Conductive Metal-organic Frameworks Research Articles

Dual active sites of N-rich triptycene-based 2D conductive metal–organic framework with 3D extended structures in high-performance lithium-ion batteries

Two-dimensional conductive metal–organic frameworks (2D c-MOFs) have attracted much attention in energy storage due to their special conjugated structures and electronic properties. However, the insufficient exposure of the active site due to layer stacking and the non-redox-active ligand molecules are detrimental to the specific capacity. In this study, a nitrogen-rich triptycene-based 2D c-MOF (M−TH5) with vertical extension was synthesized for the first time as an anode material. The triptycene-based ligand structure confers a 3D extension of the MOF alleviating the stacking problem and allowing full exposure of its active site. Furthermore, M−TH5 has a dual redox center (TH5 and MO4 units containing N sites), which can provide additional lithium storage sites. Expectedly, Mn-TH5 compared to Co-TH5 exhibits higher initial capacity (486.3 mAh·g−1 at 100 mA·g−1) and excellent long-term cycling stability (capacity retention of 91.9 % at 500 mA·g−1 after 400 cycles). Experimentally and computationally, the flower-like morphology and the nitrogen-rich system with three-dimensional (3D) expansion have more exposed active sites to facilitate Li+/e- transport. This finding provides new opportunities to improve anode material properties by integrating multiple active centers into 2D c-MOF

A Flexible Smart Healthcare Platform Conjugated with Artificial Epidermis Assembled by Three-Dimensionally Conductive MOF Network for Gas and Pressure Sensing

The rising flexible and intelligent electronics greatly facilitate the noninvasive and timely tracking of physiological information in telemedicine healthcare. Meticulously building bionic-sensitive moieties is vital for designing efficient electronic skin with advanced cognitive functionalities to pluralistically capture external stimuli. However, realistic mimesis, both in the skin’s three-dimensional interlocked hierarchical structures and synchronous encoding multistimuli information capacities, remains a challenging yet vital need for simplifying the design of flexible logic circuits. Herein, we construct an artificial epidermal device by in situ growing Cu3(HHTP)2 particles onto the hollow spherical Ti3C2Tx surface, aiming to concurrently emulate the spinous and granular layers of the skin’s epidermis. The bionic Ti3C2Tx@Cu3(HHTP)2 exhibits independent NO2 and pressure response, as well as novel functionalities such as acoustic signature perception and Morse code-encrypted message communication. Ultimately, a wearable alarming system with a mobile application terminal is self-developed by integrating the bimodular senor into flexible printed circuits. This system can assess risk factors related with asthmatic, such as stimulation of external NO2 gas, abnormal expiratory behavior and exertion degrees of fingers, achieving a recognition accuracy of 97.6% as assisted by a machine learning algorithm. Our work provides a feasible routine to develop intelligent multifunctional healthcare equipment for burgeoning transformative telemedicine diagnosis.

Tetrahydroxybenzoquinone-Based Two-Dimensional Conductive Metal–Organic Framework via π-d Conjugation Modulation for Enhanced Oxygen Evolution Reaction

Tetrahydroxybenzoquinone-Based Two-Dimensional Conductive Metal–Organic Framework via π-d Conjugation Modulation for Enhanced Oxygen Evolution Reaction

Molecular-Level Pore Tuning in 2D Conductive Metal-Organic Frameworks for Advanced Supercapacitor Performance.

Two-dimensional (2D) electrically conductive metal-organic frameworks (MOFs) have emerged as viable candidates for active electrode materials in supercapacitors due to their high electrical conductivity, high specific surface area, and intrinsic redox-active sites. Despite their promising electrochemical performance, their pseudocapacitive behavior via fast and reversible charge transfer reactions remains yet to be fully exploited. Here, we investigate the electrochemical energy storage mechanism of Cu3(HHTATP)2 (HHTATP = 2,3,6,7,10,11-hexahydroxy-1,5,9-triaminotriphenylene), a 2D conductive MOF featuring characteristic redox-active pendant aromatic amines. Cu3(HHTATP)2 exhibited pseudocapacitive charge storage with an average gravimetric capacitance of 340 ± 15 F g-1 at a discharge rate of 0.2 A g-1 and maintained a capacitance retention over 90% after 7000 galvanostatic cycles at 5 A g-1. The polar pendant amines not only enhanced capacitance via additional amine/imine redox activity but also reduced interfacial charge transfer resistance through modified electrode-electrolyte interactions. These results highlight the potential of molecular-level pore environment tuning as a strategic approach in materials design for energy storage applications.

Conductive metal-organic framework for ppb-concentration and highly selective SAW hydrogen sulfide sensing at room temperature

Hydrogen sulfide (H2S) sensing is utilized for monitoring the concentration in environment protection and industrial process control, of which high selectivity and ppb detection limit are required. Here, a ppb-concentration and highly selective surface acoustic wave (SAW) H2S sensing has been developed with the Cu3(HHTP)2 MOFs conductive metal-organic frameworks (MOFs), which have been synthesized by connecting Cu2+ with the organic ligands via hydrothermal process. Typically, as-prepared Cu3(HHTP)2 MOFs take on shapes including nanoparticles and nanorods. Beneficially, the SAW H2S sensing presents excellent selectivity to H2S and enables to detection of H2S as low as 6 ppb at room temperature (∼ 26 °C). Remarkably, the SAW sensor prototypes exhibit high sensitivity (0.02 mV/ppb) to 50–2000 ppb H2S, fast response (T90: 281 s) and 46 day-long stability at room temperature. Theoretically, such excellent H2S SAW sensing performance might be attributed to the interaction between Cu ions and H2S molecules and the strong acoustoelectric effect of SAW. Practically, our ppb-concentration and highly selective H2S SAW sensing have the potential in the real-time detection of H2S.

Diradicals as Topological Charge Carriers in Metal-Organic Toy Model Pt3(HIB)2.

We explore the eclipsed stacking of a metal-organic Kagome lattice containing heavy-metal nodes. Our model is Pt3(HIB)2, a hypothetical but viable member of a well-known family of hexaaminobenzene based metal-organic frameworks (MOFs). Applying space group theory, it is shown how molecular diradicals, brought into play by a noninnocent ligand, become topologically nontrivial bands when moving in a periodic potential. Three factors are required to enable this: (1) eclipsed stacking, which shifts the Fermi level near a symmetry-protected band crossing (2) the emergence of an electride-like band that renders the topological invariant equal to 1, thus nontrivial, and (3) Pt-induced spin-orbit coupling, to turn the crossing into a bulk band gap. The electride band, with its unforeseen role, bears kinship to the interlayer band in hexagonal superconductors. It places its charge density in the voids of the crystal, rather than around the atomic nuclei, and we name it a "pore band". While the synthesis of truly conductive MOFs has proven challenging, the analysis shows that intrinsically nonlocal physics may emerge from tunable molecular building blocks. With the richness of redox-active MOF chemistry, this offers a pathway to tailored topological electronics.

Emerging class of SrZrS3 chalcogenide perovskite solar cells: Conductive MOFs as HTLs - A game changer?

The emerging SrZrS3 chalcogenide perovskite has been suggested as a potential alternative to lead halide perovskites, offering unique optoelectronic properties while addressing concerns such as lead toxicity and instability. Our research explored its potential, demonstrating the use of conductive metal-organic frameworks (c-MOFs) Cu-MOF ({[Cu2(6-mercapto nicotinate)]·NH4}n), NTU-9, Fe2(DSBDC), Sr-MOF ({[Sr(ntca)(H2O)2]·H2O}n), Mn2(DSBDC), and Cu3(HHTP)2 as promising substitutes for traditional HTLs via SCAPS-1D. By systematically optimizing the absorber and HTL properties, maximum PCEs of 30.60 %, 29.78 %, 28.29 %, 28.44 %, 28.80 %, and 28.62 % were accomplished for solar cell devices based on the aforementioned MOFs, respectively. Comparative analysis of initial and optimized solar cells using energy band diagrams, Nyquist plots, and quantum efficiency revealed that optimized devices consistently raised quasi-Fermi levels, significantly enhanced conductivity, and boosted solar cell performance. Additionally, the high recombination resistance of 1.4 × 107 Ω cm2, improved spectral response of 35 % in the NIR region, and heightened built-in potential (∼0.99 V) resulted in the highest efficiency of 30.60 % for Cu-MOF solar cells. This research highlights the promising potential of novel SrZrS3 absorbers and the utilization of c-MOFs as HTLs in solar cells, positioning them as a game changer in the PV field.

Conductive metal-organic frameworks with redox activity as electrode materials for rechargeable batteries

Conductive metal-organic frameworks with redox activity as electrode materials for rechargeable batteries

Tailoring d‑Band Center of Single-Atom Nickel Sites for Boosted Photocatalytic Reduction of Diluted CO2 from Flue Gas.

Photocatalytic reduction of diluted CO2 from anthropogenic sources holds tremendous potential for achieving carbon neutrality, while the huge barrier to forming *COOH key intermediate considerably limits catalytic effectiveness. Herein, via coordination engineering of atomically scattered Ni sites in conductive metal-organic frameworks (CMOFs), we propose a facile strategy for tailoring the d‑band center of metal active sites towards high-efficiency photoreduction of diluted CO2. Under visible-light irradiation in pure CO2, CMOFs with Ni-O4 sites (Ni-O4 CMOFs) exhibits an outstanding rate for CO generation of 13.3 μmol h-1 with a selectivity of 94.5%, which is almost double that of its isostructural counterpart with traditional Ni-N4 sites (Ni-N4 CMOFs), outperforming most reported systems under comparable conditions. Interestingly, in simulated flue gas, the CO selectivity of Ni-N4 CMOFs decreases significantly while that of Ni-O4 CMOFs is mostly unchanged, signifying the supremacy for Ni-O4 CMOFs in leveraging anthropogenic diluted CO2. In-situ spectroscopy and density functional theory (DFT) investigations demonstrate that O coordination can move the center of the Ni sites' d-band closer to the Fermi level, benefiting the generation of *COOH key intermediate as well as the desorption of *CO and hence leading to significantly boosted activity and selectivity for CO2-to-CO photoreduction.

A Computation‐Guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two‐Dimensional Conductive Metal–Organic Framework for Efficient H2O2 Electrosynthesis

AbstractElectrochemical synthesis of hydrogen peroxide (H2O2) via the two‐electron oxygen reduction reaction (2e−‐ORR) provides an alternative method to the energy‐intensive anthraquinone method. Metal macrocycles with precise coordination are widely used for 2e−‐ORR electrocatalysis, but they have to be commonly loaded on conductive substrates, thus exposing a large number of 2e−‐ORR‐inactive sites that result in poor H2O2 production rate and efficiency. Herein, guided by first‐principle predictions, a substrate‐free and two‐dimensional conductive metal–organic framework (Ni‐TCPP(Co)), composed of CoN4 sites in porphine(Co) centers and Ni2O8 nodes, is designed as a multi‐site catalyst for H2O2 electrosynthesis. The approperiate distance between the CoN4 and Ni2O8 sites in Ni‐TCPP(Co) weakens the electron transfer between them, thus ensuring their inherent activities and creating high‐density active sites. Meanwhile, the intrinsic electronic conductivity and porosity of Ni‐TCPP(Co) further facilitate rapid reaction kinetics. Therefore, outstanding 2e−‐ORR electrocatalytic performance has been achieved in both alkaline and neutral electrolytes (>90 %/85 % H2O2 selectivity within 0–0.8 V vs. RHE and >18.2/18.0 mol g−1 h−1 H2O2 yield under alkaline/neutral conditions), with confirmed feasibility for water purification and disinfection applications. This strategy thus provides a new avenue for designing catalysts with precise coordination and high‐density active sites, promoting high‐efficiency electrosynthesis of H2O2 and beyond.

A Computation-Guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two-Dimensional Conductive Metal-Organic Framework for Efficient H2O2 Electrosynthesis.

Electrochemical synthesis of hydrogen peroxide (H2O2) via the two-electron oxygen reduction reaction (2e--ORR) provides an alternative method to the energy-intensive anthraquinone method. Metal macrocycles with precise coordination are widely used for 2e--ORR electrocatalysis, but they have to be commonly loaded on conductive substrates, thus exposing a large number of 2e--ORR-inactive sites that result in poor H2O2 production rate and efficiency. Herein, guided by first-principle predictions, a substrate-free and two-dimensional conductive metal-organic framework (Ni-TCPP(Co)), composed of CoN4 sites in porphine(Co) centers and Ni2O8 nodes, is designed as a multi-site catalyst for H2O2 electrosynthesis. The approperiate distance between the CoN4 and Ni2O8 sites in Ni-TCPP(Co) weakens the electron transfer between them, thus ensuring their inherent activities and creating high-density active sites. Meanwhile, the intrinsic electronic conductivity and porosity of Ni-TCPP(Co) further facilitate rapid reaction kinetics. Therefore, outstanding 2e--ORR electrocatalytic performance has been achieved in both alkaline and neutral electrolytes (>90 %/85 % H2O2 selectivity within 0-0.8 V vs. RHE and >18.2/18.0 mol g-1 h-1 H2O2 yield under alkaline/neutral conditions), with confirmed feasibility for water purification and disinfection applications. This strategy thus provides a new avenue for designing catalysts with precise coordination and high-density active sites, promoting high-efficiency electrosynthesis of H2O2 and beyond.

Synthesis of coralline Cu-HHTP conductive MOF as an efficient oxygen reduction catalyst to enhance the power generation of the microbial fuel cell

Synthesis of coralline Cu-HHTP conductive MOF as an efficient oxygen reduction catalyst to enhance the power generation of the microbial fuel cell

MXene@Ni3(HITP)2@AuNPs combined with NiCo@Fc-MWCNTs-LDH for electrochemical detection of extracellular vesicles

This study proposed an electrochemical sensor combining Mxene@Ni3(HITP)2@AuNPs with NiCo@Fc-MWCNTs-LDH for detecting extracellular vesicles (EVs) derived from MCF-7 cells. Mxene exhibits high conductivity and large surface area. Ni3(HITP)2 is a novel conductive metal-organic framework (MOF) with outstanding conductivity, capable of loading more gold nanoparticles (AuNPs) when combined with polyetherimide (PEI). Tetrahedra DNA (TDN) is anchored on the substrate through gold nanoparticles (AuNPs) for the specific capture of EVs, with CD63 aptamers carried at their vertices. In the signal layer, the NiCo@Fc-MWCNTs-LDH loaded with CD63 aptamers was prepared as the electrochemical sensor signal label for EVs detection. This electrochemical sensor exhibits high sensitivity, evidenced by a low limit of detection (LOD) of 13.79 particles/mL and a linear range from 1.6 × 102 to 1.6 × 106 particles/mL, underscoring its potential for early cancer diagnosis.

Conductive Framework Materials for Chemiresistive Detection and Differentiation of Toxic Gases.

ConspectusSensing complex gaseous mixtures and identifying their composition and concentration have the potential to achieve unprecedented improvements in environmental monitoring, medical diagnostics, industrial safety, and the food/agriculture industry. Electronically transduced chemical sensors capable of recognizing and differentiating specific target gases and transducing these chemical stimuli in a portable electronic device offer an opportunity for impact by bridging the utility of chemical information with global wireless connectivity. Among electronically transduced chemical sensors, chemiresistors stand out as particularly promising due to combined features of low-power requirements, room temperature operation, non-line-of-sight detection, high portability, and exceptional modularity. Relying on changes in resistance of a functional material triggered by variations in the surrounding chemical environment, these devices have achieved part-per-billion sensitivities of analytes by employing conductive polymers, graphene, carbon nanotubes (CNTs), metal oxides, metal nanoparticles, metal dichalcogenides, or MXenes as sensing materials. Despite these tremendous developments, the need for stable, selective, and sensitive chemiresistors demands continued innovation in material design in order to operate in complex mixtures with interferents as well as variations in humidity and temperature.To fill existing gaps in sensing capabilities, conductive metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have recently emerged as a promising class of materials for chemiresistive sensing. In contrast to previously reported chemiresistors, these materials offer at least three unique features for gas sensing applications: (i) bottom-up synthesis from molecularly precise precursors that allows for strategic control of material-analyte interactions, (ii) intrinsic conductivity that simultaneously facilitates charge transport and signal transduction under low power requirements, and (iii) high surface area that enables the accessibility of abundant active sites and decontamination of gas streams by coordinating to and, sometimes, detoxifying harmful analytes. Through an emphasis on molecular engineering of structure-property relationships in conductive MOFs and COFs, combined with strategic innovations in device integration strategies and device form factor (i.e., the physical dimensions and design of device components), our group has paved the way to demonstrating the multifunctional utility of these materials in the chemiresistive detection of gases and vapors. Backed by spectroscopic assessment of material-analyte interactions, we illustrated how molecular-level features lead to device performance in detection, filtration, and detoxification of gaseous analytes. By merging the bottom-up synthesis of these materials with device integration, we show the versatility and scalability of using these materials in low-power electronic sensing devices. Taken together, our achievements, combined with the progress spearheaded on this class of materials by other researchers, establish conductive MOFs and COFs as promising multifunctional materials for applications in electronically transduced, portable, low-power sensing devices.

Highly stable and antifouling solid-contact ion-selective electrode for K+ detection in complex system based on multifunctional peptide and conductive MOF

Highly stable and antifouling solid-contact ion-selective electrode for K+ detection in complex system based on multifunctional peptide and conductive MOF

Artificial olfactory memory system based on conductive metal-organic frameworks

The olfactory system can generate unique sensory memories of various odorous molecules, guiding emotional and cognitive decisions. However, most existing electronic noses remain constrained to momentary concentration, failing to trigger specific memories for different smells. Here, we report an artificial olfactory memory system utilizing conductive metal-organic frameworks (Ce-HHTP) that integrates sensing and memory and exhibits short- and long-term memory responses to alcohols and aldehydes. Experiments and theoretical calculations show that distinct memories are derived from the specific combinations of Ce-HHTP with O atoms in different guest. An unmanned aircraft equipped with this system realized the sensory memories in established areas. Moreover, the fusion of portable detection boxes and wearable flexible electrodes demonstrated the immense potential in off-site pollution monitoring and health management. This work represents an artificial olfactory memory system with two specific sensory memories under simultaneous conditions, laying the foundation for bionic design with qualities of human olfactory memory.

Sea urchin-like Ni3(HITP)2 as the substrate of molecular imprinted polymer: the voltammetric mechanism for sensitive detection of dopamine.

An electrochemical sensor composed of conductive metal-organic framework [Ni3(HITP)2] and molecular imprinted polymers (MIP) is fabricated to detect dopamine. Ni3(HITP)2 promotes electrons transfer due to the structure of in-plane charge delocalization and layered expansion conjugation. The combination of MIP with Ni3(HITP)2 improves the selectivity and conductivity, exhibiting a wide detection range (0.06 ~ 200µM) and a low detection limit (0.109µM). The kinetic mechanism on the electrode surface is an adsorption controlled process, with the equal number of electrons and protons participating in oxidation in the electrocatalytic process of catechol converting to o-quinone.

Thiatruxene-Based Conductive MOF: Harnessing Sulfur Chemistry for Enhanced Proton Transport.

Functionalizing the organic building blocks of electrically conductive MOFs (EC-MOFs) can be a powerful method for adjusting the electronic structure and introducing a specific chemistry. However, designing EC-MOF linkers with reactive functional groups for postsynthetic modification is challenging due to the requirements of d-p conjugation. This work addresses such design limitations by synthesizing an EC-MOF, Cu-thiatruxene (Cu-thiaTRX). This conductive framework incorporated a truxene-based linker with heterocyclic sulfur, allowing for efficient conjugation and an electrical conductivity of 2.2 × 10-2 S cm-1. Harnessing sulfur chemistry in Cu-thiaTRX involves a two-step postsynthetic modification: oxidation and SNAr. The sulfinic groups introduced in the framework enabled tunable proton conductivity, leading to a 200-fold improvement. These results highlight the importance of a rational linker design for functionalization.

Increasing electrochemical carbon dioxide reduction to methane via a novel copper-based conductive metal organic framework

The development of a new system for the electrochemical carbon dioxide reduction reaction (ECO2RR) to methane (CH4) is challenging, and novel conductive metal organic frameworks (c-MOFs) for efficient ECO2RR to CH4 are critical to this system. Here, we report a novel c-MOF, copper-pyromellitic dianhydride-2-methylbenzimidazole (Cu-PD-2-MBI), in which the introduction of electron-withdrawing 2-methylbenzimidazole (2-MBI) into the copper-pyromellitic dianhydride (Cu-PD) interlayer elevated the valence of copper (Cu) ions, which improved the ECO2RR performance of Cu-PD-2-MBI. Cu-PD-2-MBI was tested in a flow cell, and the Faradaic efficiency of CH4 reached 73.7 %, with a corresponding partial current density of −428.3 mA·cm−2 at −1.3 V, which was higher than those of most reported Cu-based catalysts. Further exploration via theoretical calculations indicated that the intercalated 2-MBI in Cu-PD-2-MBI induced a shift in the d-band center in the Cu sites from −2.63 to −1.86 eV and reduced the formation energy of the *COOH and *CHO intermediates in the process of generating CH4 compared with those of the reference Cu-PD catalyst.

Sulfurized Two-Dimensional Conductive Metal-Organic Framework as a High-Performance Cathode Material for Rechargeable Mg Batteries.

Rechargeable Mg batteries are a promising energy storage technology to overcome the limitations inherent to Li ion batteries. A critical challenge in advancing Mg batteries is the lack of suitable cathode materials. In this work, we report a cathode design that incorporates S functionality into two-dimensional metal-organic-frameworks (2D-MOFs). This new cathode material enables good Mg2+ storage capacity and outstanding cyclability. It was found that upon the initial Mg2+ insertion and disinsertion, there is an apparent structural transformation that crumbles the layered 2D framework, leading to amorphization. The resulting material serves as the active material to host Mg2+ through reduction and/or oxidation of S and, to a limited extent, O. The reversible nature of S and O redox chemistry was confirmed by spectroscopic characterizations and validated by density functional calculations. Importantly, during the Mg2+ insertion and disinsertion process, the 2D nature of the framework was maintained, which plays a key role in enabling the high reversibility of the MOF cathode.