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. A hybridization strategy is demonstrated synergistically deploying conductive MOFs (cMOFs) and conductive polymers (cPs) as two complementary mixed ionic-electronic conductors in high-performing stand-alone chemiresistors. This work presents significant improvement in i) sensor recovery kinetics, ii) cycling stability, and iii) dynamic range at room temperature. The effect of hybridization across well-studied cMOFs is demonstrated based on 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7,10,11-hexaiminotriphenylene (HITP) ligands with varied metal nodes (Co, Cu, Ni). A comprehensive mechanistic study is conducted to relate energy band alignments at the heterojunctions between the MOFs and the polymer with sensing thermodynamics and binding kinetics. The 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 is further supported by density functional theory calculations on sorbate-analyte interactions. It is also found 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.

Highly Sensitive and Selective Real-Time Breath Isoprene Detection using the Gas Reforming Reaction of MOF-Derived Nanoreactors.

Real-time breath isoprene sensing provides noninvasive methods for monitoring human metabolism and early diagnosis of cardiovascular diseases. Nonetheless, the stable alkene structure and high humidity of the breath hinder sensitive and selective isoprene detection. In this work, we derived well-defined Co3O4@polyoxometalate yolk-shell structures using a metal-organic framework template. The inner space, including highly catalytic Co3O4 yolks surrounded by a semipermeable polyoxometalate shell, enables stable isoprene to be reformed to reactive intermediate species by increasing the gas residence time and the reaction with the inner catalyst. This sensor exhibited selective isoprene detection with an extremely high chemiresistive response (180.6) and low detection limit (0.58 ppb). The high sensing performance can be attributed to electronic sensitization and catalytic promotion effects. In addition, the reforming reaction of isoprene is further confirmed by the proton transfer reaction-quadrupole mass spectrometry analysis. The practical feasibility of this sensor in smart healthcare applications is exhibited by monitoring muscle activity during the workout.

MOF-Based Chemiresistive Gas Sensors: Toward New Functionalities.

The sensing performances of gas sensors must be improved and diversified to enhance quality of life by ensuring health, safety, and convenience. Metal-organic frameworks (MOFs), which exhibit an extremely high surface area, abundant porosity, and unique surface chemistry, provide a promising framework for facilitating gas-sensor innovations. Enhanced understanding of conduction mechanisms of MOFs has facilitated their use as gas-sensing materials, and various types of MOFs have been developed by examining the compositional and morphological dependences and implementing catalyst incorporation and light activation. Owing to their inherent separation and absorption properties and catalytic activity, MOFs are applied as molecular sieves, absorptive filtering layers, and heterogeneous catalysts. In addition, oxide- or carbon-based sensing materials with complex structures or catalytic composites can be derived by the appropriate post-treatment of MOFs. This review discusses the effective techniques to design optimal MOFs, in terms of computational screening and synthesis methods. Moreover, the mechanisms through which the distinctive functionalities of MOFs as sensing materials, heterostructures, and derivatives can be incorporated in gas-sensor applications are presented.

Visible-Light-Activated Type II Heterojunction in Cu3(hexahydroxytriphenylene)2/Fe2O3 Hybrids for Reversible NO2 Sensing: Critical Role of π-π* Transition.

Metal-organic frameworks (MOFs) with high surface area, tunable porosity, and diverse structures are promising platforms for chemiresistors; however, they often exhibit low sensitivity, poor selectivity, and irreversibility in gas sensing, hindering their practical applications. Herein, we report that hybrids of Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) nanoflakes and Fe2O3 nanoparticles exhibit highly sensitive, selective, and reversible detection of NO2 at 20 °C. The key parameters to determine their response, selectivity, and recovery are discussed in terms of the size of the Cu3(HHTP)2 nanoflakes, the interaction between the MOFs and NO2, and an increase in the concentration and lifetime of holes facilitated by visible-light photoactivation and charge-separating energy band alignment of the hybrids. These photoactivated MOF-oxide hybrids suggest a new strategy for designing high-performance MOF-based gas sensors.

Exclusive and ultrasensitive detection of formaldehyde at room temperature using a flexible and monolithic chemiresistive sensor.

Formaldehyde, a probable carcinogen, is a ubiquitous indoor pollutant, but its highly selective detection has been a long-standing challenge. Herein, a chemiresistive sensor that can detect ppb-level formaldehyde in an exclusive manner at room temperature is designed. The TiO2 sensor exhibits under UV illumination highly selective detection of formaldehyde and ethanol with negligible cross-responses to other indoor pollutants. The coating of a mixed matrix membrane (MMM) composed of zeolitic imidazole framework (ZIF-7) nanoparticles and polymers on TiO2 sensing films removed ethanol interference completely by molecular sieving, enabling an ultrahigh selectivity (response ratio > 50) and response (resistance ratio > 1,100) to 5 ppm formaldehyde at room temperature. Furthermore, a monolithic and flexible sensor is fabricated successfully using a TiO2 film sandwiched between a flexible polyethylene terephthalate substrate and MMM overlayer. Our work provides a strategy to achieve exclusive selectivity and high response to formaldehyde, demonstrating the promising potential of flexible gas sensors for indoor air monitoring.

A Transparent Nanopatterned Chemiresistor: Visible-Light Plasmonic Sensor for Trace-Level NO2 Detection at Room Temperature.

The highly selective detection of trace gases using transparent sensors at room temperature remains challenging. Herein, transparent nanopatterned chemiresistors composed of aligned 1D Au-SnO2 nanofibers, which can detect toxic NO2 gas at room temperature under visible light illumination is reported. Ten straight Au-SnO2 nanofibers are patterned on a glass substrate with transparent electrodes assisted by direct-write, near-field electrospinning, whose extremely low coverage of sensing materials (≈0.3%) lead to the high transparency (≈93%) of the sensor. The sensor exhibits a highly selective, sensitive, and reproducible response to sub-ppm levels of NO2 , and its detection limit is as low as 6 ppb. The unique room-temperature NO2 sensing under visible light emanates from the localized surface plasmonic resonance effect of Au nanoparticles, thereby enabling the design of new transparent oxide-based gas sensors without external heaters or light sources. The patterning of nanofibers with extremely low coverage provides a general strategy to design diverse compositions of gas sensors, which can facilitate the development of a wide range of new applications in transparent electronics and smart windows wirelessly connected to the Internet of Things.

Highly Selective Detection of Benzene and Discrimination of Volatile Aromatic Compounds Using Oxide Chemiresistors with Tunable Rh-TiO2 Catalytic Overlayers.

Volatile aromatic compounds are major air pollutants, and their health impacts should be assessed accurately based on the concentration and composition of gas mixtures. Herein, novel bilayer sensors consisting of a SnO2 sensing layer and three different xRh-TiO2 catalytic overlayers (x = 0.5, 1, and 2 wt%) are designed for the new functionalities such as the selective detection, discrimination, and analysis of benzene, toluene, and p-xylene. The 2Rh-TiO2/SnO2 bilayer sensor shows a high selectivity and response toward ppm- and sub-ppm-levels of benzene over a wide range of sensing temperatures (325-425 °C). An array of 0.5Rh-, 1Rh-, and 2Rh-TiO2/SnO2 sensors exhibits discrimination and composition analyses of aromatic compounds. The conversion of gases into more active species at moderate catalytic activation and the complete oxidation of gases into non-reactive forms by excessive catalytic promotion are proposed as the reasons behind the enhancement and suppression of analyte gases, respectively. Analysis using proton transfer reaction-quadrupole mass spectrometer (PTR-QMS) is performed to verify the above proposals. Although the sensing characteristics exhibit mild moisture interference, bilayer sensors with systematic and tailored control of gas selectivity and response provide new pathways for monitoring aromatic air pollutants and evaluating their health impacts.

Metal-Organic Framework-Derived Hollow Hierarchical Co3O4 Nanocages with Tunable Size and Morphology: Ultrasensitive and Highly Selective Detection of Methylbenzenes.

Nearly monodisperse hollow hierarchical Co3O4 nanocages of four different sizes (∼0.3, 1.0, 2.0, and 4.0 µm) consisting of nanosheets were prepared by controlled precipitation of zeolitic imidazolate framework-67 (ZIF-67) rhombic dodecahedra, followed by solvothermal synthesis of Co3O4 nanocages using ZIF-67 self-sacrificial templates, and subsequent heat treatment for the development of high-performance methylbenzene sensors. The sensor based on hollow hierarchical Co3O4 nanocages with the size of ∼1.0 µm exhibited not only ultrahigh responses (resistance ratios) to 5 ppm p-xylene (78.6) and toluene (43.8) but also a remarkably high selectivity to methylbenzene over the interference of ubiquitous ethanol at 225 °C. The unprecedented and high response and selectivity to methylbenzenes are attributed to the highly gas-accessible hollow hierarchical morphology with thin shells, abundant mesopores, and high surface area per unit volume as well as the high catalytic activity of Co3O4. Moreover, the size, shell thickness, mesopores, and hollow/hierarchical morphology of the nanocages, the key parameters determining the gas response and selectivity, could be well-controlled by tuning the precipitation of ZIF-67 rhombic dodecahedra and solvothermal reaction. This method can pave a new pathway for the design of high-performance methylbenzene sensors for monitoring the quality of indoor air.