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.

Highly Selective and Sensitive Detection of Breath Isoprene by Tailored Gas Reforming: A Synergistic Combination of Macroporous WO3 Spheres and Au Catalysts.

Precise detection of breath isoprene can provide valuable information for monitoring the physical and physiological status of human beings or for the early diagnosis of cardiovascular diseases. However, the extremely low concentration and low chemical reactivity of breath isoprene hamper the selective and sensitive detection of isoprene using oxide semiconductor chemiresistors. Herein, we report that macroporous WO3 microspheres whose inner macropores are surrounded by Au nanoparticles exhibit a high response (resistance ratio = 11.3) to 0.1 ppm isoprene under highly humid conditions at 275 °C and an extremely low detection limit (0.2 ppb). Furthermore, the sensor showed excellent selectivity to isoprene over five interferants that could be exhaled by humans. Notably, the selectivity to isoprene is critically dependent on the location of Au nanocatalysts and macroporosity. The mechanism underlying the selective isoprene detection is investigated in relation to the reforming of less reactive isoprene into more reactive intermediate species promoted by macroporous catalytic reactors, which is confirmed by the analysis using a proton transfer reaction quadrupole mass spectrometer. The sensor for breath analysis has high potential for simple physical and physiological monitoring as well as disease diagnosis.

General Strategy for Designing Highly Selective Gas-Sensing Nanoreactors: Morphological Control of SnO2 Hollow Spheres and Configurational Tuning of Au Catalysts.

Catalyst-loaded hollow spheres are effective at detecting ethanol with high chemical reactivity. However, this has limited the widespread use of catalyst-loaded hollow spheres in designing highly selective gas sensors to less-reactive gases such as aromatics (e.g., xylene). Herein, we report the preparation of xylene-selective Au-SnO2 nanoreactors by loading Au nanoclusters on the inner surface of SnO2 hollow shells using the layer-by-layer assembly technique. The results revealed that the sensor based on SnO2 hollow spheres loaded with Au nanoclusters on the inner surface exhibited unprecedentedly high xylene selectivity and an ultrahigh xylene response, high enough to be used for indoor air quality monitoring, whereas the sensor based on SnO2 hollow spheres loaded with Au nanoclusters on the outer surface exhibited the typical ethanol-sensitive sensing behaviors as frequently reported in the literature. In addition, the xylene selectivity and response were optimized when the hollow shell was sufficiently thin (∼25 nm) and semipermeable (pore size = ∼3.5 nm), while the selectivity and response decreased when the shell was thick or highly gas permeable with large mesopores (∼30 nm). Accordingly, the underlying mechanism responsible for the unprecedentedly high xylene sensing performance is discussed in relation to the configuration of the loaded Au nanoclusters and the morphological characteristics including shell thickness and pore size distribution. This novel nanoreactor concept can be widely used to design highly selective gas sensors especially to less-reactive gases such as aromatics, aldehydes, and ketones.

A New Strategy for Detecting Plant Hormone Ethylene Using Oxide Semiconductor Chemiresistors: Exceptional Gas Selectivity and Response Tailored by Nanoscale Cr2O3 Catalytic Overlayer.

A highly selective and sensitive detection of the plant hormone ethylene, particularly at low concentrations, is essential for controlling the growth, development, and senescence of plants, as well as for ripening of fruits. However, this remains challenging because of the non-polarity and low reactivity of ethylene. Herein, a strategy for detecting ethylene at a sub-ppm-level is proposed by using oxide semiconductor chemiresistors with a nanoscale oxide catalytic overlayer. The SnO2 sensor coated with the nanoscale catalytic Cr2O3 overlayer exhibits rapid sensing kinetics, good stability, and an unprecedentedly high ethylene selectivity with exceptional gas response (R a/R g - 1, where R a represents the resistance in air and R g represents the resistance in gas) of 16.8 at an ethylene concentration of 2.5 ppm at 350 °C. The sensing mechanism underlying the ultraselective and highly sensitive ethylene detection in the unique bilayer sensor is systematically investigated with regard to the location, configuration, and thickness of the catalytic Cr2O3 overlayer. The mechanism involves the effective catalytic oxidation of interfering gases into less- or non-reactive species, without limiting the analyte gas transport. The sensor exhibits a promising potential for achieving a precise quantitative assessment of the ripening of five different fruits.