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Activation of metal oxides by light is a robust yet facile approach to manipulating their surface chemistry for favorable reactions with target molecules in heterogeneous catalysis and gas sensors. However, a limited understanding of interface chemistry and the involved mechanism impedes the development of a rational design of oxide interfaces for light‐activated gas sensing. Herein, the TiOx‐assisted photosensitization of In2O3 toward NO2 sensing is investigated as a case study to elucidate the detailed mechanism of light‐activated surface chemistry at the metal/gas interface. The resultant heterogeneous oxides exhibit outstanding NO2 sensing performance under light irradiation thanks to abundant photoexcited electrons and holes that serve as adsorption and desorption sites, respectively, to accelerate both surface reactions. Furthermore, the facile transfer of electrons and holes across the TiOx‐In2O3 interface contributes to improving the reversibility of sensing kinetics. Through this study, the mechanistic understanding is established of how the surface chemistry of metal oxide surfaces can be tuned by light activation providing an effective route to the design fabrication of high‐performance gas sensors. [ABSTRACT FROM AUTHOR]

Transition metal dichalcogenides (TMDs) have attracted significant interest as gas‐sensing materials due to their unique crystal structure and surface. However, there are still issues when it comes to expanding the types of sensing gases for the TMD gas sensors. To extend gas‐sensing selectivity for the TMD gas sensors in this study, a monolayer (ML) 2D metal–organic framework (MOF) is introduced on top of the PtSe2 gas sensor, thereby tuning the major sensing analyte of PtSe2 from NO2 to H2S. Density functional theory calculations elucidate that the metal species of ML MOFs are attributed to the tuned selectivity of the analytes, based on the difference in binding energies. It is also demonstrated that ML MOF maintained the high responsivity of the pristine PtSe2 even at a low concentration of gas (200 ppb). This is further confirmed through the molecular dynamics simulations, which reveal that the ML feature of the ML MOF is highly essential to preserve the intrinsic ultra‐low limit detection properties of pristine PtSe2. [ABSTRACT FROM AUTHOR]

Flexible and mechanically robust gas sensors are the key technologies for wearable and implantable electronics. Herein, the authors demonstrate the high-performance, flexible nitrogen dioxide (NO2) chemiresistors using a series of n-type conjugated polymers (CPs: PNDIT2/IM-x) and a polymer dopant (poly(ethyleneimine), PEI). Imine double bonds (C = N) are incorporated into the backbones of the CPs with different imine contents (x) to facilitate strong and selective interactions with NO2. The PEI provides doping stability, enhanced electrical conductivity, and flexibility. As a result, the NO2 sensors with PNDIT2/IM-0.1 and PEI (1:1 by weight ratio) exhibit outstanding sensing performances, such as excellent sensitivity (𝚫R/Rb = 240%@1 ppm), ultralow detection limit (0.1 ppm), high selectivity (𝚫R/Rb < 8%@1 ppm of interfering analytes), and high stability, thereby outperforming other state-of-the-art CP-based chemiresistors. Furthermore, the thin film of PNDIT2/IM-0.1 and PEI blend is stretchable and mechanically robust, providing excellent flexibility to the NO2 sensors. Our study contributes to the rational design of high-performance flexible gas sensors. [ABSTRACT FROM AUTHOR]

[Display omitted] • Synthesis of atomically thin 2D metal oxide NSs by a chemical exfoliation process. • A comparative study on the humidity sensing performances of 2D Ru oxide and Mn oxide NSs. • Demonstration of real-time breath humidity monitoring using a wearable sensing module. Collecting real-time breath humidity data is important for calibrating gas sensors from interfering signals in breath components, ultimately for accurately monitoring a patient's physiological information for applications in non-invasive and point-of-care diagnostics. In this work, atomically thin 2D metal oxide nanosheets (NSs) were synthesized by a liquid phase exfoliation process and their humidity sensing properties were investigated. Interestingly, Opposite humidity sensing responses (R D /R H) were observed between semiconducting oxide and metallic oxide NSs. For the semiconducting manganese (Mn) oxide NSs, decreasing resistance transitions were obtained with the response of 24.01 at 44.5% RH at low humidity levels (i.e., 6.1–45% RH), which was governed by proton (H+) conduction. On the other hand, the metallic ruthenium (Ru) oxide NSs exhibited increasing resistance transitions with the response of 0.28 at 96.3% RH at a high humidity range (i.e., 50–99.9% RH) as a result of proton trapping by accepting electrons upon the exposure to excess water molecules. Ru oxide NSs exhibited the response and recovery times of 68 sec and 8 sec, respectively, at 96.3% RH. Real-time breath humidity monitoring is demonstrated by integrating Ru oxide NSs with a wristband-type wireless sensing module, which can transmit the sensing data to a mobile device. [ABSTRACT FROM AUTHOR]

[Display omitted] Electrodeposition and electropolymerization have emerged as versatile tools for the fabrication of chemical and biosensors. The literature in this area, published since 2017, is the main focus of this review. Electropolymerization has played a particularly prominent role in sensor development since its discovery in 1980 by Diaz at IBM. The ability to entrain receptors such as antibodies, engineered virus particles, and metal chelating agents into a conductive polymer sensing element during electropolymerization has proven to be a powerful means of preparing chemiresistors for a variety of analyses. Electrodeposition has also been used to prepare nanostructured metal indicator microelectrodes, enabling of a new modality for transducing biosensors. Electrodeposited metal nanowires have formed the basis for rapid and sensitive sensors for hydrogen gas. Electrodeposition has also been exploited as a powerful means for amplifying weak biosensor signals, extending their dynamic range. Opportunities for the application of electrodeposition and electropolymerization for chemical and biological sensor fabrication and function are discussed. [ABSTRACT FROM AUTHOR]

[Display omitted] • 2D-MOF is connected to 3D-MOF with coordination bond to form Ni-HHTP@UiO-66NH 2. • 2D-MOF@3D-MOF affords porosity, conductivity, and active interface for sensing. • Ni-HHTP@UiO-66NH 2 shows superior sensitivity and low detection limit toward H 2 S. • A plausible mechanism is proposed from the joint experimental/computational data. Research to develop ideal sensing devices for toxic gases is on the rise, and amongst various materials, metal–organic frameworks (MOFs) have opened up promising vistas as chemiresistive sensors due to their high structural and functional tunability. Here, we report the composites of dimensionally (2D and 3D) and functionally (conductive and porous) different two MOFs in the form of a well-integrated core–shell structure. The hierarchically assembled 2D-MOF@3D-MOF exhibits new interfacial properties that are responsible for synergetically enhanced sensing performances toward toxic H 2 S gas with the lowest recorded limit of detection (1.4 ppb), superior sensitivity (ΔR/R 0 = 3.37), and outstanding selectivity at room temperature in air. The sensing mechanisms are proposed by combinational studies of experiments and calculation, which indicates that multiple changes (e.g., local structural change of the shell MOF, secondary binding sites generation from the core MOF, and free radicals formation) play a critical role in achieving synergetic chemiresistive sensing. [ABSTRACT FROM AUTHOR]

[Display omitted] • A simple but powerful solution to overcome the chronic bottleneck of the nanocatalyst delivery on oxide support: the carbothermal shock driven nanocatalyst formation on carbon nanofibers (CNFs) with small sizes and fine distribution can be delivered to oxide structures of choice while retaining high uniformity. • Fabrication of catalyst delivered porous oxide structures: the asymmetric sputtering of oxide on CNFs can induce the formation of openly porous hemi-tubular structures with tunable porosity and thickness. A simple subsequent calcination results in the transfer of catalysts from the CNF template to the porous oxide structures. • Superior hydrogen sulfide sensing properties: Uniform distribution of Pt nanoparticles on SnO 2 hemitubes showed superior H 2 S sensing performances (Response Rair/Rgas > 1500 at 5 ppm H 2 S) compared to state-of-the-art H 2 S sensors. To achieve powerful gas sensors oxide semiconductor chemiresistors, the uniform functionalization of nanocatalysts on the desired metal oxides is considered as a key strategy. However, still, it is challenging to achieve the nanocatalysts decoration on desired oxides without deterioration of target materials. In this study, thermal-shock (rapid joule-heating method) was applied to uniformly decorate Pt nanoparticles (NPs) on the surface of carbon nanofibers (CNFs) to achieve the uniform distribution of Pt NPs on one-dimensional structures. And then, SnO 2 was physically deposited on the Pt NPs loaded CNFs and continuous heat-treatment was conducted to transfer the Pt NPs to desired SnO 2 porous hemitubes. Thanks to the well-distributed Pt NPs on porous SnO 2 hollow structures, the Pt laoded SnO 2 hemitubes showed an exceptional sensitivity (R air /R gas = 1500 at 5 ppm) in H 2 S. Also, it showed high selectivity for H 2 S and high stability even under continuous gas exposure, confirming its potential as an effective H 2 S sensor. [ABSTRACT FROM AUTHOR]

• The non-noble metals are introduced on graphene-based fiber as a sensitizer for the high-performance chemiresistor. • Metal oxides on graphene fibers naturally are converted into metals at a relatively low temperature annealing (under 700 °C) due to catalytic effect of graphene. • The graphene fiber acts as a flexible conductive support as well as a catalyst for the deoxidation of metal oxide. • The metal/metal oxide/graphene fibers exhibited a 16 times higher response to NO 2 gas and recovery than metal oxide/graphene fiber without metal. • The proposed strategy opens a new avenue for the realization of high-performance devices, such as chemical catalysts, photoactive devices. [Display omitted] Noble metal/metal-oxide-based hybrid gas sensors exhibit a low operating temperature, remarkable sensitivity, and fast recovery. As additives, noble metals induce a catalytic sensitization effect, which promotes charge transfer from the metal oxide to the analyte molecules, the so-called spillover mechanism. This suggests that metal catalysts can improve gas sensing performance. Herein, for the first time, non-noble metals are introduced on hybrid metal oxide/graphene fibers as sensitizers to fabricate high-performance chemiresistive sensors. The formation of metal components can be effectively controlled by annealing the metal oxide on graphene. Remarkably, compared with the corresponding metal oxide/graphene fiber sensors without metal components, the metal/metal oxide/graphene fiber sensors exhibit over a 16-fold higher response to NO 2 gas as well as effective recovery characteristics. Specifically, the Cu/Cu 2 O/graphene and Ni/NiO/graphene fiber sensors operating at 150 °C exhibit sensitivities of 18.90 % and 0.82 %, respectively, for 5 ppm NO 2 gas. The proposed strategy to achieve flexible graphene fiber chemiresistors by decorating them with non-noble metal and metal oxide nanoparticles opens a new avenue for realizing high-performance devices, such as photovoltaic devices, photocatalysts, and chemical catalysts. [ABSTRACT FROM AUTHOR]

• Porosity control of nanofibers: The high porosity of the metal oxide nanofibers is the key to achieving the dual sensitization owing to their high gas permeability and numerous active sites. Both saponin and water-ethanol co-solvent play critical roles in modifying morphology of nanofibers into elliptical nanofibers during electrospinning. Additionally, saponin forms numerous pores in the nanofibers when being burnt out during calcination. These porous, elliptical nanofibers possess a larger surface area and porosity.Saponin and water-ethanol co-solvent enabled porous, elliptical nanofibers to emerge. • Bifunctional Ga doping: Ga dopants enhanced sensing performance via conductivity improvement and grain growth inhibition. • Functionalization of Pt catalysts : Spill-over effects and chemical sensitization of remarkably improved C 2 H 2 sensitivity. Herein, we demonstrate a sensitization strategy via solid-solution doping and catalytic metal nanoparticles (NPs) onto porous metal oxide nanofibers (NFs) for superior acetylene (C 2 H 2) sensing capabilities. The introduction of dopants and catalysts not only increases the inherent reactivity of metal oxides, but also induces the spillover of C 2 H 2 onto metal oxides, significantly improving the sensing properties. We elucidate that the high porosity of the metal oxide NFs, prepared by electrospinning and utilizing saponin as a sacrificial template, is the key to achieving high gas permeability and numerous active sites. Consequently, Ga-doped ZnO porous NFs functionalized with Pt catalysts exhibited the highest C 2 H 2 sensing responses among the current state-of-the-art C 2 H 2 sensors (R a /R g = 26.2 at 400 °C) with a fast response time (10.2 s), at a particularly low concentration of 5 ppm. Moreover, these NFs showed excellent selectivity against the interfering gas (H 2 , C 7 H 8 , CO, CH 4 , C 8 H 10 , CH 3 COCH 3 , HCHO and C 2 H 5 OH) and outstanding stability up to 20 sensing cycles to 0.4 ppm of C 2 H 2. These results provide an efficient strategy to tailor composites of metal oxide nanostructures, dopants, and catalysts for highly sensitive gas sensors. [ABSTRACT FROM AUTHOR]