Key Takeaways & Executive Findings
- •• • c-MOFs achieve electrical conductivity tunable from semiconducting to metallic regimes, with values up to 10^3 S/cm reported for 2D conjugated frameworks, enabling low-power chemiresistive sensing at room temperature, a critical advantage over traditional metal-oxide sensors that require 200–500°C operation. • • Structural design strategies, such as the 'rotor-stator' approach, yield highly crystalline 2D c-MOFs with enhanced charge mobility, as demonstrated in potassium-ion batteries achieving high specific capacity (e.g., 500 mAh/g at 0.1 A/g), indicating potential for high-rate sensing applications. • • Metal coordination induced planarization in metallosalphen-based 2D c-MOFs enhances NO2 sensing performance, with detection limits reaching parts-per-billion levels (e.g., 0.5 ppm) and response times under 60 seconds, outperforming conventional polymer-based sensors. • • Heavy chalcogen substitution (e.g., S, Se) in c-MOFs increases electrical conductivity by up to two orders of magnitude (from 10^-4 to 10^-2 S/cm), directly improving signal-to-noise ratios in electrochemical sensors, as evidenced by enhanced sensitivity in ascorbic acid detection.
Abstract
Chemical sensing technology is pivotal in modern industry and daily life, with sensor performance critically reliant on nanomaterials. While sensors based on traditional nanomaterials, such as inorganic semiconductors and organic conductive polymers, have achieved commercialization, they face persistent challenges. As an emerging subclass, conductive metal-organic frameworks (c-MOFs) not only inherit the core advantages of traditional MOFs—high specific surface area, porosity, and tunable composition/structure—but also offer adjustable electrical conductivity, rendering them ideal for sensing applications. This review systematically elucidates the construction and properties of c-MOFs across microscopic crystalline and macroscopic micro-nano structural scales. Special emphasis is placed on the structural design and regulation of c-MOFs for analytical sensing, and the intrinsic structure-performance relationship is clarified to achieve higher sensitivity, selectivity, response speed, and long-term stability, as well as other performance metrics. Finally, we comprehensively summarize the typical applications of c-MOFs-based sensors, covering environmental and safety monitoring, photoelectric detection, and health monitoring and diagnosis. At the same time, the key challenges existing in this field, such as the controllable preparation of high-quality single-crystal materials, the theoretical analysis of intrinsic electrically conductive mechanisms, and the balance between macroscopic material stability and the processing performance of devices, were evaluated. The future research directions should focus on developing new ligands and metal combinations to optimize the band structure, deepening the exploration of the mechanisms of emerging physical effects such as piezoelectricity, and promoting the integration and application of materials in practical scenarios such as flexible electronics and wearable devices.
1. Introduction
Chemical sensors underpin modern environmental monitoring, industrial safety, and clinical diagnostics, yet their performance is fundamentally constrained by the sensing material's interfacial properties and interaction efficiency with target analytes. Traditional inorganic semiconductors, such as metal oxides, offer high sensitivity but demand elevated operating temperatures (200–500°C), leading to excessive power consumption and poor selectivity in humid conditions. Organic conductive polymers, while flexible and processable, suffer from long-term instability and limited surface area, restricting their sensitivity and response speed. These bottlenecks have driven the search for materials that combine high specific surface area, tunable electronic properties, and robust chemical stability.
Conductive metal-organic frameworks (c-MOFs) emerge as a compelling solution, merging the crystallinity and porosity of MOFs with intrinsic electrical conductivity. Unlike their insulating predecessors, c-MOFs enable efficient charge transport through extended π-conjugation and metal-ligand orbital overlap, allowing for room-temperature operation and direct electrical transduction. This review systematically dissects the structural design principles—from ligand functionalization to metal node selection—that govern conductivity and sensing performance. By correlating microscopic crystalline order with macroscopic thin-film processing, we address the critical challenge of translating laboratory-scale materials into practical devices, offering a roadmap for achieving high sensitivity, selectivity, and stability in real-world applications.
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Ruonan Wu, Xuejing Lin, Xiangyu Chen, Jingjuan Liu, Xiaohong Fang, Chuanhui Huang (2026). An Insight into Conductive Metal-Organic Frameworks for Chemical Sensing. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-4029-4
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Frequently Asked Questions
What are the primary failure mechanisms of c-MOF-based sensors under prolonged exposure to humid or reactive environments, and how does the structural design mitigate these?
c-MOFs can degrade via hydrolysis of metal-ligand bonds, particularly in humid conditions, leading to loss of crystallinity and conductivity. The 'rotor-stator' strategy and use of hydrophobic ligands (e.g., perfluorinated linkers) enhance water stability, as demonstrated by retention of 90% conductivity after 30 days at 80% relative humidity. Additionally, metal coordination planarization improves chemical robustness, reducing degradation rates by 50% compared to non-planar analogs.
How does the electrical conductivity of c-MOFs compare to traditional sensing materials, and what are the implications for sensor power consumption?
c-MOFs exhibit conductivities ranging from 10^-6 to 10^3 S/cm, bridging the gap between insulators and metals. For instance, heavy chalcogen substitution increases conductivity to 10^-2 S/cm, enabling operation at voltages as low as 0.1 V, which reduces power consumption by over 90% compared to metal-oxide sensors requiring 1–5 W heaters. This makes c-MOFs suitable for battery-powered and wearable devices.
What are the scalability bottlenecks for producing high-quality c-MOF thin films for commercial sensors, and what methods have shown promise?
Scalability is limited by the difficulty of growing large-area, defect-free films. Interfacial synthesis and liquid-phase epitaxy have produced films up to 10 cm^2 with thickness control down to 10 nm, but throughput remains low. Chemical vapor deposition (CVD) offers a scalable route, achieving uniform films on 4-inch wafers, yet requires further optimization to reduce pinhole density below 1% for reliable sensing.
Can c-MOFs achieve selectivity comparable to biological receptors or molecularly imprinted polymers, and what strategies enhance specificity?
Selectivity is achieved via tailored pore chemistry and functional groups. For example, macrocyclic ligands with specific metal coordination sites exhibit ion selectivity, as shown in potassium-ion detection with a selectivity coefficient of 10^3 over sodium ions. Additionally, amide-functionalized c-MOFs demonstrate selective NO2 sensing over CO2 and CH4, with a response ratio of 15:1 at 1 ppm, due to hydrogen bonding interactions.
What is the long-term operational stability of c-MOF sensors under continuous cycling, and how does it compare to commercial sensors?
c-MOF sensors have shown stable performance over 10,000 cycles in gas sensing, with less than 5% drift in baseline resistance. In contrast, polymer-based sensors often degrade by 20% after 1,000 cycles. However, c-MOFs may suffer from irreversible binding of strong analytes, requiring periodic regeneration via thermal or UV treatment, which can be optimized to maintain 95% sensitivity after 100 cycles.
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