 2.2.1 · Figs. 9-18
Mode Of Proton Motion
Proton conduction mechanisms
The proton section distinguishes proton hopping through hydrogen-bond networks from diffusion of solvated proton carriers.
Categories: Grotthuss mechanism · vehicular mechanism
p. 40 · 3.2. Mechanism · Fig. 49
Humidity And Temperature RegimeAuthor-proposed
Proton-conductive MOF operating classes
The review organises proton conductors by water assistance, anhydrous operation, dual functionality, membrane processing and glass-state behaviour.
Categories: aqueous condition below 100 C · anhydrous condition · both anhydrous and humidified conditions · proton-conductive MOF films · glass-state MOFs
p. 2 · 1. Introduction · Scheme 2
Location And Chemical Nature Of Proton CarriersAuthor-proposed
Proton source types
The review classifies proton sources by whether they are intrinsic counterions/framework acid groups or guest species in pores.
Categories: Type I pore counterions · Type II dangling acid functional groups · Type III protic guest molecules or nonvolatile acids
p. 41 · 3.3. Proton sources · Fig. 50
Material families
Review-defined families retain their representative materials and conduction descriptions.
Benzene-derived conductive MOFs
2D Films, Pellets And Nanosheets2D MOFs based on compact benzene-derived linkers bearing hydroxyl, imino, thiol, amino-thiol or selenolate groups.
Conduction: Short linkers promote strong orbital overlap; topology may be hexagonal porous or Kagome-like nonporous.
Representative materials: Ni-BHT · Cu-BHT · Cu3HIB2 · Cu3HSB
Nodes / linkers: Cu · Ni · Pd · Pt · Ag · HHB · HIB · HTB/BHT · TTB · HSB
p. 9 · 2.2.1 · Fig. 10 and Table 1
Carboxylate and phosphonate proton-conductive MOFs
2D Layers, 3D Channels And 1D Inorganic ChainsMOFs using carboxylate or phosphonate frameworks with acid groups, imidazole/imidazolium guests or ordered phosphate chains.
Conduction: Acidic groups, guest carriers and H-bond chains tune hydrous and anhydrous proton transport.
Representative materials: In-IA-2D-1 · Im@NENU-3 · BUT-8(Cr)A · PCMOF-5 · ZrP
Nodes / linkers: In · Zn · Cr · Zr · isophthalate · imidazolium carboxylate · sulfonated dicarboxylate · phosphonate
p. 45 · 3.4.1
Doped MOFs and guest@MOFs
3D Porous Host Frameworks And Thin FilmsConductive composites where redox-active dopants or donor-acceptor guests introduce carriers or charge-transfer pathways.
Conduction: Guest/dopant interactions can oxidise/reduce framework units or bridge host nodes to dramatically enhance conductivity.
Representative materials: I2@Cu[Ni(pdt)2] · KxFe2(BDP)3 · TCNQ@Cu3(BTC)2 · NiCB@NU-1000 · C60@NU-901
Nodes / linkers: Cu · Ni · Fe · Zr · pdt · BDP · BTC · pyrene linkers
p. 19 · 2.2.3 · Fig. 22
Glass-state CPs/MOFs for proton conductivity
Amorphous/Glassy Materials Derived From Crystalline CPsMelt-quenched or mechanically amorphised coordination polymers/MOFs whose glass state enhances proton dynamics and processability.
Conduction: Glass formation can weaken proton-limiting interactions, enhance acidity and create flexible proton pathways.
Representative materials: CdTz · a-CdTz-40 · a-CdTz-240 · a-CdTz-500 · melted imidazole phosphates
Nodes / linkers: Cd · Zn · triazole · phosphate · imidazole
p. 53 · 3.4.5 · Fig. 68
Metal-sulfur chain and plane MOFs
1D Chains To 2D PlanesConductive MOFs containing extended (-M-S-)n chains or planes with strong metal-chalcogen orbital overlap.
Conduction: Sulfur coordination lowers hopping barriers and, when expanded to planes, supports dense charge-transfer pathways.
Representative materials: Fe2(DSBDC) · Mn2(DSBDC) · [Cu2(6-Hmna)(6-mn).NH4]n
Nodes / linkers: Fe · Mn · Cu · DSBDC · Hmna/mn sulfur ligands
p. 18 · 2.2.2 · Fig. 21
Oxalate-based proton-conductive MOFs
1D Water Chains, 2D Layers And 3D Channel NetworksHydrous proton-conducting MOFs whose oxalate frameworks host water, ammonium or hydrophilic channels.
Conduction: Hydrogen-bond networks and water/protonated counterions mediate Grotthuss-like transport.
Representative materials: Fe(ox).2H2O · (NH4)2(adp)[Zn2(ox)3].nH2O · (NH4)4[MnCr2(ox)6].4H2O · [Eu2(CO3)(ox)2(H2O)2].4H2O
Nodes / linkers: Fe · Zn · Mn/Cr · Eu · oxalate · adipate co-linker
p. 41 · 3.4.1
Phthalocyanine-derived conductive MOFs
2D Layered Molecular Meshes2D conductive MOFs using phthalocyanine macrocycles with amino or hydroxyl groups and metal-centred square lattices.
Conduction: Macrocyclic pi systems and metal linkages offer tunable conductivity, sensing, electrocatalysis and magnetic ordering.
Representative materials: NiPc-M · NiNPc-M · K3Fe2[PcFe-O8] · PcCu-O8-Co
Nodes / linkers: Ni · Cu · Fe · Co · octaamino phthalocyanine · octahydroxy phthalocyanine · naphthalocyanine derivatives
p. 12 · 2.2.1 · Fig. 14
2D pi-conjugated planar multidentate MOFs
Primarily 2D Layered FrameworksLayered MOFs assembled from planar multidentate ligands and planar metal-complex nodes with delocalised pi electrons.
Conduction: In-plane metal-ligand conjugation and interlayer interactions can support high electrical conductivity, sometimes metallic or band-like behaviour.
Representative materials: Ni3HITP2 · Cu3HHTP2 · Cu-BHT · PTC-Fe
Nodes / linkers: Cu · Ni · Co · Fe · HITP · HHTP · BHT/HTB · perthiolated coronene
p. 8 · 2.2.1
Pi-stacked 3D conductive MOFs
3D Porous Frameworks With 1D StacksFrameworks where non-covalent pi-pi stacks of electroactive ligands create charge-transport pathways.
Conduction: Short intermolecular contacts and stacked donor units enable through-space mobility and large conductivity enhancements.
Representative materials: Zn2(TTFTB) · M2(TTFTB) · ANMOF-74
Nodes / linkers: Zn · Mn · Co · Cd · Mg · Ni · tetrathiafulvalene tetrabenzoate · anthracene dicarboxylate
p. 17 · 2.2.2 · Fig. 19
Redox-active and mixed-valence MOFs
3D Porous Frameworks And 2D MagnetsMOFs whose conductivity is controlled by ligand redox manifolds, mixed-valence metal nodes or their combination.
Conduction: Redox manifolds and partially oxidised metal centres create charge carriers and hopping/delocalisation pathways.
Representative materials: (NBu4)2Fe2(dhbq)3 · Fe2(BDT)3 · Fe(tri)2(BF4)x
Nodes / linkers: Fe · V · benzoquinone-derived ligands · triazolate · BDT
p. 17 · 2.2.2 · Fig. 20
Triphenylene-derived MOFs
2D Layered Frameworks And FilmsConductive MOFs based on HHTP, HITP, HTTP or HSTP triphenylene linkers.
Conduction: Extended planar linkers support pi-d conjugation, stacking-dependent transport and possible metallic or thermoelectric behaviour.
Representative materials: Ni3HITP2 · Cu3HHTP2 · Co3HTTP2 · Fe3HTTP2
Nodes / linkers: Ni · Cu · Co · Fe · lanthanides · HHTP · HITP · HTTP · HSTP
p. 11 · 2.2.1 · Fig. 12
Synthesis strategies
Review-level synthesis principles remain separate from primary-study recipes.
Air-liquid interfacial HITP film formation
Hydrophilic-to-hydrophobic ligand transitions and water-surface nucleation yield free-standing Ni3HITP2 films.
Claimed effects: Produces smooth, large-area crack-free Ni3HITP2 films for porous FETs and Li-S separators.
Controlling variables: ligand wettability transition · nucleation at water surface · film thickness · transfer/stamping conditions
Representative materials: Ni3HITP2 film · Ni3HITP2/PP membrane
Caveat: Device performance still depends on interface quality and film crystallinity.
p. 5 · 2.1.2 · Fig. 5
Guest-mediated charge transfer
Electron-deficient or redox-active guest molecules are incorporated into porous hosts to create donor-acceptor pathways.
Claimed effects: Can transform insulating MOFs into conductive guest@MOFs without rebuilding the host framework.
Controlling variables: guest redox level · host donor/acceptor sites · pore connectivity · guest loading
Representative materials: TCNQ@Cu3(BTC)2 · NiCB@NU-1000 · C60@NU-901
Caveat: Mechanisms and stability depend strongly on host-guest interaction strength.
p. 20 · 2.2.3
Hydro-/solvothermal crystal growth
Autoclave synthesis in aqueous/non-aqueous solutions increases solubility/reactivity and supports crystal growth for 3D and some 2D conductive MOFs.
Claimed effects: Can give high-yield, low-cost conductive MOF crystals but is sensitive to conditions and hard to observe in real time.
Controlling variables: temperature · pressure · solvent · surfactant additives · precursor concentration
Representative materials: M-CAT · Ni3HITP2 · M2(TTFTB) · PTC-Fe
Caveat: Sealed autoclaves impede real-time observation; process is energy-consuming and parameter-sensitive.
p. 3 · 2.1.1
Liquid-liquid and gas-liquid interfacial growth
Interfaces between immiscible liquid phases or liquid/air are used to form conductive MOF films and nanosheets with controlled thickness.
Claimed effects: Enables high-quality thin films and nanosheets for device integration.
Controlling variables: interface type · solvent choice · air sensitivity · temperature · reactant concentration · container size
Representative materials: Ni-BHT · Cu-BHT · Ag-BHT · M-HIB films
Caveat: Film crystallinity and intrinsic transport can be damaged by poor crystallinity, grain boundaries or air sensitivity.
p. 4 · 2.1.2
Langmuir-Blodgett monolayer growth
Sub-monolayer organic linkers are compressed at the air-water interface before metal ions diffuse from the subphase to coordinate single layers.
Claimed effects: Allows molecular-level control of single-layer conductive MOF films and very thin device layers.
Controlling variables: surface pressure · monomer packing density · metal ion diffusion · water subphase composition
Representative materials: Ni3HTTP2 · Cu-CAT-1
Caveat: Single-layer formation is specialised and may not directly address large-scale device robustness.
p. 5 · 2.1.2 · Fig. 6
Liquid-solid interface integration
Template bottom-up assembly, layer-by-layer liquid-phase epitaxy and vapour-assisted conversion grow conductive MOFs directly on electrodes/substrates.
Claimed effects: Integrates conductive MOFs into sensors, photovoltaic/FET substrates and supercapacitor electrodes.
Controlling variables: substrate chemistry · growth cycle count · template composition · vapour conversion conditions · orientation
Representative materials: Cu3HHTP2 · Ni-CAT · M-CAT-1
Caveat: Each method trades off structural control, preparation time and substrate compatibility.
p. 6 · 2.1.2
On-surface self-assembly
Single-layer conductive MOFs are assembled directly on metal surfaces and characterised by STM/DFT.
Claimed effects: Reveals sub-molecular structures, band gaps and possible topological phases in single-layer MOFs.
Controlling variables: metal substrate · surface adsorption · single-layer registry · charge transfer to substrate
Representative materials: Cu3(C6O6) · Ni3HITP2 on Au(111)
Caveat: Surface-bound phases may differ from free-standing or bulk materials.
p. 7 · 2.1.2 · Fig. 8
Proton carrier and pathway design
Proton conductivity is increased by adding counterions, dangling acid groups, guest carriers or ordered hydrogen-bond pathways.
Claimed effects: Creates hydrous or anhydrous proton transport routes and can improve fuel-cell-relevant conductivity.
Controlling variables: carrier concentration · pKa matching · humidity · ordered protic-site alignment · activation energy
Representative materials: (NH4)2(adp)[Zn2(ox)3].3H2O · Im@NENU-3 · ZrP · Cu-TCPP nanofilm
Caveat: Processability, stability and high-temperature operation remain limiting for PEMFC use.
p. 55 · 4. Challenges and perspectives
Redox doping of conductive MOFs
Oxidation or reduction of redox-active ligands/metal nodes introduces carriers and changes conductivity.
Claimed effects: Can enhance conductivity by orders of magnitude and tune spin/photo/magnetic behaviour.
Controlling variables: oxidant/reductant identity · doping level · redox-active framework unit · structural robustness
Representative materials: I2@Cu[Ni(pdt)2] · KxFe2(BDP)3 · ZnNDI
Caveat: Precise dopant-level control and doped-system robustness remain challenging.
p. 20 · 2.2.3
Review claims
These are the review authors’ synthesis, not newly measured results.
Author InterpretationHigh supportCaveat
High-temperature anhydrous proton-conductive MOFs are still rare; most reported examples operate below 200 C and below 0.01 S cm-1.
Evidence basis: review_reasoning
Caveat: This is review status as of 2020 and should be updated for any later thesis claims.
p. 51 · 3.4.2
Author InterpretationMedium supportTransport Mechanism
Band-like transport is emerging in semiconducting MOFs but requires well-dispersed bands, low scattering and high-quality structural order.
Evidence basis: single_reference
Caveat: The review notes that defects, impurities and boundaries lower scattering time and mobility.
p. 23 · 2.4.1
Consensus SummaryHigh supportDefinition Scope
Most MOFs are electrical or protonic insulators, so conductive MOF design is framed as enabling electronic, electrochemical and fuel-cell technologies.
Evidence basis: review_reasoning
Caveat: This is a review-level generalisation rather than a measured value for a specific framework.
p. 54 · 4. Challenges and perspectives
Author InterpretationHigh supportCaveat
Redox doping and guest@MOF strategies can strongly enhance conductivity, but dopant-level precision and robustness remain major limitations.
Evidence basis: multi_reference
Caveat: The review distinguishes doped MOFs from host-guest charge-transfer systems.
p. 20 · 2.2.3
Author InterpretationMedium supportApplication Relevance
The review interprets conductive MOFs as promising electrodes, separators or hosts for supercapacitors and batteries because conductivity and porosity can coexist.
Evidence basis: multi_reference
Caveat: Low surface area, fragile films and device-scale processing limit current applications.
p. 33 · 2.5.2
Author InterpretationHigh supportConsensus
The field needs coordinated synthesis, precise measurement, theory and computation to establish structure-property relationships for conductive MOFs.
Evidence basis: review_reasoning
Caveat: Outlook statement from review authors.
p. 55 · 4. Challenges and perspectives
Author InterpretationMedium supportMaterial Comparison
Glass-state CPs/MOFs are presented as promising because they combine processability with altered proton dynamics compared with crystals.
Evidence basis: single_reference
Caveat: The review gives representative examples rather than a broad performance survey.
p. 53 · 3.4.5
Author InterpretationMedium supportStructure Property Link
Metal-sulfur chains and planes are highlighted as a route to stronger orbital overlap and lower hopping barriers than oxygen analogues.
Evidence basis: multi_reference
Caveat: Generality beyond cited M-S examples requires more primary evidence.
p. 18 · 2.2.2
Consensus SummaryHigh supportMeasurement Interpretation
Conductivity values in MOFs are method- and sample-dependent; contact resistance, geometry, homogeneity and anisotropy must be recorded.
Evidence basis: review_reasoning
Caveat: Review warns that pressed pellets and polycrystalline films often obscure intrinsic transport.
p. 21 · 2.3.1
Author InterpretationMedium supportMaterial Comparison
Conductive MOFs are usually semiconductors, but several BHT/HIB/HTTP examples exhibit metallic signatures or metallic-like transitions.
Evidence basis: multi_reference
Caveat: Experimental metallicity can be masked by grain boundaries and structural disorder.
p. 23 · 2.4.2
Consensus SummaryHigh supportTransport Mechanism
Electronic conductivity in MOFs requires both high charge density and high carrier mobility; metal nodes and organic linkers can both provide carriers.
Evidence basis: review_reasoning
Caveat: Specific mechanisms depend on framework composition and sample quality.
p. 22 · 2.4
Author InterpretationHigh supportMaterial Comparison
The review treats 2D pi-conjugated planar multidentate MOFs as the most conductive known MOF family.
Evidence basis: multi_reference
Caveat: No regular relation is yet observed between PAH extension and electrical transport.
p. 8 · 2.2.1
Author InterpretationHigh supportCaveat
Practical PEMFC use is limited by membrane/processability issues because most proton-conducting MOFs are pellets or single crystals.
Evidence basis: multi_reference
Caveat: The review cites early nanofilm work but does not claim broad device readiness.
p. 52 · 3.4.4
Consensus SummaryHigh supportTransport Mechanism
The review uses activation energy as a diagnostic: Grotthuss transport generally has lower Ea than vehicular transport.
Evidence basis: review_reasoning
Caveat: Activation-energy assignment is a heuristic and must be supported by structural evidence.
p. 41 · 3.2
Consensus SummaryHigh supportStructure Property Link
High proton conductivity in MOFs depends on carrier concentration, motion entropy, three-dimensional pathways and low activation energy.
Evidence basis: review_reasoning
Caveat: Humidity and guest volatility can dominate practical performance.
p. 41 · 3.2
Consensus SummaryHigh supportTransport Mechanism
Redox-active ligands and mixed-valence metal centres can increase carrier density and enable hopping/delocalised transport.
Evidence basis: multi_reference
Caveat: Mixed-valence states must be stabilised without degrading framework order.
p. 18 · 2.2.2
Consensus SummaryHigh supportApplication Relevance
Conductive 2D MOFs are attractive chemiresistive sensors because high conductivity, porosity and modular metal/linker chemistry can convert adsorption into electrical signals.
Evidence basis: multi_reference
Caveat: Mechanistic insight into host-guest interactions remains incomplete.
p. 28 · 2.5.1
Author InterpretationHigh supportMeasurement Interpretation
Single-domain films and single crystals are identified as the best forms for intrinsic anisotropic charge-transport studies.
Evidence basis: review_reasoning
Caveat: Such samples are difficult to synthesise, especially for 2D conductive MOFs.
p. 21 · 2.3.1
Consensus SummaryHigh supportStructure Property Link
Terminal groups, metal centres, stacking modes, crystal orientation, crystallinity, grain boundaries and defects can dramatically alter transport in conductive MOFs.
Evidence basis: review_reasoning
Caveat: The review emphasises that simple ligand-size trends are insufficient.
p. 9 · 2.2.1
Author InterpretationMedium supportApplication Relevance
Conductive MOFs are promising thermoelectrics because they can combine crystalline electronic transport with low thermal conductivity from porous/nanostructured frameworks.
Evidence basis: multi_reference
Caveat: Reported ZT values remain modest relative to practical thermoelectrics.
p. 39 · 2.5.4
Consensus SummaryHigh supportTransport Mechanism
Pi-pi stacking provides through-space transport when neighbouring ligands have short contacts and good orbital overlap.
Evidence basis: multi_reference
Caveat: Stacking geometry must be experimentally and computationally resolved.
p. 17 · 2.2.2
Secondary benchmarks
Every row remains visibly secondary and links to a primary dossier only where the mapping is verified.
| Material | Property | Reported value | Context and quality | Primary evidence | Review source |
|---|---|---|---|---|---|
| Secondarya-CdTz-500 | proton conductivity | 1.0 x 10^-4 S cm-1 | below glass crystallisation temperature; glass-state CP Text · Exact Reported | No verified corpus mapping | p. 53 · 3.4.5 |
| Secondary(NH4)2(adp)[Zn2(ox)3].3H2O | proton conductivity | 8 x 10^-3 S cm-1 at 25 C and 85% RH | 25 C, 85% RH Text · Exact Reported | research_0220 | p. 41 · 3.4.1 |
| SecondaryAg5HTB / Ag-BHT | electrical conductivity | 250 S cm-1 | film, 4-probe, room temperature; review Table 1 Table · Exact Reported | research_0735 | p. 10 · 2.2.1 · Table 1 |
| SecondaryCu-BHT | electron mobility | 116 cm2 V-1 s-1 | film FET at 300 K Text · Exact Reported | research_0006 | p. 22 · 2.3.3 |
| SecondaryCu3HTB / Cu-BHT | electrical conductivity | 1580 S cm-1 | film, 4-probe, room temperature; review Table 1 Table · Exact Reported | research_0006 | p. 10 · 2.2.1 · Table 1 |
| SecondaryCu3HSB | electrical conductivity | 110 S cm-1 | pellet, 4-probe, room temperature; review Table 1 Table · Exact Reported | No verified corpus mapping | p. 10 · 2.2.1 · Table 1 |
| Secondary[Cu2(6-Hmna)(6-mn).NH4]n | electrical conductivity | 10.96 S cm-1 | single crystal, 4-probe; review Table 2/text Text · Exact Reported | research_0104 | p. 19 · 2.2.2 · Fig. 21 |
| SecondaryCu-TCPP nanofilm | proton conductivity | 3.9 x 10^-3 S cm-1 at 98% RH | 25 C/ambient text context, 98% RH Text · Exact Reported | No verified corpus mapping | p. 53 · 3.4.4 |
| SecondaryFe(ox).2H2O | proton conductivity | 1.3 x 10^-3 S cm-1 at 25 C and 98% RH | 25 C, 98% RH Text · Exact Reported | No verified corpus mapping | p. 41 · 3.4.1 |
| SecondaryFe3(THT)2(NH4)3 | charge mobility | ~220 cm2 V-1 s-1 | TRTS/Hall effect; semiconducting 2D MOF Text · Approximate | research_0001 | p. 22 · 2.3.3 |
| SecondaryNi3HITP2 | electrical conductivity | 150 S cm-1 | single crystal, 4-probe, room temperature; review Table 1 Table · Exact Reported | research_0005 | p. 10 · 2.2.1 · Table 1 |
| SecondaryNi3HITP2 | electrical conductivity | 40 S cm-1 | film, van der Pauw, room temperature; review Table 1 Table · Exact Reported | No verified corpus mapping | p. 10 · 2.2.1 · Table 1 |
| SecondaryNi3HITP2 | thermal conductivity | 0.21 W m-1 K-1 | thermoelectric MOF; room-temperature context Text · Exact Reported | research_0072 | p. 40 · 2.5.4 |
| SecondaryNi3HITP2 | normalised capacitance | ~18 microF cm-2 | EDLC electrode, 10000 cycles with 90% retention Text · Approximate | No verified corpus mapping | p. 29 · 2.5.2 |
| SecondaryNi3HITP2 | thermoelectric ZT | 1.19 x 10^-3 at room temperature | room temperature Text · Exact Reported | research_0072 | p. 40 · 2.5.4 |
| Secondaryoxidized Ni-BHT | electrical conductivity | 1.6 x 10^2 S cm-1 at 300 K | oxidized film/nanosheet, 300 K Text · Exact Reported | research_0361 | p. 23 · 2.4.2 |
| SecondaryTCNQ@Cu3(BTC)2 | electrical conductivity | 0.07 S cm-1 | film/device; guest@MOF Text · Exact Reported | research_0088 | p. 20 · 2.2.3 |
| SecondaryTCNQ@Cu3(BTC)2 | thermoelectric ZT | 7 x 10^-5 at 25 C | 25 C thin film Text · Exact Reported | research_0450 | p. 39 · 2.5.4 |
| SecondaryTCNQ@Cu3(BTC)2 | Seebeck coefficient | 375 microV K-1 | thin film thermoelectric measurement Text · Exact Reported | research_0450 | p. 39 · 2.5.4 |
| SecondaryZn2(TTFTB) | intrinsic charge mobility | 0.2 cm2 V-1 s-1 | FP-TRMC; pi-stacked MOF Text · Exact Reported | research_0030 | p. 17 · 2.2.2 |
| SecondaryZrP, (NH4)3[Zr(H2/3PO4)3] | anhydrous proton conductivity | 1.45 x 10^-3 S cm-1 at 180 C | 180 C, anhydrous Text · Exact Reported | No verified corpus mapping | p. 52 · 3.4.3 |
| SecondaryZrP, (NH4)3[Zr(H2/3PO4)3] | proton conductivity | 1.21 x 10^-2 S cm-1 at 90 C and 95% RH | 90 C, 95% RH Text · Exact Reported | No verified corpus mapping | p. 52 · 3.4.3 |
Research gaps
Open questions are presented as review-author priorities, not conclusions from the primary database.
Sample quality and defects
HighHigh-quality single crystals and single-domain films are scarce, especially for 2D conductive MOFs, limiting intrinsic transport measurements.
Proposed direction: Develop synthesis and characterisation routes for defect-controlled crystals/films.
p. 54 · 4. Challenges and perspectives
Controlled doping
MediumDoped conductive MOFs need better control of dopant level and robustness.
Proposed direction: Develop moderate, reversible and structurally benign doping strategies.
p. 20 · 2.2.3
Intrinsic electronic transport mechanisms
HighFundamental understanding of electron-lattice interactions and charge pathways in MOFs remains limited.
Proposed direction: Combine high-quality experiments with precise theoretical calculations to resolve mechanisms.
p. 2 · 1. Introduction
Measurement comparability
HighConductivity values vary with measurement method, geometry, contact resistance and sample morphology.
Proposed direction: Report current/voltage windows, geometry, contact scheme, anisotropy and sample quality consistently.
p. 20 · 2.3
PEMFC deployment
HighMOF proton conductors still need simultaneous high conductivity, stability, mechanical strength and membrane processability.
Proposed direction: Evaluate repeated hydration/dehydration, high-temperature operation and mechanical durability.
p. 55 · 4. Challenges and perspectives
Anhydrous proton conduction
HighFew MOFs combine high-temperature tolerance above 200 C with proton conductivity above 0.01 S cm-1.
Proposed direction: Design nonvolatile carrier systems and thermally stable frameworks for Nafion alternatives.
p. 51 · 3.4.2
Proton-conductor processability
HighMost proton-conductive MOFs remain pellets or single crystals rather than practical membranes.
Proposed direction: Advance oriented films, membranes and mixed-matrix approaches while preserving conductivity.
p. 52 · 3.4.4
Stability of electronic MOFs
HighConductive MOFs can lack robustness under heat, pressure and acid/base conditions.
Proposed direction: Prioritise robust frameworks and stability testing under device-relevant conditions.
p. 54 · 4. Challenges and perspectives
Host-guest sensing mechanisms
MediumConductive MOF chemiresistor mechanisms and host-guest interactions are not fully characterised.
Proposed direction: Use in situ spectroscopy, computation and systematic analyte studies to identify adsorption-to-transport links.
p. 28 · 2.5.1
Conductivity-porosity trade-off
MediumMany highly conductive MOFs have surface areas below 1000 m2 g-1, challenging multifunctional porous conductors.
Proposed direction: Design frameworks balancing accessible surface area with high orbital overlap and carrier density.
p. 54 · 4. Challenges and perspectives
Cited-study map
Mappings show which printed review references have a verified counterpart in the frozen primary corpus.
Show 40 cited-study records
| Reference | Study | Role and context | Corpus mapping |
|---|---|---|---|
| Ref. 132009 | Electroconductive porous coordination polymer Cu[Cu(pdt)2] composed of donor and acceptor building units | historical_origin · through_bond_transportReview identifies this as one of the earliest electronically conductive MOF/PCP reports and a through-bond example. | research_0201 |
| Ref. 232009 | Rational designs for highly proton-conductive metal-organic frameworks | proton_benchmark · rational_designUsed for rational incorporation of proton carriers and two-dimensional H-bond networks in oxalate MOFs. | research_0220 |
| Ref. 252009 | High proton conductivity of one-dimensional ferrous oxalate dihydrate | proton_benchmarkUsed as a water-assisted oxalate proton conductor benchmark. | Unmapped |
| Ref. 462012 | New porous crystals of extended metal-catecholates | material_family · benchmarkReview uses this study for extended metal-catecholate/HHTP conductive MOFs. | Unmapped |
| Ref. 472014 | High electrical conductivity in Ni3(2, 3, 6, 7, 10, 11-hexaiminotriphenylene)2, a semiconducting metal-organic graphene analogue | material_family · benchmarkCited for HITP-based conductive MOFs and conductivity/BET values in Table 1. | Unmapped |
| Ref. 492012 | High charge mobility in a tetrathiafulvalene-based microporous metal-organic framework | transport_benchmark · pi_stackKey through-space/pi-stacked MOF mobility example. | research_0030 |
| Ref. 532019 | Integration of a (-Cu-S-)n plane in a metal-organic framework affords high electrical conductivity | benchmark · metal_sulfur_planeExample of 2D Cu-S plane enabling high single-crystal conductivity. | research_0104 |
| Ref. 572013 | pi-conjugated nickel bis(dithiolene) complex nanosheet | historical_development · material_familyReview presents Ni-BHT as an early pi-conjugated nickel bis(dithiolene) nanosheet and metallic-state platform. | Unmapped |
| Ref. 612015 | A two-dimensional pi-d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour | benchmark · thin_film_deviceCentral high-conductivity Cu-BHT thin-film and FET mobility case. | research_0006 |
| Ref. 622018 | Highly conducting neutral coordination polymer with infinite two-dimensional silver-sulfur networks | benchmark · metallic_stateSilver-sulfur network with high conductivity and metallic features. | research_0735 |
| Ref. 642017 | Metallic conductivity in a two-dimensional cobalt dithiolene metal-organic framework | metallic_state · material_familyReview uses this for metallic conductivity in triphenylene dithiolene MOFs. | Unmapped |
| Ref. 652019 | Room temperature metallic conductivity in a metal-organic framework induced by oxidation | metallic_state · material_familyReview uses this for Fe-HTTP metallic-like behaviour induced by oxidation. | Unmapped |
| Ref. 662017 | Porous field-effect transistors based on a semiconductive metal-organic framework | thin_film_device · benchmarkAir-liquid interfacial Ni3HITP2 film and porous FET benchmark. | research_0015 |
| Ref. 672018 | Large-Area preparation of crack-free crystalline microporous conductive membrane to upgrade high energy lithium-sulfur batteries | thin_film_device · battery_separatorLarge-area conductive MOF membrane separator for Li-S batteries. | Unmapped |
| Ref. 752017 | Layer-by-layer assembled conductive metal-organic framework nanofilms for room-temperature chemiresistive sensing | synthesis_strategy · thin_film_deviceLayer-by-layer liquid-phase epitaxy for oriented conductive MOF films. | research_0115 |
| Ref. 762019 | Oriented thin films of electroactive triphenylene catecholate-based two-dimensional metal-organic frameworks | synthesis_strategy · thin_film_deviceVapour-assisted conversion strategy for oriented M-CAT films. | Unmapped |
| Ref. 822017 | Signature of metallic behavior in the metal-organic frameworks M3(hexaiminobenzene)2 (M = Ni, Cu) | benchmark · metallic_stateHIB benchmark for metallic behaviour in M3HIB2 frameworks. | Unmapped |
| Ref. 862019 | [Cu3(C6Se6)]n: the first highly conductive 2D pi-d conjugated coordination polymer based on benzenehexaselenolate | benchmark · selenolate_linkerBenzenehexaselenolate 2D pi-d conductive polymer benchmark. | Unmapped |
| Ref. 892019 | Single crystals of electrically conductive two-dimensional metal-organic frameworks: structural and electrical transport properties10.1021/acscentsci.9b01006 | benchmark · single_crystal_transportSingle-crystal 2D conductive MOF transport benchmark. | research_0005 |
| Ref. 992015 | Electronic conductivity, ferrimagnetic ordering, and reductive insertion mediated by organic mixed-valence in a ferric semiquinoid metal-organic framework | mixed_valence · magnetic_semiconductorMixed-valence semiquinoid MOF with conductivity and magnetic ordering. | research_0186 |
| Ref. 1002018 | Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework | mixed_valence · benchmarkReview uses this for Fe mixed-valence tuning and conductivity enhancement. | Unmapped |
| Ref. 1012010 | Conductivity, doping, and redox chemistry of a microporous dithiolene-based metal-organic framework | doped_mof · through_bond_transportIodine oxidation/doping example in a microporous dithiolene MOF. | research_0203 |
| Ref. 1032019 | A highly crystalline anthracene-based MOF-74 series featuring electrical conductivity and luminescence | pi_stack · material_familyAnthracene MOF-74 pi-stacking route to enhanced conductivity. | research_0165 |
| Ref. 1072018 | Electron delocalization and charge mobility as a function of reduction in a metal-organic framework | doped_mof · mobility_benchmarkPotassium-reduced Fe2(BDP)3 example with anisotropic conductivity and mobility increase. | research_0029 |
| Ref. 1092014 | Tunable electrical conductivity in metal-organic framework thin-film devices | guest_mof · thermoelectric_benchmarkGuest-induced conductivity and thermoelectric benchmark in HKUST-1. | research_0088 |
| Ref. 1142014 | Redox control and high conductivity of nickel bis(dithiolene) complex pi-nanosheet: a potential organic two-dimensional topological insulator | redox_control · topological_insulatorRedox-controlled Ni-BHT conductivity and potential topological-insulator context. | research_0361 |
| Ref. 1172018 | High-mobility band-like charge transport in a semiconducting two-dimensional metal-organic framework | mobility_benchmark · band_transportRecord band-like mobility case from TRTS/Hall measurements. | research_0001 |
| Ref. 1432015 | Chemiresistive sensor arrays from conductive 2D metal-organic frameworks | application_context · sensing2D conductive MOF chemiresistive sensor arrays. | research_0145 |
| Ref. 1572017 | Conductive MOF electrodes for stable supercapacitors with high areal capacitance | application_context · supercapacitorConductive MOF electrode with high areal capacitance in EDLCs. | Unmapped |
| Ref. 1612018 | Multielectron-Transfer-based rechargeable energy storage of two-dimensional coordination frameworks with non-innocent ligands | application_context · batteryNon-innocent ligand 2D framework for Li-ion cathode. | Unmapped |
| Ref. 1872016 | Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2 | application_context · ORRNi3HITP2 ORR electrocatalysis benchmark/context. | research_0003 |
| Ref. 2192015 | Thin film thermoelectric metal-organic framework with high seebeck coefficient and low thermal conductivity | thermoelectric_benchmarkThin-film thermoelectric MOF benchmark. | research_0450 |
| Ref. 2202017 | A microporous and naturally nanostructured thermoelectric metal-organic framework with ultralow thermal conductivity | thermoelectric_benchmarkMicroporous Ni3HITP2 thermoelectric benchmark. | research_0072 |
| Ref. 2462014 | Control of crystalline proton-conducting pathways by water-induced transformations of hydrogen-bonding networks in a metal-organic framework | proton_pathway · water_adsorptionWater-induced phase and H-bond pathway control in oxalate MOF. | research_0324 |
| Ref. 2522014 | High proton conduction at above 100 C mediated by hydrogen bonding in a lanthanide metal-organic framework | proton_benchmark · high_temperatureHumidity-independent high-temperature lanthanide oxalate proton conductor. | Unmapped |
| Ref. 2592017 | Straightforward loading of imidazole molecules into metal organic framework for high proton conduction | proton_guestImidazole-loaded MOF with guest-assisted proton conduction. | Unmapped |
| Ref. 2612017 | A flexible metal-organic framework with a high density of sulfonic acid sites for proton conduction | proton_benchmark · sulfonic_acid_sitesFlexible sulfonic-acid-rich MOF proton conductor. | Unmapped |
| Ref. 2842018 | Unique proton transportation pathway in a robust inorganic coordination polymer leading to intrinsically high and sustainable anhydrous proton conductivity | proton_benchmark · fuel_cellRobust inorganic coordination polymer with humidified and anhydrous proton transport and fuel-cell test. | Unmapped |
| Ref. 2902013 | Superprotonic conductivity in a highly oriented crystalline metal-organic framework nanofilm | proton_film · benchmarkHighly oriented proton-conductive MOF nanofilm benchmark. | Unmapped |
| Ref. 2992016 | Glass formation of a coordination polymer crystal for enhanced proton conductivity and material flexibility | glass_state · proton_benchmarkGlass-state coordination polymer proton-conductivity benchmark. | Unmapped |