Chemiresistive gas sensors based on semiconducting metal oxides typically rely on noble metal catalysts to enhance their sensitivity and selectivity. However, noble metal catalysts have several drawbacks for practical utilization, including their high cost, their propensity for spontaneous agglomeration, and poisoning effects with certain types of gases. As such, in the interest of commercializing the chemiresistive gas sensor technology, we propose an alternative design for a noble-metal-free sensing material through the case study of Co-doped ceria (Co-CeO2) catalysts embedded in a SnO2 matrix. In this investigation, we utilized electrospinning and subsequent calcination to prepare Co-CeO2 catalyst nanoparticles integrated with SnO2 nanofibers (NFs) with uniform particle distribution and particle size regulation down to the sub-2 nm regime. The resulting Co-CeO2@SnO2 NFs exhibited superior gas sensing characteristics toward isoprene (C5H8) gas, a significant biomarker for monitoring the onset of various diseases through breath diagnostics. In particular, we identified that the Co-CeO2 catalysts, owing to the transition metal doping, facilitated the spillover of chemisorbed oxygen species to the SnO2 sensing body. This resulting in the sensor having a 27.4-fold higher response toward 5 ppm of C5H8 (compared to pristine SnO2), exceptionally high selectivity, and a low detection limit of 100 ppb. The sensor also exhibited high stability for prolonged response-recovery cycles, attesting to the strong anchoring of Co-CeO2 catalysts in the SnO2 matrix. Based on our findings, the transition metal-doped metal oxide catalysts, such as Co-CeO2, demonstrate strong potential to completely replace noble metal catalysts, thereby advancing the development of the commercially viable chemiresistive gas sensors free from noble metals, capable of detecting target gases at sub-ppm levels.

Perovskite oxides are promising candidates for chemiresistive-type gas sensors owing to their exceptional thermal and chemical stability during solid-gas reactions. However, perovskites suffer from critical issues such as low surface area and poor surface activity, which negatively influence the sensing characteristics. While metal nanoparticles can be incorporated in perovskites to improve their reactivity, the fundamental incompatibility between catalytic metals and perovskite oxides often leads to substantial structural degradation as well as phase instability. Herein, we overcome this challenge through the introduction of an intermediary phase that forms coherent interfaces with both the perovskite phase and catalyst metals. Specifically, we present the case study of p-type La0.8Ca0.2Fe0.98Pt0.02O3 perovskite, whose hole accumulation layer was modulated by the incorporation of metal-organic framework (MOF)-derived n-type alpha-Fe2O3 nanoparticles decorated with highly dispersed Pt catalysts. The resulting composite exhibited significantly improved surface activity over the nonmodified La0.8Ca0.2FeO3 perovskite, leading to exceptional chemiresistive sensing performance toward acetone gas (R g/R a = 39.8 toward 10 ppm of acetone at 250 degrees C) with high cross-sensitivity against interfering gases. Importantly, our findings reaffirm the critical influence of interfacial engineering in facilitating surface chemical reactions on perovskite oxides and, by doing so, effectively provide a general synthetic guideline to the design of perovskite-based chemiresistors.

To rationalize the noninvasive disease diagnosis by breath analysis, developing a high-performance gas sensor with exceptional sensitivity and selectivity is important to detect trace biomarkers in complex exhaled breath under harsh conditions. Among the various technological innovations, catalyst design and synthesis techniques are the foremost challenges, because gas sensing properties are predominantly determined by surface chemical reactions governed by catalytic activities. Conventional nanoparticle-based catalysts, with their simple structural features, have technical limitations in achieving the requirement for accurate breath analysis. Innovative strategies have been pursued to synthesize unconventional catalyst types with enhanced catalytic capabilities. This Perspective provides a comprehensive overview of recent advancements in catalyst technology for chemiresistive-type gas sensors used in breath analysis. It discusses various emerging catalysts, such as doping catalysts, single-atom catalysts (SACs), bimetallic alloy catalysts, high-entropy alloy (HEA) catalysts, exsolution catalysts, and catalytic filter membranes, along with their unique chemical activation mechanisms that enhance gas sensing properties for detecting target biomarkers in exhaled breath. The review also explores novel strategies for catalyst design, including computational prediction, advanced synthesis techniques, and the integration of sensor arrays with artificial intelligence (AI) to improve diagnostic reliability. By highlighting the crucial role of these emerging catalysts, this review provides valuable insights into the catalytic, synthetic, and analytical aspects that are essential for advancing breath analysis technology.

Perovskite oxides (PO) possess a crystal structure known as ABO3, where rare-earth metal atoms occupy the A sites, transition metal atoms are found at the B sites, and oxygen is the anion. Elements from nearly 90% of the periodic table can occupy A or B sites, resulting in various crystal structures and compositions within the PO family. Due to this flexibility, PO exhibits outstanding physicochemical and electronic properties, such as high oxygen ion conductivity and excellent redox reaction characteristics. Additionally, their ability to be synthesized at high temperatures contributes to their superior thermal and chemical stability, enabling widespread use in applications such as electrocatalysis-based energy storage and chemical looping combustion. Recently, the fourth industrial revolution and advancements in nanomaterials have amplified the importance of gas-sensing technology in environmental monitoring, industrial safety, and healthcare. Therefore, extensive research in gas sensors highlights the development of highly sensitive, selective, and stable sensors.PO-based chemiresistive sensors have attracted significant attention due to their ability to tailor the chemical structures of active sites for selective gas reaction, control the amount of oxygen adsorption, and offer a reliable sensing performance. However, enhancing the sensing performance of PO-based sensors faces challenges due to the low intrinsic surface activity of p-type PO. Various efforts to overcome this limitation include nanostructure engineering to increase the surface area and porosity of PO, compositional modulation, such as partial substitutions, and the formation of heterostructures. Moreover, functionalizing PO as catalysts onto sensing layers can enhance sensing performance by influencing the adsorption/desorption kinetics of the target gas, making it a promising approach.In this Account, we delve into versatile methodologies for maximizing gas sensing performance using the p-type PO, highlighting key advancements within our research group. Beginning with explaining operation mechanisms and essential design factors of chemiresistive sensors based on PO, various strategies are introduced, each tailored to specific roles in chemiresistive sensors, including the sensing layer, reaction promoter, and supports for the catalysts. These include electrospinning to control the PO morphology and the galvanic replacement reaction on PO for simultaneous changes in the morphology and composition of PO sensing layers. Additionally, the enhanced surface activity achieved by loading catalytic PO particles on sensing layers and the latest technologies involving ex-solution and single-atom catalysts on PO are discussed. Finally, this Account concludes with a summary and a discussion of the remaining challenges and future tasks, providing in-depth insights into PO-based chemiresistive sensors.

Metal-organic frameworks (MOFs) have emerged as attractive chemical sensing materials due to their exceptionally high porosity and chemical diversity. Nevertheless, the utilization of MOFs in chemiresistive type sensors has been hindered by their inherent limitation in electrical conductivity. The recent emergence of two-dimensional conductive MOFs (2D c-MOFs) has addressed this limitation by offering enhanced electrical conductivity, while still retaining the advantageous properties of MOFs. In particular, c-MOFs have shown promising advantages for the fabrication of sensors capable of operating at room temperature. Thus, active research on gas sensors utilizing c-MOFs is currently underway, focusing on enhancing sensitivity and selectivity. To comprehend the potential of MOFs as chemiresistive sensors for future applications, it is crucial to understand not only the fundamental properties of conductive MOFs but also the state-of-the-art works that contribute to improving their performance. This comprehensive review delves into the distinctive characteristics of 2D c-MOFs as a new class of chemiresistors, providing in-depth insights into their unique sensing properties. Furthermore, we discuss the proposed sensing mechanisms associated with 2D c-MOFs and provide a concise summary of the strategies employed to enhance the sensing performance of 2D c-MOFs. These strategies encompass a range of approaches, including the design of metal nodes and linkers, morphology control, and the synergistic use of composite materials. In addition, the review thoroughly explores the prospects of 2D c-MOFs as chemiresistors and elucidates their remarkable potential for further advancements. The insights presented in this review shed light on future directions and offer valuable opportunities in the chemical sensing research field.

This study introduces a promising technique to enhance the sensitivity of p-type semiconductors in gas-sensing applications. By utilizing a glycerate-templated synthesis approach, a unique hierarchical W-doped Co3O4 yolk-shell sphere (YSS)-based sensor was developed, exhibiting exceptional sensitivity toward acetone gas. The synthesized YSSs feature a yolk-shell structure with a diameter of approximately 500 nm and a large surface area of 117.46 m2/g, which allows for efficient gas interaction and high sensitivity toward acetone gas. Furthermore, the incorporation of tungsten (W), a non-noble metal, as a dopant significantly enhances the surface activity of Co3O4, leading to a remarkably high response of 16.5 toward 5 ppm acetone, which is substantially higher than that of the pure Co3O4 YSS (2.9). The W-doped Co3O4 YSS also exhibits excellent selectivity to other interfering gases and the ability to detect ultralow concentrations of acetone as low as 10 ppb. The proposed non-noble metal doping strategy presents a practical solution for enhancing the sensitivity and selectivity of p-type semiconductor-based gas sensors. This approach holds great potential for practical gas-sensing applications due to their affordability and abundance, making them a cost-effective and versatile alternative to noble metal-catalyzed sensors.

The process of exsolution for the synthesis of strongly anchored metal nanoparticles (NPs) on host oxide lattices has been proposed as a promising strategy for designing robust catalyst-support composite systems. However, because conventional exsolution processes occur in harsh reducing environments at high temperatures for long periods of time, the choice of support materials and dopant metals are limited to those with inherently high thermal and chemical stability. Herein, we report the exsolution of a series of noble metal catalysts (Pt, Rh, and Ir) from metal oxide nanofibers (WO3 NFs) supports in an entirely ambient environment induced by intense pulsed light (IPL)-derived momentary photothermal treatment (>1000 °C). Since the exsolution process spans an extremely short period of time (<20 ms), unwanted structural artifacts such as decreased surface area and phase transition of the support materials are effectively suppressed. At the same time, exsolved NPs (<5 nm) with uniform size distributions could successfully be formed. To prove the practical utility of exsolved catalytic NPs functionalized on WO3 NFs, the chemiresistive gas sensing characteristics of exsolved Pt-decorated WO3 NFs were analyzed, exhibiting high durability (>200 cyclic exposures), enhanced response (Rair/Rgas > 800 @ 1 ppm/350 °C), and selectivity toward H2S target gas. Altogether, we successfully demonstrated that ultrafast exsolution within a few milliseconds could be induced in ambient conditions using the IPL-derived momentary photothermal treatment and contributed to expanding the practical viability of the exsolution-based synthetic approaches for the production of highly stable catalyst systems.

This work presents the synthesis of LaFeO3/SnO2 nanotubes (NTs) based on the GRR process, with perovskite LaFeO3 NTs prepared by electrospun nanofibers as the starting material resulting in a significantly enhanced catalytic activity.

Although p-type semiconductors exhibit highly selective and stable chemiresistive gas sensing performances compared to conventional n-type semiconductors, their low sensitivity had long impeded their practical development. In this work, we developed highly porous Co3O4/CoMoO4 heterostructure nanosheets (NSs) with enhanced sensitivity and superior stability toward acetone gas through a facile solution-based approach with Mo-impregnated Co-based metal-organic frameworks as the starting material. The spontaneous formation of a large number of p-p heterojunctions at the Co3O4-CoMoO4 interface would facilitate the adsorption of oxygen and acetone molecules, as verified by density functional theory calculations. Consequently, experimental results showed that the Co3O4/CoMoO4 NSs have a greatly enhanced response of 8.5 toward 5 ppm acetone, which is 7.1 times higher than that of pure Co3O4 NS, without involving any noble metal catalysts. Moreover, the limit of detection of the Co3O4/CoMoO4 NSs was as low as 10 ppb. Altogether, we propose that our synthetic approach for the engineering of p-p heterojunctions is an effective strategy for the future development of highly practical and sensitive gas sensors based on p-type semiconductors.