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.

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.