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.

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.

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 Cu 3 (HHTP) 2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) nanoflakes and Fe 2 O 3 nanoparticles exhibit highly sensitive, selective, and reversible detection of NO 2 at 20 °C. The key parameters to determine their response, selectivity, and recovery are discussed in terms of the size of the Cu 3 (HHTP) 2 nanoflakes, the interaction between the MOFs and NO 2 , 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.

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.

Water poisoning, the dependence of gas‐sensing characteristics on moisture, in oxide chemiresistors remains a long‐standing challenge. Various approaches are explored to mitigate water poisoning but they are often accompanied by significant deterioration of sensing capabilities such as gas response deterioration, gas selectivity alteration, and sensor resistance increase up to unmeasurable levels. Herein, a novel sensor design with a moisture‐blocking Tb4O7 overlayer is suggested as a facile and universal strategy to remove moisture poisoning without sacrificing intrinsic sensing properties. A submicrometer‐thick coating of Tb4O7 overlayer on In2O3 sensors effectively eliminates the humidity dependence of the gas‐sensing characteristics without significantly altering the gas response, selectivity, and sensor resistance. Furthermore, the general validity of the water‐blocking effect using the Tb4O7 overlayer is confirmed in diverse gas sensors using SnO2, ZnO, and Pd/SnO2. The negligible moisture interference of the bilayer sensor is explained in terms of the hydrophobic nature of the Tb4O7 overlayer and the prevention of formation of the OH radical by the interaction between Tb4O7 and In2O3. A universal solution to design diverse humidity‐independent gas sensors with different gas selectivities can open up new pathways toward building accurate and robust gas sensors with new functionalities and high‐performance artificial olfaction.