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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]

Single‐atom catalysts (SACs) supported on inorganic materials have attracted much attention in numerous research fields for their high catalytic performance. However, such SACs have been limited by the low metal loading, especially on different types of inorganic supports. Herein, a general approach is presented for preparing SACs on metallic, metal oxide, and perovskite nanosheet (NS) supports to reach a high metal loading of up to 3.94 wt%, by utilizing N‐doped graphene as a sacrificial template that spatially confines the single atoms (SAs). Specifically, the target support material precursors are adsorbed onto the SAs‐stabilized sacrificial template, followed by subsequent heat treatment to transfer the SAs to the support material and to remove the graphene layer. Pt SAs on oxide support exhibits little to no aggregation throughout >10 000 min of annealing at 275 °C, demonstrating high thermal stability, as also supported by ex situ post‐anneal electron microscopy and X‐ray absorption fine structure studies. As a proof‐of‐concept, Pt SACs on SnO2 NSs exhibit high catalytic activity toward chemiresistive sensing of acetone gas (response = 95.4 at 10 ppm, 7.6‐fold enhancement compared with pristine SnO2 NSs) and unprecedented stability under highly humid conditions (27.4% response deterioration at 95% relative humidity). [ABSTRACT FROM AUTHOR]

Chemical gas sensors have attracted much attention with the purposes of environmental hazardous gas detection and health monitoring via exhaled breath analysis. In particular, semiconducting metal oxide (SMO)‐based chemiresistors have been considered as one of the most attractive sensing platforms owing to its simple operation, low cost, ease of miniaturization and integration to mobile devices. However, SMO‐based sensors suffer from sluggish gas reactions and poor responses. To enhance their sensing characteristics, one‐dimensional (1D) nanostructures with large surface area and high porosity are desired, since sensing reactions with analytes mainly occur at the surface of the sensing layers. In addition, uniform catalyst functionalization on SMO supports is beneficial in terms of gas response, reaction speed, and selectivity. In this review, we comprehensively highlight recent progresses on diverse hollow 1D nanofibrous structures prepared using a well‐reputed technique of electrospinning, and their unique morphological advantages as highly sensitive chemical sensing layers. Finally, future perspectives on the synthesis and sensing characterizations of hollow nanofibrous sensing materials functionalized with robust catalysts are discussed. [ABSTRACT FROM AUTHOR]

This review reports on the most updated technological aspects of Li–air battery cathode materials. It provides the reader with recent developments, alongside critical views. The requirements for air‐cathodes, as well as the classification and characterization of carbon‐based and carbon‐free air cathodes, are listed. The effects of two major substituent groups of materials, namely carbon and advanced materials (metals, metal‐oxides, metal‐carbides, and metal‐nitrides) aimed at replacing carbon, are discussed in terms of their chemical and electrochemical stability. The report covers aspects of surface chemistry and structure influence on the electrolyte and discharge products stability. The review also reports on the efforts to suppress side reactions and deterioration of the polymeric binders (if a composite electrode is being considered). This is recognized as a means to enhance Li–air battery performance. The report concludes with an outlook and perspective, providing the readers with some insight on other factors and their impact on the long road toward a viable air‐cathode suitable for Li–air battery operations. [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]

Ultra-fast responding and recovering C2H5OH sensors were prepared using nanoscale SnO2hollow spheres with NiO-functionalized inner walls. The exceptional ultra-fast recovery characteristics were attributed to the catalytic surface reaction assisted by NiO at the inner shell. [ABSTRACT FROM AUTHOR]

2D heterogeneous oxide nanosheets (NSs) have attracted much attention in various scientific fields owing to their exceptional physicochemical properties. However, the fabrication of 2D oxide NSs with abundant p–n interfaces and large amounts of mesopores is extremely challenging. Here, a facile synthesis of highly porous 2D heterogeneous oxide NSs (e.g., SnO2/CoOx) is suggested through a 2D oxide exfoliation approach combined with a fast galvanic replacement reaction (GRR). The ultrathin (<5 nm) layered CoOx NSs are simply prepared by ion‐exchange exfoliation and a subsequent GRR process that induces a rapid phase transition from p‐type CoOx to n‐type SnO2 metal oxides (<10 min). The controlled GRR process enables the creation of heterogeneous SnO2/CoOx NSs consisting of small SnO2 grain sizes (<10 nm), high porosity, numerous heterojunctions, and sub‐10 nm thickness, which are highly advantageous characteristics for chemiresistive sensors. Due to the advantage of these features, the porous SnO2/CoOx NSs exhibit an unparalleled HCHO‐sensing performance (Rair/Rgas > 35 @ 5 ppm with a response speed of 9.34 s) with exceptional selectivity compared to that of the state‐of‐the‐art metal oxide‐based HCHO gas sensors. [ABSTRACT FROM AUTHOR]

Metal oxide nanosheets having high mesoporosity, grain size distribution of 5–10 nm, and ultrathin thickness have attracted much attention due to their intriguing properties such as high surface‐to‐volume ratio and superior chemical activities. However, 2D nanostructures tend to restack, inducing a decrease in accessible surface area and a number of pores. To solve this problem, herein, a unique synthetic method of crumpled metal oxide nanosheets using spray pyrolysis of metal ion–coated graphene oxide, followed by heat treatment, is reported. This method is applicable not only to single‐component metal oxides but also to heterogeneous multicomponent metal oxides in which composition can be controlled. Crumpled SnO2, ZnO, and Co3O4 as well as SnO2/ZnO and SnO2/Co3O4 nanosheets with heterogeneous interfaces are successfully synthesized and used as superior gas sensing layers. Because of the abundant reaction sites, well‐developed porosity for high gas accessibility, the formation of heterojunctions, the crumpled SnO2/ZnO and SnO2/Co3O4 nanosheets exhibit outstanding sensing performance (Rair/Rgas = 20.25 toward 5 ppm formaldehyde, and Rair/Rgas = 14.13 toward 5 ppm acetone, respectively). This study can contribute to the realization of a family of heterogeneous crumpled metal oxide nanosheets that can be applied to various research fields. [ABSTRACT FROM AUTHOR]

Electrospinning–etching strategy was employed to synthesize Pt-loaded SnO 2 hollow microbelts (Pt_SnO 2 HBLs) based chemiresistive-type sensor demonstrating high sensitivity and selectivity toward acetone gas. This strategy overcomes a major hurdle toward achieving ubiquitous gas diffusion in electrospun structures, and provides highly porous thin-walled HBLs with large surface area and small crystallites. [Display omitted] • In situ templating of SnO 2 with SiO 2 was employed to form Pt-loaded SiO 2 @SnO 2 core–shell microbelts. • Etching away of SiO 2 in the Pt-loaded SiO 2 @SnO 2 microbelts yielded Pt-loaded SnO 2 hollow microbelts. • The Pt-loaded SnO 2 hollow microbelts exhibited good response (R a /R g = 93.5) and selectivity toward 2 ppm acetone at 350 °C. Challenges for ubiquitous diffusion of gas analytes into semiconducting metal oxides (SMOs) based sensing layers have necessitated the introduction of unprecedented synthesis techniques for thin, porous and high-performance gas sensing materials. In this work, electrospinning and calcination were employed to prepare unprecedented SiO 2 –SnO 2 core–shell microbelts (hereinafter referred to as SiO 2 @SnO 2 BLs) followed by etching away of SiO 2 in NaOH solution (pH 12) to achieve hollow SnO 2 BLs (hereinafter referred to as SnO 2 HBLs) with mean crystal size of 14.01 nm, large BET surface area (143.5 m2‧g–1), high porosity (mean pore size of 5.7 nm), and shell thickness of 58.3 ± 11.4 nm. Sensitization of SnO 2 HBLs with apoferritin-templated platinum nanoparticles (Pt NPs) enhanced their detection capability toward acetone. Response (defined as R a /R g , where R a and R g are sensor resistances in air and target gas, respectively) of Pt(0.12 %)_SnO 2 HBLs toward 2 ppm acetone was up to 7.8 times higher compared to that of pristine SnO 2 HBLs, and exhibited faster response (9.2 s). The Pt(0.12 %)_SnO 2 HBLs based sensor indicated a promising long-term stability, and outstanding repeatability of response (R a /R g = 93.7 ± 0.89) toward 25 cycles of 2 ppm acetone exposure in a humid environment of 90 % relative humidity. This performance could be attributed to the unique morphology of HBLs, sensitization effects of catalytic Pt NPs, and enlargement of the electron-depleted layer resulting from a Schottky barrier between Pt NPs and SnO 2 grains. [ABSTRACT FROM AUTHOR]

Semiconducting metal oxides (SMOs) based gas sensors are inherently hampered by requirement of high working temperature because of their wide bandgaps. Consequently, there are remain challenges to utilize SMOs based gas sensors with regard to continuous gas monitoring platform with low power consumption. To address the inherent limitation, nitridation (i.e., N doping) of WO 3 NFs to WO x N y NFs was herein introduced for realization of low-temperature NO 2 sensing. Importantly, nitridation was conducted at intervals of 50 °C from 400 to 600 °C to adjust the degree of phase transition from semiconducting WO 3 to conductive WON phases. To further optimize the conductivity and improve the sensing characteristics, i.e., reduction of optimal operating temperature and enhancement of sensitivity, WO x N y NFs were functionalized with platinum (Pt) catalytic nanoparticles (NPs) by physical mixing. Pt NPs functionalized WO x N y NFs nitrided at 550 °C exhibited improved normalized resistance change and superior selectivity against C 2 H 5 OH, C 7 H 8 , CH 4 , CO, NH 3 , and NO at 50 °C. The noble metal catalyst–metal oxynitride hybrid system is suggested as an effective NO 2 sensing platform for low-temperature chemical sensor. [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]

In this work, highly porous WO 3 nanotubes (NTs) were synthesized by facile layer-by-layer (LbL) self-assembly on polymeric nanofiber (NF) templates followed by calcination. Polymeric NFs using poly(methyl methacrylate) (PMMA) were prepared by electrospinning as sacrificial templates. Then, ionic polymers were coated on PMMA to modify the surface charge of PMMA NFs. Catalyst-loaded WO 3 NTs were synthesized by self-assembly of tungsten precursor and catalytic precursor on the surface of the polymeric PMMA NFs followed by calcination at 500 °C for 1 h. Gas sensing performances were evaluated in highly humid atmosphere (90% RH) using pristine WO 3 NTs, Pt-loaded WO 3 NTs (Pt-WO 3 NTs), and Pd-loaded WO 3 NTs (Pd-WO 3 NTs). Pristine WO 3 NTs exhibited a high NO response ( R gas / R air = 63.59 at 5 ppm) at 350 °C and cross-selectivity toward toluene ( R air / R gas = 1.05 at 5 ppm). On the other hand, Pt-WO 3 NTs and Pd-WO 3 NTs exhibited a high toluene response ( R air / R gas = 2.24 for the Pt-WO 3 NTs and R air / R gas = 2.35 for the Pd-WO 3 NTs at 5 ppm) at 400 °C and a negligible NO response ( R gas / R air = 1.25 for the Pt-WO 3 NTs and R gas / R air = 1.04 for the Pd-WO 3 NTs at 5 ppm) at 400 °C. These results demonstrated that LbL synthesis is a highly promising method for producing hollow semiconductor metal oxide NTs functionalized with various catalysts, which leads to potential application in exhaled breath analysis for asthma and lung cancer diagnosis. [ABSTRACT FROM AUTHOR]

Abstract: This work presents a simple and versatile route to produce macroporous p-type metal oxide thin films. Two-dimensional arrays of p-type NiO films with a hollow hemisphere structure were fabricated by colloidal templating and RF-sputtering followed by a subsequent heat treatment. The diameter and shell thickness of the NiO hemisphere were 800nm and 20nm, respectively. X-ray diffraction and high-resolution transmission electron microscopy analysis indicate that the pure NiO phase with grain size of 10nm was obtained at calcination temperatures that exceeded 450°C. Close-packed arrays of hollow NiO hemispheres were found to exhibit p-type gas sensing properties against (CO, H2, C3H8, CH4, NO2, and C2H5OH), leading to significantly enhanced responses to C2H5OH (R gas /R air =5.0 at 200ppm). [Copyright &y& Elsevier]

Abstract: This work presents a new route to enhance the sensitivity of nanocrystalline TiO2 fibers based gas sensors. Pure and Pd-doped TiO2 nanofiber mats were synthesized by electrospinning and subsequent calcination. Highly porous fibrillar morphology was observed in the resultant nanocrystalline TiO2 fibers. In addition to anatase TiO2 crystallites, tiny (∼2nm) PdO crystallites were observed in the Pd-doped TiO2 fibers. The sensors using Pd-doped TiO2 fibers showed promising gas sensing characteristics, such as low operation temperature (180°C) and sufficient gas response (R/R o =38 to 2.1ppm NO2). The techniques outlined here offer new means for preparing novel metal-oxide nanofibers with catalytic dopants. [ABSTRACT FROM AUTHOR]

Abstract: To enhance the sensitivity of a metal oxide-based gas sensor, we introduce a novel electrical method that relies jointly on the use of impedance and an applied DC bias. We used polycrystalline ZnO–NiO composite thin films prepared by pulsed layer deposition as CO gas sensor material. The applied DC bias lowers the interface barrier between oxide grains and thereby enhances the sensitivity. Our approach enhances the sensitivity to CO gas by approximately 200% more than a conventional DC method. The enhancement effect is more pronounced when the CO concentration is lowered. This method offers an efficient characterization tool for modulating the sensitivity of gas sensors using semiconducting metal oxides. [Copyright &y& Elsevier]

Abstract: We report on high mobility ZnO thin film transistors (TFTs) (<5V), utilizing a room temperature grown MgO–Bi1.5Zn1.0Nb1.5O7 (BZN) composite gate insulator on a glass substrate. 30mol% MgO added BZN composite gate insulators exhibited greatly enhanced leakage current characteristics (~<2×10−8 A/cm2 at 0.3MV/cm) due to the high breakdown strength of MgO, while retaining an appropriate high-k dielectric constant of 32. The ZnO-TFTs with MgO–BZN composite gate insulators showed a high field-effect mobility of 37.2cm2/Vs, a reasonable on–off ratio of 1.54×105, a subthreshold swing of 460mV/dec, and a low threshold voltage of 1.7V. [Copyright &y& Elsevier]

• 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]

• To control the porosity, the e-spraying and PS beads templating route are combined, resulting in highly porous structure. • Pt functionalized PH-SnO 2 spheres exhibited high response (R air /R gas = 44.83) toward 5 ppm of acetone. • Pt-PH-SnO 2 spheres exhibited exceptional selectivity toward acetone against interfering molecules. Tailoring of semiconducting metal oxides (SMOs) nanostructures with high porosity is of importance for enhanced gas sensing performance. Hierarchically-assembled SMOs possess high surface area but often suffer from low porosity. Here, bimodal pore-loaded hierarchical SnO 2 (PH-SnO 2) spheres were successfully synthesized via electrostatic spraying method (e-spraying) combined with colloidal templating route using polystyrene beads. The resulting porous PH-SnO 2 spheres were used as sensing layers for detection of acetone, which exhibited about 20 % enhanced response compared with hierarchical SnO 2 (H-SnO 2) spheres without pores. In addition, e-spraying is a fascinating technique for uniform catalytic functionalization through a simple dispersion of catalytic nanoparticle (NPs) in the e-spraying solution to improve the sensing performance. As a result, the Pt-functionalized PH-SnO 2 (Pt-PH-SnO 2) spheres showed dramatically improved acetone detection capability with a response (R air /R gas) of 44.83 at 5 ppm as compared to PH-SnO 2 spheres (R air /R gas = 6.61) as well as superior selectivity. In this work, the unique combination of e-spraying and PS templating route paves the way for robust and facile synthetic method for bimodal pore loaded 3D hierarchical SMOs, and demonstrates the feasibility for application in exhaled breath sensors. [ABSTRACT FROM AUTHOR]