Target-Driven Z-Scheme Heterojunction Formation for ppb H2S Detection from Exhaled Breath at Room Temperature

As a biomarker of periodontitis, sensitive and timely monitoring of hydrogen sulfide (H2S) in exhaled breath at room temperature (RT) is important for the early intervention of oral diseases. However, the required high operation temperature to achieve high sensitivity is still a technical challenge for directly monitoring exhaled breath. In this study, by integrating metal-organic frameworks (MOFs) into self-aligned TiO2 nanotube arrays (NTs), a chemiresistor gas sensor with outstanding sensitivity and selectivity was constructed for the detection of H2S at RT. The precise regulation of a Co(III)-based MOF CoBDC-NH2 (BDC-NH2 = 2-aminoterephthalic acid) not only induced more active surface for the preconcentration of the target gas but also caused a buildup of Z-scheme heterojunctions in the H2S atmosphere that induced an ultrahigh sensitivity at RT via 365 nm light-emitting diode irradiation. The response and recovery times decreased to ∼50 and ∼28%, respectively, when this system was exposed to UV light. The sensing chips based on the as-prepared TiO2/CoBDC-NH2 NTs exhibited the highest-ranking H2S sensing performance, i.e., a limit of detection of 1.3 ppb and excellent selectivity even to 100 times high concentration of interference gases, owing to the synergistic chemical environment provided by NH2-functionalized Co-MOFs and abundant photogenerated electrons provided by Z-scheme heterojunctions. This sensing chip was also used in a practical application for the timely monitoring of halitosis from direct exhaled breath. This study provides a reliable and sensitive design for clinically aiding the timely detection of H2S in a complex oral environment.