Conductive Metal-organic Frameworks Research Articles

Gas‐Induced Electrical and Magnetic Modulation of Two‐Dimensional Conductive Metal–Organic Framework

AbstractControlled modulation of electronic and magnetic properties in stimuli‐responsive materials provides valuable insights for the design of magnetoelectric or multiferroic devices. This paper demonstrates the modulation of electrical and magnetic properties of a semiconductive, paramagnetic metal−organic framework (MOF) Cu3(C6O6)2 with small gaseous molecules, NH3, H2S, and NO. This study merges chemiresistive and magnetic tests to reveal that the MOF undergoes simultaneous changes in electrical conductance and magnetization that are uniquely modulated by each gas. The features of response, including direction, magnitude, and kinetics, are modulated by the physicochemical properties of the gaseous molecules. This study advances the design of multifunctional materials capable of undergoing simultaneous changes in electrical and magnetic properties in response to chemical stimuli.

Aliovalent Substitution Tunes Physical Properties in a Conductive Bis(dithiolene) Two-Dimensional Metal-Organic Framework.

Two-dimensional conductive metal-organic frameworks have emerged as promising electronic materials for applications in (opto)electronic, thermoelectric, magnetic, electrocatalytic, and energy storage devices. Many bottom-up or postsynthetic protocols have been developed to isolate these materials or further modulate their electronic properties. However, some methodologies commonly used in classic semiconductors, notably, aliovalent substitution, are conspicuously absent. Here, we demonstrate how aliovalent Fe(III) to Ni(II) substitution enables the isolation of a Ni bis(dithiolene) material from a previously reported Fe analogue. Detailed characterization supports the idea that aliovalent substitution of Fe(III) to Ni(II) results in an in situ oxidation of the organic dithiolene linker. This substitution-induced redox tuning modulates the electronic properties in the system, leading to higher electrical conductivity and Hall mobility but slightly lower carrier densities and weaker antiferromagnetic interactions. Moreover, this aliovalent substitution improves the material's electrochemical stability and thus enables pseudocapacitive behavior in the Ni material. These results demonstrate how classic aliovalent substitution strategies in semiconductors can also be leveraged in conductive MOFs and add further support to this class of compounds as emerging electronic materials.

Robust Chemiresistive Behavior in Conductive Polymer/MOF Composites.

Metal-organic frameworks (MOFs) are promising materials for gas sensing but are often limited to single-use detection. We demonstrate a hybridization strategy synergistically deploying conductive MOFs (cMOFs) and conductive polymers (cPs) as two complementary mixed ionic-electronic conductors in high-performing stand-alone chemiresistors. Our work presents significant improvement in i) sensor recovery kinetics, ii) cycling stability, and iii) dynamic range at room temperature. We demonstrate the effect of hybridization across well-studied cMOFs based on 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7,10,11-hexaiminotripphenylene (HITP) ligands with varied metal nodes (Co, Cu, Ni). We conduct a comprehensive mechanistic study to relate energy band alignments at the heterojunctions between the MOFs and the polymer with sensing thermodynamics and binding kinetics. Our findings reveal that hole enrichment of the cMOF component upon hybridization leads to selective enhancement in desorption kinetics, enabling significantly improved sensor recovery at room temperature, and thus long-term response retention. This mechanism was further supported by density functional theory calculations on sorbate-analyte interactions. We also find that alloying cPs and cMOFs enables facile thin film co-processing and device integration, potentially unlocking the use of these hybrid conductors in diverse electronic applications. This article is protected by copyright. All rights reserved.

Two-Dimensional Conjugated Metal-Organic Frameworks with a Ring-in-Ring Topology and High Electrical Conductance.

Electrically conducting two-dimensional (2D) metal-organic frameworks (MOFs) have garnered significant interest due to their remarkable structural tunability and outstanding electrical properties. However, the design and synthesis of high-performance materials face challenges due to the limited availability of specific ligands and pore structures. In this study, we have employed a novel highly branched D3h symmetrical planar conjugated ligand, dodechydroxylhexabenzotrinaphthylene (DHHBTN) to fabricate a series of 2D conductive MOFs, named M-DHHBTN (M = Co, Ni, and Cu). This new family of MOFs offers two distinct types of pores, elevating the structural complexity of 2D conductive MOFs to a more advanced level. The intricate tessellation patterns of the M-DHHBTN are elucidated through comprehensive analyses involving powder X-ray diffraction, theoretical simulations, and high-resolution transmission electron microscope. Optical-pump terahertz-probe spectroscopic measurements unveiled carrier mobility in DHHBTN-based 2D MOFs spanning from 0.69 to 3.10 cm2 V-1 s-1. Among M-DHHBTN famility, Cu-DHHBTN displayed high electrical conductivity reaching 0.21 S cm-1 at 298 K with thermal activation behavior. This work leverages the "branched conjugation" of the ligand to encode heteroporosity into highly conductive 2D MOFs, underscoring the significant potential of heterogeneous double-pore structures for future applications.

Triazacoronene‐Based 2D Conductive Metal–Organic Framework for High‐Capacity Lithium Storage

Abstract2D conductive metal–organic frameworks (2D c‐MOFs) have attracted increasing attention as promising electrode materials for rechargeable batteries due to their designable periodic motifs, large specific surface areas, and prominent electrical conductivity. However, the development of 2D c‐MOF electrode materials with functionality remains a significant challenge because of the limited electroactive ligand motifs available. Herein, a hexahydroxy‐substituted triazacoronene ligand (6OH‐TAC) is deliberately designed and synthesized, which coordinates with Cu2+ ions to form an unprecedented 2D c‐MOF (Cu‐TAC) with functionality sites of efficient lithium storage. The synergistic effect of TAC and CuO4 enables Cu‐TAC as an anode for lithium‐ion batteries with a superior reversible capacity of 772.4 mAh g−1 at 300 mA g−1, remarkable rate performance, and outstanding long‐term cyclability (83% capacity retention at 300 mA g−1 for 600 cycles). These metrics outperform almost all 2D c‐MOF‐based electrodes, shedding light on new opportunities for energy storage devices.

Acid-Dependent Charge Transport in a Solution-Processed 2D Conductive Metal-Organic Framework.

The development of conductive metal-organic frameworks (MOFs) presents a unique challenge in materials chemistry because it is unclear how to dope them. Here, we demonstrate that the inclusion of pendant amines on hexahydroxytriphenylene linkages results in two-dimensional (2D) polycrystalline frameworks Cu3(HHTATP)2, isostructural to its Cu3(HHTP)2 parent, and exhibits the highest electrical conductivity of 1.21 S/cm among 2D MOFs featuring CuO4 metal nodes. Moreover, the bulk material can be treated with acid, resulting in a protonation-dependent increase in the conductivity. By spin-coating the acidic solution, we fabricated large-area thin films and collectively demonstrated an intuitive route to solution-processable, dopable, conductive MOFs.

Photocatalytic Hydrogen Peroxide Production through Functionalized Semiconductive Metal-Organic Frameworks.

Hydrogen peroxide (H2O2) holds significance as a vital chemical with the potential to serve as an energy carrier. Compared with the conventional anthraquinone process, photocatalytic H2O2 production has emerged as an appealing alternative because of its energy efficiency and environmental sustainability. However, the existing photocatalysts suffer from low catalytic efficiency, limited tunability of optical properties, and reliance on sacrificial agents due to high energy loss caused by inefficient charge separation. Therefore, developing catalysts with tunable optical properties and efficient charge separation is desirable. In this work, we introduce postsynthetic functionalization into an electrically conductive metal-organic framework, namely, DPT-MOF. Leveraging DPT (3,6-di(4-pyridyl)-1,2,4,5-tetrazine) as a pillar ligand, we exploited click-type chemistry to manipulate band position and charge separation efficiency, allowing for photocatalytic nonsacrificial H2O2 production. Notably, the fluorine-functionalized MOF exhibited the highest H2O2 production rate of 1676 μmol g-1 h-1 under visible light in O2-saturated water among our other samples. This high production rate is attributed to the tuned electronic structure and prolonged charge lifetime facilitated by the fluorine groups. This work highlights the effectiveness of postsynthetic methodology in tuning optical properties, opening a promising avenue for advancing the field of semiconductive MOF-based photocatalysis.

Gas-Induced Electrical and Magnetic Modulation of Two-Dimensional Conductive Metal-Organic Framework.

Controlled modulation of electronic and magnetic properties in stimuli-responsive materials provides valuable insights for the design of magnetoelectric or multiferroic devices. This paper demonstrates the modulation of electrical and magnetic properties of a semiconductive, paramagnetic metal-organic framework Cu3(C6O6)2 with small gaseous molecules, NH3, H2S, and NO. This study merges chemiresistive and magnetic tests to reveal that the MOF undergoes simultaneous changes in electrical conductance and magnetization that are uniquely modulated by each gas. The features of response, including direction, magnitude, and kinetics, are modulated by the physicochemical properties of the gaseous molecules. This study advances the design of multifunctional materials capable of undergoing simultaneous changes in electrical and magnetic properties in response to chemical stimuli.

Radially oriented Ni3(HITP)2 microspheres as high-performance anode materials for Li-ion capacitors with exceptional energy density and cycling stability

Developing of high-energy, high-power-density energy storage devices is challenging. Despite being promising electrode materials for these devices, metal–organic frameworks (MOFs) have poor electrical conductivity and weak ligand–metal coordination. Here, the highly conductive MOF, Ni3(HITP)2, which comprises radially oriented microspheres, is adopted as the anode for Li-ion capacitors (LICs). The half-cell demonstrates high reversible capacity (834 mAh g−1) at 50 mA g−1 with minimal capacity reduction, attributable to the participation of C and N functional groups of the ligand and Ni2+ in the redox reactions during charge/discharge. Especially, density functional theory calculations show that, apart from the inner rings, participation of the outer rings of Ni3(HITP)2 in the redox reactions is responsible for the high Li + storage capacity. An LIC with a Ni3(HITP)2 anode and commercial activated-carbon cathode demonstrates high specific energy (120.7 Wh kg−1) at 89.2 W kg−1, nearly twice as high as that of graphite-based LICs, and maintains specific energy of 25.8 Wh kg−1 even at high specific power (7.16 kW kg−1), over the range 1–4.4 V, along with high cycling stability (76% capacity retention over 10000 cycles). The proposed radially oriented Ni3(HITP)2 microspheres have potential for application as the anode in high-performance energy storage devices.

Thermal‐Conductive MOFs@BN Self‐Supporting Foams for Synchronously Boosting CO2 Adsorption/Desorption

AbstractSynchronous boosting adsorption and desorption efficiency is a great challenge for CO2 adsorption capture, especially for metal–organic frameworks (MOFs) having high adsorption uptakes. Herein, a novel “self‐supporting foam” strategy is proposed to fabricate a thermally conductive MOFs@boron nitride nanosheets (BNNS) composite foam (MOFs@BNNS‐PEI) via polyethyleneimine (PEI) cross‐linkage. The “rebar” BNNS and the “aggregate” MOFs are packed against each other to form a self‐supporting structure, effectively reducing the reliance on polymers to maintain high MOFs loading. Furthermore, this approach enables the successful fabrication of three different types of typical MOFs, including HKUST‐1, MIL‐100(Fe), and ZIF‐8. This unique design maintains a high specific surface area (SSA) of the MOFs foam and generates nitrogen‐rich microporosity contributing to CO2 adsorption. Additionally, PEI serves as a thermal bridge to reduce the interfacial thermal resistance between BNNS and MOFs, accelerating the thermal desorption of CO2 within the MOFs foam. Benefiting from these advantages, the MOFs@BNNS‐PEI exhibits a higher CO2 adsorption capacity (1.35–1.42 times that of pure MOFs) and a significant increase in the desorption rate for CO2 (5.0–5.7 times that of pure MOFs). Thus, the thermally conductive MOFs foam can be a viable option for efficient CO2 capture in practical applications.

Two‐Dimensional Conjugated Metal–Organic Frameworks with a Ring‐in‐Ring Topology and High Electrical Conductance

Electrically conducting two‐dimensional (2D) metal‐organic frameworks (MOFs) have garnered significant interest due to their remarkable structural tunability and outstanding electrical properties. However, the design and synthesis of high‐performance materials face challenges due to the limited availability of specific ligands and pore structures. In this study, we have employed a novel highly branched D3h symmetrical planar conjugated ligand, dodechydroxylhexabenzotrinaphthylene (DHHBTN) to fabricate a series of 2D conductive MOFs, named M‐DHHBTN (M = Co, Ni, and Cu). This new family of MOFs offers two distinct types of pores, elevating the structural complexity of 2D conductive MOFs to a more advanced level. The intricate tessellation patterns of the M‐DHHBTN are elucidated through comprehensive analyses involving powder X‐ray diffraction, theoretical simulations, and high‐resolution transmission electron microscope. Optical‐pump terahertz‐probe spectroscopic measurements unveiled carrier mobility in DHHBTN‐based 2D MOFs spanning from 0.69 to 3.10 cm2 V‐1 s‐1. Among M‐DHHBTN famility, Cu‐DHHBTN displayed high electrical conductivity reaching 0.21 S cm−1 at 298 K with thermal activation behavior. This work leverages the “branched conjugation” of the ligand to encode heteroporosity into highly conductive 2D MOFs, underscoring the significant potential of heterogeneous double‐pore structures for future applications.

Highly electrically conductive MOF/conducting polymer nanocomposites toward tunable electromagnetic wave absorption

Metal-organic frameworks (MOFs) have attracted significant interest as self-templates and precursors for the synthesis of carbon-based composites aimed at electromagnetic wave (EMW) absorption. However, the utilization of high-temperature treatments has introduced uncertainties regarding the compositions and microstructures of resulting derivatives. Additionally, complete carbonization has led to diminished yields of the produced carbon composites, significantly limiting their practical applications. Consequently, the exploration of pristine MOF-based EMW absorbers presents an intriguing yet challenging endeavor, primarily due to inherently low electrical conductivity. In this study, we showcase the utilization of structurally robust Zr-MOFs as scaffolds to build highly conductive Zr-MOF/PPy composites via an inner-outer dual-modification approach, which involves the production of conducting polypyrrole (PPy) both within the confined nanoporous channels and the external surface of Zr-MOFs via post-synthetic modification. The interconnection of confined PPy and surface-lined PPy together leads to a consecutive and extensive conducting network to the maximum extent. This therefore entails outstanding conductivity up to ∼14.3 S cm−1 in Zr-MOF/PPy composites, which is approximately 1-2 orders of magnitude higher than that for conductive MOF nanocomposites constructed from either inner or outer modification. Benefiting from the strong and tunable conduction loss, as well as the induced dielectric polarization originated from the porous structures and MOF-polymer interfaces, Zr-MOF/PPy exhibits excellent microwave attenuation capabilities and a tunable absorption frequency range. Specifically, with only 15 wt.% loading, the minimum reflection loss (RLmin) can reach up to -67.4 dB, accompanied by an effective absorption bandwidth (EAB) extending to 6.74 GHz. Furthermore, the microwave absorption characteristics can be tailored from the C-band to the Ku-band by adjusting the loading of PPy. This work provides valuable insights into the fabrication of conductive MOF composites by presenting a straightforward pathway to enhance and regulate electrical conduction in MOF-based nanocomposites, thus paving a way to facilely fabricate pristine MOF-based microwave absorbers.

On-liquid-gallium surface synthesis of ultrasmooth thin films of conductive metal–organic frameworks

On-liquid-gallium surface synthesis of ultrasmooth thin films of conductive metal–organic frameworks

Electro-Induced Phase Transformation of a Conductive Metal-Organic Framework Film for Nonlinear Optical Switching.

Achieving metal-organic frameworks (MOFs) with nonlinear optical (NLO) switching is profoundly important. Herein, the conductive MOFs Cu-TCNQ phase I (Ph-I) and phase II (Ph-II) films were prepared using the liquid-phase-epitaxial layer-by-layer spin-coating method and steam heating method, respectively. Electronic experiments showed that the Ph-II film could be changed into the Ph-I film under an applied electric field. The third-order NLO results revealed that the Ph-I film had a third-order nonlinear reverse saturation absorption (RSA) response and the Ph-II film displayed a third-order nonlinear saturation absorption (SA) response. With increases in the heating time and applied voltage, the third-order NLO response realized the reversible transition between SA and RSA. The theoretical calculations indicated that Ph-I possessed more interlayer charge transfer, resulting in a third-order nonlinear RSA response that was stronger than that of Ph-II. This work applies phase-transformed MOFs to third-order NLO switching and provides new insights into the nonlinear photoelectric applications of MOFs.

Conductive Metal-Organic Framework Grown on the Nickel-Based Hydroxide to Realize High-Performance Electrochemical Glucose Sensing.

Glucose holds significant importance in disease diagnosis as well as beverage quality monitoring. The high-efficiency electrochemical sensor plays a crucial role in the electrochemical conversion technology. Ni(OH)2 nanosheets are provided with high specific surface area and redox activity that are widely used in electrochemistry. Conductive metal-organic frameworks (cMOFs) perfectly combine the structural controllability of organic materials with the long-range ordering of inorganic materials that possess the characteristic of high electron mobility. Based on the above considerations, the combination of Ni(OH)2 and Ni-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) as an electrode modification material is designed to enhance electrochemical performance. In this work, to improve glucose detection, a sequence of Ni(OH)2@NiCo-HHTP and NiM-LDH@Ni-HHTP (M = Co2+, Mn2+, Cu2+, LDH = layered double hydroxide) are successfully synthesised by doping metals into Ni-HHTP and Ni(OH)2, respectively. As a result, NiCu-LDH@Ni-HHTP showed the best excellent glucose detection sensitivity.

Electrochemical Capacitance Traces with Interlayer Spacing in Two‐dimensional Conductive Metal–Organic Frameworks

AbstractElectrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni3(HIR3‐TAT)2 (TAT=triazatruxene; R=H, Et, n‐Bu, n‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni3(HIH3‐TAT)2 to Ni3(HIBu3‐TAT)2. Partial exfoliation of Ni3(HIBu3‐TAT)2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC.

Electrochemical Capacitance Traces with Interlayer Spacing in Two-dimensional Conductive Metal-Organic Frameworks.

Electrically conductive metal-organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double-layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure-function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene-based 2D layered conductive MOFs with variable alkyl functional groups, Ni3(HIR3-TAT)2 (TAT=triazatruxene; R=H, Et, n-Bu, n-Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in-plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double-layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni3(HIH3-TAT)2 to Ni3(HIBu3-TAT)2. Partial exfoliation of Ni3(HIBu3-TAT)2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox-active sites may motivate further design and engineering of electrode materials for EC.

De Novo Design and Facile Synthesis of Highly Crystalline 2D Conductive Metal-Organic Frameworks: A "Rotor-Stator" Strategy.

Two-dimensional conductive metal-organic frameworks (2D c-MOFs), which feature high electrical conductivity and large charge carrier mobility, hold great promise in electronics and optoelectronics. Nevertheless, the limited solubility of commonly used planar ligands inevitably brings challenges in synthesis and purification and causes laborious coordination conditions for screening. Moreover, most reported 2D c-MOFs are polycrystalline powders with relatively low crystallinity and irregular morphology, hindering the unveiling of the detailed structure-function relationship. Herein, we developed a "rotor-stator" molecular design strategy to construct 2D c-MOFs using a delicately designed nonplanar biscarbazole ligand (8OH-DCB). Benefiting from the special "rotor-stator" structure of the ligand, crystals of Cu-DCB-MOF were successfully prepared, allowing for the precise determination of their crystal structure. Interestingly, the crystals of Cu-DCB-MOF can be obtained in various organic solvents, indicating excellent solvent compatibility. The versatility of the "rotor-stator" molecular design strategy was further demonstrated by another two new ligands with a "rotor-stator" structure, and afford corresponding 2D c-MOF crystals (Cu-DCBT-MOF and Cu-DCBBT-MOF). The current work presents a facile approach toward the rational design and direct construction of highly crystalline 2D c-MOFs using nonplanar ligands.

Triggering Anodic Luminol Electrochemiluminescence through Electrostatic Interactions: An Innovative Approach Utilizing Conductive Metal–Organic Framework Co-HHTP

Triggering Anodic Luminol Electrochemiluminescence through Electrostatic Interactions: An Innovative Approach Utilizing Conductive Metal–Organic Framework Co-HHTP

High-Performance Ni3(HHTP)2 Film-Based Flexible Field-Effect Transistor Gas Sensors.

Conductive metal-organic frameworks (MOFs) have received increasing attention in recent years and present high application potential as sensing elements in electronic sensors. In this study, flexible field-effect transistor (FET) sensors based on conductive MOF, i.e., Ni3(HHTP)2, have been constructed. This Ni3(HHTP)2 sensor has high sensitivity (detection limit of 56 ppb) as well as superior selectivity for NO2 detection at room temperature, which is demonstrated by accurate gas detection in a mixed gas atmosphere. Moreover, by employing six flexible substrates, i.e., polyimide (PI), tape (PET), facemask, paper cup, tablecloth, and take-out bag (textile), we successfully demonstrate the universality of the flexible sensor construction with conductive MOF as sensing film on various substrates. This study of conductive MOF-based flexible electronic sensors offers a new opportunity for a wide range of sensing applications with wearable and portable electronic devices.