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The sensing performances of gas sensors must be improved and diversified to enhance quality of life by ensuring health, safety, and convenience. Metal-organic frameworks (MOFs), which exhibit an extremely high surface area, abundant porosity, and unique surface chemistry, provide a promising framework for facilitating gas-sensor innovations. Enhanced understanding of conduction mechanisms of MOFs has facilitated their use as gas-sensing materials, and various types of MOFs have been developed by examining the compositional and morphological dependences and implementing catalyst incorporation and light activation. Owing to their inherent separation and absorption properties and catalytic activity, MOFs are applied as molecular sieves, absorptive filtering layers, and heterogeneous catalysts. In addition, oxide- or carbon-based sensing materials with complex structures or catalytic composites can be derived by the appropriate post-treatment of MOFs. This review discusses the effective techniques to design optimal MOFs, in terms of computational screening and synthesis methods. Moreover, the mechanisms through which the distinctive functionalities of MOFs as sensing materials, heterostructures, and derivatives can be incorporated in gas-sensor applications are presented., (© 2023 Wiley-VCH GmbH.)

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 Co 3 O 4 @polyoxometalate yolk-shell structures using a metal-organic framework template. The inner space, including highly catalytic Co 3 O 4 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.

The accurate detection and identification of volatile aromatic hydrocarbons, which are highly toxic pollutants, are essential for assessing indoor and outdoor air qualities and protecting humans from their sources. However, real-time and on-site monitoring of aromatic hydrocarbons has been limited by insufficient sensor selectivity. Addressing the issue, bilayer oxide chemiresistors are developed using Rh-SnO 2 gas-sensing films and catalytic CeO 2 overlayers for rapidly and cost-effectively detecting traces of aromatic hydrocarbons in a highly discriminative and quantitative manner, even in gas mixtures. The sensing mechanism underlying the exceptional performance of bilayer sensor is systematically elucidated in relation to oxidative filtering of interferants by the CeO 2 overlayer. Moreover, CeO 2 -induced selective detection is validated using SnO 2 , Pt-SnO 2 , Au-SnO 2 , In 2 O 3 , Rh-In 2 O 3 , Au-In 2 O 3 , WO 3 , and ZnO sensors. Furthermore, sensor arrays are employed to enable pattern recognition capable of discriminating between aromatic gases and non-aromatic interferants and quantifying volatile aromatic hydrocarbon classifications., (© 2023. The Author(s).)

Oxide chemiresistors have mostly been used to detect reactive gases such as ethanol, acetone, formaldehyde, nitric dioxide, and carbon monoxide. However, the selective and sensitive detection of volatile aromatic compounds such as benzene, toluene, and xylene, which are extremely toxic and harmful, using oxide chemiresistors remains challenging because of the molecular stability of benzene rings containing chemicals. Moreover, the performance of the sensing materials is insufficient to detect trace concentration levels of volatile aromatic compounds, which lead to harmful effects on human beings. Here, the strategies for designing highly selective and sensitive volatile aromatic compound gas sensors using oxide chemiresistors were suggested and reviewed. Key approaches include the use of thermal activation, design of sensing materials with high catalytic activity, the utilization of catalytic microreactors and bilayer structures with catalytic overlayer, and the pretreatment of analyte gases or post analysis of sensing signals. In addition, future perspectives from the viewpoint of designing sensing materials and sensor structures for high-performance and robust volatile aromatic compounds gas sensors are provided. Finally, we discuss possible applications of the sensors and sensor arrays.

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 WO 3 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.

Solid oxide cells (SOCs) are promising sustainable and efficient electrochemical energy conversion devices. The application of a bilayer electrolyte comprising wide electrolytic oxide and highly conductive oxide is essential to lower the operating temperatures while maintaining high performance. However, a structurally and chemically ideal bilayer has been unattainable through cost-effective conventional ceramic processes. Here, we describe a strategy of naturally diffused sintering aid allowing the fabrication of defect-free doped-zirconia/doped-ceria bilayer electrolyte with full density and reduced interdiffusion layer at lower sintering temperature owing to the supply of small but appropriate amount of sintering aid from doped zirconia to doped ceria that makes the thermal shrinkages of both layers perfectly congruent. The resulting SOCs exhibit a minimal ohmic loss of 0.09 ohm cm 2 and remarkable performances in both fuel cell (power density exceeding 1.3 W cm −2 ) and electrolysis (current density of −1.27 A cm −2 at 1.3 V) operations at 700°C.

Formaldehyde, a probable carcinogen, is a ubiquitous indoor pollutant, but its highly selective detection has been a long-standing challenge. Herein, a chemiresistive sensor that can detect ppb-level formaldehyde in an exclusive manner at room temperature is designed. The TiO 2 sensor exhibits under UV illumination highly selective detection of formaldehyde and ethanol with negligible cross-responses to other indoor pollutants. The coating of a mixed matrix membrane (MMM) composed of zeolitic imidazole framework (ZIF-7) nanoparticles and polymers on TiO 2 sensing films removed ethanol interference completely by molecular sieving, enabling an ultrahigh selectivity (response ratio > 50) and response (resistance ratio > 1,100) to 5 ppm formaldehyde at room temperature. Furthermore, a monolithic and flexible sensor is fabricated successfully using a TiO 2 film sandwiched between a flexible polyethylene terephthalate substrate and MMM overlayer. Our work provides a strategy to achieve exclusive selectivity and high response to formaldehyde, demonstrating the promising potential of flexible gas sensors for indoor air monitoring., (© 2021. The Author(s).)

Metal-organic frameworks (MOFs) with high surface area, tunable porosity, and diverse structures are promising platforms for chemiresistors; however, they often exhibit low sensitivity, poor selectivity, and irreversibility in gas sensing, hindering their practical applications. Herein, we report that hybrids of Cu 3 (HHTP) 2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) nanoflakes and Fe 2 O 3 nanoparticles exhibit highly sensitive, selective, and reversible detection of NO 2 at 20 °C. The key parameters to determine their response, selectivity, and recovery are discussed in terms of the size of the Cu 3 (HHTP) 2 nanoflakes, the interaction between the MOFs and NO 2 , and an increase in the concentration and lifetime of holes facilitated by visible-light photoactivation and charge-separating energy band alignment of the hybrids. These photoactivated MOF-oxide hybrids suggest a new strategy for designing high-performance MOF-based gas sensors., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Nanotransfer printing (nTP) has attracted much attention due to its high pattern resolution, simple process, and low processing cost for useful nanofabrication. Here, we introduce a thermally assisted nTP (T-nTP) process for the effective fabrication of various periodic three-dimensional (3D) nanosheets, such as concavo-convex lines, spine lines, square domes, and complex multi-line patterns. The T-nTP method allows continuous nanoscale 3D patterns with functionality to be transferred onto both rigid and flexible substrates by heat without any collapse of uniform convex nanostructures with nanochannels. We also show the pattern formation of multi-layered hybrid structures consisting of two or more materials by T-nTP. Furthermore, the formation of silicon oxide nanodots (0D) within a printed metallic nanowave structure (3D) can be achieved by the combined method of T-nTP and the self-assembly of poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) block copolymers. Moreover, we demonstrate how to obtain well-defined oxide-metal hybrid nanostructures (0D-in-3D) through the spontaneous accommodation of PDMS spheres in the confined spaces of an Au-wave nanotemplate. This approach is applicable during the nanofabrication of various high-resolution devices with complex geometrical nanopatterns.

The highly selective detection of trace gases using transparent sensors at room temperature remains challenging. Herein, transparent nanopatterned chemiresistors composed of aligned 1D Au-SnO 2 nanofibers, which can detect toxic NO 2 gas at room temperature under visible light illumination is reported. Ten straight Au-SnO 2 nanofibers are patterned on a glass substrate with transparent electrodes assisted by direct-write, near-field electrospinning, whose extremely low coverage of sensing materials (≈0.3%) lead to the high transparency (≈93%) of the sensor. The sensor exhibits a highly selective, sensitive, and reproducible response to sub-ppm levels of NO 2 , and its detection limit is as low as 6 ppb. The unique room-temperature NO 2 sensing under visible light emanates from the localized surface plasmonic resonance effect of Au nanoparticles, thereby enabling the design of new transparent oxide-based gas sensors without external heaters or light sources. The patterning of nanofibers with extremely low coverage provides a general strategy to design diverse compositions of gas sensors, which can facilitate the development of a wide range of new applications in transparent electronics and smart windows wirelessly connected to the Internet of Things., (© 2021 Wiley-VCH GmbH.)

Volatile aromatic compounds are major air pollutants, and their health impacts should be assessed accurately based on the concentration and composition of gas mixtures. Herein, novel bilayer sensors consisting of a SnO 2 sensing layer and three different x Rh-TiO 2 catalytic overlayers ( x = 0.5, 1, and 2 wt%) are designed for the new functionalities such as the selective detection, discrimination, and analysis of benzene, toluene, and p -xylene. The 2Rh-TiO 2 /SnO 2 bilayer sensor shows a high selectivity and response toward ppm- and sub-ppm-levels of benzene over a wide range of sensing temperatures (325-425 °C). An array of 0.5Rh-, 1Rh-, and 2Rh-TiO 2 /SnO 2 sensors exhibits discrimination and composition analyses of aromatic compounds. The conversion of gases into more active species at moderate catalytic activation and the complete oxidation of gases into non-reactive forms by excessive catalytic promotion are proposed as the reasons behind the enhancement and suppression of analyte gases, respectively. Analysis using proton transfer reaction-quadrupole mass spectrometer (PTR-QMS) is performed to verify the above proposals. Although the sensing characteristics exhibit mild moisture interference, bilayer sensors with systematic and tailored control of gas selectivity and response provide new pathways for monitoring aromatic air pollutants and evaluating their health impacts., Competing Interests: The authors declare no conflict of interest., (© 2021 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

2D materials, such as graphene, exhibit great potential as functional materials for numerous novel applications due to their excellent properties. The grafting of conventional micropatterning techniques on new types of electronic devices is required to fully utilize the unique nature of graphene. However, the conventional lithography and polymer-supported transfer methods often induce the contamination and damage of the graphene surface due to polymer residues and harsh wet-transfer conditions. Herein, a novel strategy to obtain micropatterned graphene on polymer substrates using a direct curing process is demonstrated. Employing this method, entirely flexible, transparent, well-defined self-activated graphene sensor arrays, capable of gas discrimination without external heating, are fabricated on 4 in. wafer-scale substrates. Finite element method simulations show the potential of this patterning technique to maximize the performance of the sensor devices when the active channels of the 2D material are suspended and nanoscaled. This study contributes considerably to the development of flexible functional electronic devices based on 2D materials., (© 2020 Wiley-VCH GmbH.)

Artificial olfaction based on gas sensor arrays aims to substitute for, support, and surpass human olfaction. Like mammalian olfaction, a larger number of sensors and more signal processing are crucial for strengthening artificial olfaction. Due to rapid progress in computing capabilities and machine-learning algorithms, on-demand high-performance artificial olfaction that can eclipse human olfaction becomes inevitable once diverse and versatile gas sensing materials are provided. Here, rational strategies to design a myriad of different semiconductor-based chemiresistors and to grow gas sensing libraries enough to identify a wide range of odors and gases are reviewed, discussed, and suggested. Key approaches include the use of p-type oxide semiconductors, multinary perovskite and spinel oxides, carbon-based materials, metal chalcogenides, their heterostructures, as well as heterocomposites as distinctive sensing materials, the utilization of bilayer sensor design, the design of robust sensing materials, and the high-throughput screening of sensing materials. In addition, the state-of-the-art and key issues in the implementation of electronic noses are discussed. Finally, a perspective on chemiresistive sensing materials for next-generation artificial olfaction is provided., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

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-SnO 2 nanoreactors by loading Au nanoclusters on the inner surface of SnO 2 hollow shells using the layer-by-layer assembly technique. The results revealed that the sensor based on SnO 2 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 SnO 2 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.

Graphene-based electronic textile (e-textile) gas sensors have been developed for detecting hazardous NO 2 gas. For the e-textile gas sensor, electrical conductivity is a critical factor because it directly affects its sensitivity. To obtain a highly conductive e-textile, biomolecules have been used for gluing the graphene to the textile surface, though there remain areas to improve, such as poor conductivity and flexibility. Herein, we have developed a dopamine-graphene hybrid electronic textile yarn (DGY) where the dopamine is used as a bio-inspired adhesive to attach graphene to the surface of yarns. The DGY shows improved electrical conductivity (∼40 times) compared to conventional graphene-based e-textile yarns with no glue. Moreover, it exhibited improved sensing performance in terms of short response time (∼2 min), high sensitivity (0.02 μA/ppm), and selectivity toward NO 2 . The mechanical flexibility and durability of the DGY were examined through a 1000-cycle bending test. For a practical application, the DGY was attempted to detect the NO x emitted from vehicles, including gasoline, diesel, and fuel cell electric vehicles. Our results demonstrated that the DGYs-as a graphene-based e-textile gas sensor for detecting NO 2 -are simple to fabricate, cheap, disposable, and mechanically stable.

Sulfide solid electrolytes (SEs) with high Li-ion conductivities (σ ion ) and soft mechanical properties have limited applications in wet casting processes for commercial all-solid-state batteries (ASSBs) because of their inherent atmospheric and chemical instabilities. In this study, we fabricated sulfide SEs with a novel core-shell structure via environmental mechanical alloying, while providing sufficient control of the partial pressure of oxygen. This powder possesses notable atmospheric stability and chemical resistance because it is covered with a stable oxysulfide nanolayer that prevents deterioration of the bulk region. The core-shell SEs showed a σ ion of more than 2.50 mS cm -1 after air exposure (for 30 min) and reaction with slurry chemicals (mixing and drying for 31 min), which was approximately 82.8% of the initial σ ion . The ASSB cell fabricated through wet casting provided an initial discharge capacity of 125.6 mAh g -1 . The core-shell SEs thus exhibited improved powder stability and reliability in the presence of chemicals used in various wet casting processes for commercial ASSBs., Competing Interests: The authors declare no competing financial interest.

Potassium-ion batteries (KIBs) are considered as promising alternatives to lithium-ion batteries owing to the abundance and affordability of potassium. However, the development of suitable electrode materials that can stably store large-sized K ions remains a challenge. This study proposes a facile impregnation method for synthesizing ultrafine cobalt-iron bimetallic selenides embedded in hollow mesoporous carbon nanospheres (HMCSs) as superior anodes for KIBs. This involves loading metal precursors into HMCS templates using a repeated "drop and drying" process followed by selenization at various temperatures, facilitating not only the preparation of bimetallic selenide/carbon composites but also controlling their structures. HMCSs serve as structural skeletons, conductive templates, and vehicles to restrain the overgrowth of bimetallic selenide particles during thermal treatment. Various analysis strategies are employed to investigate the charge-discharge mechanism of the new bimetallic selenide anodes. This unique-structured composite exhibits a high discharge capacity (485 mA h g -1 at 0.1 A g -1 after 200 cycles) and enhanced rate capability (272 mA h g -1 at 2.0 A g -1 ) as a promising anode material for KIBs. Furthermore, the electrochemical properties of various nanostructures, from hollow to frog egg-like structures, obtained by adjusting the selenization temperature, are compared., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nanotransfer printing (nTP) has attracted considerable attention due to its good pattern resolution, process simplicity, and cost-effectiveness. However, the development of a large-area nTP process has been hampered by critical reliability issues related to the uniform replication and regular transfer printing of functional nanomaterials. Here, we present a very practical thermally assisted nanotransfer printing (T-nTP) process that can easily produce well-ordered nanostructures on an 8-inch wafer via the use of a heat-rolling press system that provides both uniform pressure and heat. We also demonstrate various complex pattern geometries, such as wave, square, nut, zigzag, and elliptical nanostructures, on diverse substrates via T-nTP. Furthermore, we demonstrate how to obtain a high-density crossbar metal-insulator-metal memristive array using a combined method of T-nTP and directed self-assembly. We expect that the state-of-the-art T-nTP process presented here combined with other emerging patterning techniques will be especially useful for the large-area nanofabrication of various devices., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Although several crystalline materials have been developed as Li-ion conductors for use as solid electrolytes in all-solid-state batteries (ASSBs), producing materials with high Li-ion conductivities is time-consuming and cost-intensive. Herein, we introduce a superionic halogen-rich Li-argyrodite (HRLA) and demonstrate its innovative synthesis using ultimate-energy mechanical alloying (UMA) and rapid thermal annealing (RTA). UMA with a 49 G-force milling energy provides a one-pot process that includes mixing, glassification, and crystallization, to produce as-milled HRLA powder that is ∼70% crystallized; subsequent RTA using an infrared lamp increases this crystallinity to ∼82% within 25 min. Surprisingly, this HRLA exhibits the highest Li-ion conductivity among Li-argyrodites (10.2 mS cm -1 at 25 °C, cold-pressed powder compact) reported so far. Furthermore, we confirm that this superionic HRLA works well as a promising solid electrolyte without a decreased intrinsic electrochemical window in various electrode configurations and delivers impressive cell performance (114.2 mAh g -1 at 0.5 C).

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 SnO 2 sensor coated with the nanoscale catalytic Cr 2 O 3 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 Cr 2 O 3 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., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

Highly efficient anode materials with novel compositions for Li-ion batteries are actively being researched. Multicomponent metal selenite is a promising candidate, capable of improving their electrochemical performance through the formation of metal oxide and selenide heterostructure nanocrystals during the first cycle. Here, the binary nickel-cobalt selenite derived from Ni-Co Prussian blue analogs (PBA) is chosen as the first target material: the Ni-Co PBA are selenized and partially oxidized in sequence, yielding (NiCo)SeO 3 phase with a small amount of metal selenate. The conversion mechanism of (NiCo)SeO 3 for Li-ion storage is studied by cyclic voltammetry, in situ X-ray diffraction, ex situ X-ray photoelectron spectroscopy, in situ electrochemical impedance spectroscopy, and ex situ transmission electron microscopy. The reversible reaction mechanism of (NiCo)SeO 3 with the Li ions is described by the reaction: NiO + CoO + xSeO 2 + (1 - x)Se + (4x + 6)Li + + (4x + 6)e - ↔ Ni + Co + (2x + 2)Li 2 O + Li 2 Se. To enhance electrochemical properties, polydopamine-derived carbon is uniformly coated on (NiCo)SeO 3 , resulting in excellent cycling and rate performances for Li-ion storage. The discharge capacity of C-coated (NiCo)SeO 3 is 680 mAh g -1 for the 1500th cycle when cycled at a current density of 5 A g -1 ., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Noble metals or oxide catalysts have traditionally been loaded or doped to enhance the gas sensing properties of oxide semiconductor chemiresistors. However, the selective detection of various chemicals for a wide range of new applications remains a challenging problem. In this paper, we propose a novel bilayer design with an oxide chemiresistor sensing layer and nanoscale catalytic Au overlayer to provide high controllability for gas sensing characteristics. The Au nanocluster overlayer significantly enhances the methylbenzene response of a SnO 2 thick film sensor by reforming gases into more reactive species and suppresses the responses to reactive interference gases through oxidative filtering, leading to excellent selectivity to methylbenzene. Gas sensing characteristics can be tuned by controlling the morphology, amount, and number density of Au nanoclusters through the variation in the Au coating thickness (0.5-3 nm) and thermal annealing conditions (0.5-4 h at 550 °C). Furthermore, the general validity of the proposed Au-coated bilayer sensor design was confirmed through the enhancement of response and selectivity toward methylbenzenes by coating Au nanoclusters onto ZnO and Co 3 O 4 sensors. The sensing mechanism, advantages, and potential applications of bilayer sensors are discussed from the perspective of the separation of sensing and catalytic reactions, as well as the reforming and oxidation of analyte gases in association with the configuration of the sensing layer and Au catalytic overlayer.

Pure and 3-12 at. % Pr-doped In 2 O 3 macroporous spheres were fabricated by ultrasonic spray pyrolysis and their acetone-sensing characteristics under dry and humid conditions were investigated to design humidity-independent gas sensors. The 12 at. % Pr-doped In 2 O 3 sensor exhibited approximately the same acetone responses and sensor resistances at 450 °C regardless of the humidity variation, whereas the pure In 2 O 3 exhibited significant deterioration in gas-sensing characteristics upon the change in the atmosphere, from dry to humid (relative humidity: 80%). Moreover, the 12 at. % Pr-doped In 2 O 3 sensor exhibited a high response to acetone with negligible cross responses to interfering gases (NH 3 , CO, benzene, toluene, NO 2 , and H 2 ) under the highly humid atmosphere. The mechanism for the humidity-immune gas-sensing characteristics was investigated by X-ray photoelectron and diffuse reflectance infrared Fourier transform spectroscopies together with the phenomenological gas-sensing results and discussed in relation with Pr 3+ /Pr 4+ redox pairs, regenerative oxygen adsorption, and scavenging of hydroxyl groups.

Multicomponent materials with various double cations have been studied as anode materials of lithium-ion batteries (LIBs). Heterostructures formed by coupling different-bandgap nanocrystals enhance the surface reaction kinetics and facilitate charge transport because of the internal electric field at the heterointerface. Accordingly, metal selenites can be considered efficient anode materials of LIBs because they transform into metal selenide and oxide nanocrystals in the first cycle. However, few studies have reported synthesis of uniquely structured metal selenite microspheres. Herein, synthesis of high-porosity CoSeO 3 microspheres is reported. Through one-pot oxidation at 400 °C, CoSe x -C microspheres formed by spray pyrolysis transform into CoSeO 3 microspheres showing unordinary cycling and rate performances. The conversion mechanism of CoSeO 3 microspheres for lithium-ion storage is systematically studied by cyclic voltammetry, in situ X-ray diffraction and electrochemical impedance spectroscopy, and transmission electron microscopy. The reversible reaction mechanism of the CoSeO 3 phase from the second cycle onward is evaluated as CoO + xSeO 2 + (1 - x)Se + 4(x + 1)Li + + 4( x + 1)e - ↔ Co + (2x + 1)Li 2 O + Li 2 Se. The CoSeO 3 microspheres show a high reversible capacity of 709 mA h g -1 for the 1400th cycle at a current density of 3 A g -1 and a high reversible capacity of 526 mA h g -1 even at an extremely high current density of 30 A g -1 ., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Graphene is one of the most promising materials for high-performance gas sensors due to its unique properties such as high sensitivity at room temperature, transparency, and flexibility. However, the low selectivity and irreversible behavior of graphene-based gas sensors are major problems. Here, we present unprecedented room temperature hydrogen detection by Au nanoclusters supported on self-activated graphene. Compared to pristine graphene sensors, the Au-decorated graphene sensors exhibit highly improved gas-sensing properties upon exposure to various gases. In particular, an unexpected substantial enhancement in H2 detection is found, which has never been reported for Au decoration on any type of chemoresistive material. Density functional theory calculations reveal that Au nanoclusters on graphene contribute to the adsorption of H atoms, whereas the surfaces of Au and graphene do not bind with H atoms individually. The discovery of such a new functionality in the existing material platform holds the key to diverse research areas based on metal nanocluster/graphene heterostructures.

Three PbTiO 3 nanostructures were synthesized using a one-step hydrothermal reaction with different TiO 2 powders as Ti sources, and their gas-sensing properties were investigated. The sensor comprising PbTiO 3 nanoplates (NPs) exhibited a high response (resistance ratio = 80.4) to 5 ppm ethanol at 300 °C and could detect trace concentrations of ethanol down to 100 ppb. Moreover, the sensor showed high ethanol selectivity and nearly the same sensing characteristics despite the wide range of humidity variation from 20 to 80% RH. The mechanism for humidity-independent gas sensing was elucidated using diffuse reflectance infrared Fourier transform spectra. PbTiO 3 NPs are new and promising sensing materials that can be used for detecting ethanol in a highly sensitive and selective manner with negligible interference from ambient humidity.

Detection and monitoring of harmful and toxic gases have gained increased interest in relation to worldwide environmental issues. Semiconducting metal oxide gas sensors have been considered promising for the facile remote detection of gases and vapors over the past decades. However, their sensing performance is still a challenge to meet the demands for practical applications where excellent sensitivity, selectivity, stability, and response/recovery rate are imperative. Therefore, sensing materials with novel architectures and fabrication processes have been pursued with a flurry of research activity. In particular, the preparation of ordered macroporous metal oxide nanostructures is regarded as an intriguing candidate wherein ordered aperture sizes in the range from 50 nm to 1.5 μm can increase the chemical diffusion rate and considerably strengthen the performance stability and repeatability. This review highlights the recent advances in the fabrication of ordered macroporous nanostructures with different dimensions and compositions, discusses the sensing behavior evolution governed by structural layouts, hierarchy, doping, and heterojunctions, as well as considering their general principles and future prospects. This would provide a clear scale for others to tune the sensing performance of porous materials in terms of specific components and structural designs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Ultrahigh gas selectivity and response for ppb levels of xylene are achieved by doping Pt in CoCr2O4 hollow spheres, whereas the addition of Au or Pd is less effective or even deteriorated the performance.

Ammonia (NH 3 ) is an irritant gas with a unique pungent odor; sub-parts per million-level breath ammonia is a medical biomarker for kidney disorders and Helicobacter pylori bacteria-induced stomach infections. The humidity varies in both ambient environment and exhaled breath, and thus humidity dependence of gas-sensing characteristics is a great obstacle for real-time applications. Herein, flexible, humidity-independent, and room-temperature ammonia sensors are fabricated by the thermal evaporation of CuBr on a polyimide substrate and subsequent coating of a nanoscale moisture-blocking CeO 2 overlayer by electron-beam evaporation. CuBr sensors coated with a 100 nm-thick CeO 2 overlayer exhibits an ultrahigh response (resistance ratio) of 68 toward 5 ppm ammonia with excellent gas selectivity, rapid response, reversibility, and humidity-independent sensing characteristics at room temperature. In addition, the sensing performance remains stable after repetitive bending and long-term operation. Moreover, the sensors exhibit significant response to the simulated exhaled breath of patients with H. pylori infection; the simulated breath contains 50 ppb NH 3 . The sensors thus show promising potential in detecting sub-parts per million-level NH 3 , regardless of humidity fluctuations, which can open up new applications in wearable devices for in situ medical diagnosis and indoor/outdoor environment monitoring.

The chemiresistive sensing characteristics of metal oxide gas sensors depend closely on ambient humidity. Herein, we report that gas sensors using Tb-doped SnO 2 yolk-shell spheres can be used for reliable acetone detection, regardless of the variations in humidity. Pure SnO 2 and Tb-doped SnO 2 yolk-shell spheres were prepared via ultrasonic spray pyrolysis and their chemiresistive sensing characteristics were studied. The sensor resistance and gas response of the pure SnO 2 yolk-shell spheres significantly changed and deteriorated upon exposure to moisture. In stark contrast, the Tb-doped SnO 2 yolk-shell spheres exhibited similar gas responses and sensor resistances in both dry and humid [relative humidity (RH) 80%] atmospheres. In addition, the Tb-doped SnO 2 yolk-shell sensors showed a high gas response (resistance ratio) of 1.21 to the sub-ppm-levels (50 ppb) of acetone with low responses to the other interference gases. The effects of Tb oxide and the chemical interactions among the Tb oxide, SnO 2 , and water vapor on this humidity-independent gas sensing behavior of the Tb-doped SnO 2 yolk-shell sensors were investigated. This strategy can provide a new road to achieve highly sensitive, selective, and humidity-independent sensing of acetone, which will facilitate miniaturized and real-time exhaled breath analysis for diagnosing diabetes.

Sn-doped NiO multiroom spheres with unique microreactor morphology were prepared by facile ultrasonic spray pyrolysis of a solution containing tin oxalate, nickel nitrate, and dextrin and subsequent heat treatment. The multiroom structure was formed by phase segregation between the molten metal source and liquidlike dextrin and sequent decomposition of dextrin during spray pyrolysis, which played the dual roles of enhancing gas response and selectivity. The response (resistance ratio) of the Sn-doped NiO multiroom spheres to 1 ppm p-xylene was as high as 65.4 at 300 °C, which was 50.3 and 9.0 times higher than those of pure NiO multiroom spheres and Sn-doped NiO dense spheres, respectively. In addition, the Sn-doped NiO multiroom sensors showed a high selectivity to xylene. The unprecedented high response that enables the sensing of sub-ppm xylene was explained by the high gas accessibility of the multiroom structures and the Sn-doping-induced change in oxygen adsorption as well as the charge carrier concentration, whereas the high xylene selectivity was attributed to the decomposition/re-forming of xylene into smaller or more active species within the unique multiroom structure of Sn-doped NiO microreactors characterized by high catalytic activities. The multiroom oxide spheres can be used as a new and generalized platform to design high-performance gas sensors.

Nearly monodisperse hollow hierarchical Co 3 O 4 nanocages of four different sizes (∼0.3, 1.0, 2.0, and 4.0 μm) consisting of nanosheets were prepared by controlled precipitation of zeolitic imidazolate framework-67 (ZIF-67) rhombic dodecahedra, followed by solvothermal synthesis of Co 3 O 4 nanocages using ZIF-67 self-sacrificial templates, and subsequent heat treatment for the development of high-performance methylbenzene sensors. The sensor based on hollow hierarchical Co 3 O 4 nanocages with the size of ∼1.0 μm exhibited not only ultrahigh responses (resistance ratios) to 5 ppm p-xylene (78.6) and toluene (43.8) but also a remarkably high selectivity to methylbenzene over the interference of ubiquitous ethanol at 225 °C. The unprecedented and high response and selectivity to methylbenzenes are attributed to the highly gas-accessible hollow hierarchical morphology with thin shells, abundant mesopores, and high surface area per unit volume as well as the high catalytic activity of Co 3 O 4 . Moreover, the size, shell thickness, mesopores, and hollow/hierarchical morphology of the nanocages, the key parameters determining the gas response and selectivity, could be well-controlled by tuning the precipitation of ZIF-67 rhombic dodecahedra and solvothermal reaction. This method can pave a new pathway for the design of high-performance methylbenzene sensors for monitoring the quality of indoor air.

Co 3 O 4 sensors with a nanoscale TiO 2 or SnO 2 catalytic overlayer were prepared by screen-printing of Co 3 O 4 yolk-shell spheres and subsequent e-beam evaporation of TiO 2 and SnO 2 . The Co 3 O 4 sensors with 5 nm thick TiO 2 and SnO 2 overlayers showed high responses (resistance ratios) to 5 ppm xylene (14.5 and 28.8) and toluene (11.7 and 16.2) at 250 °C with negligible responses to interference gases such as ethanol, HCHO, CO, and benzene. In contrast, the pure Co 3 O 4 sensor did not show remarkable selectivity toward any specific gas. The response and selectivity to methylbenzenes and ethanol could be systematically controlled by selecting the catalytic overlayer material, varying the overlayer thickness, and tuning the sensing temperature. The significant enhancement of the selectivity for xylene and toluene was attributed to the reforming of less reactive methylbenzenes into more reactive and smaller species and oxidative filtering of other interference gases, including ubiquitous ethanol. The concurrent control of the gas reforming and oxidative filtering processes using a nanoscale overlayer of catalytic oxides provides a new, general, and powerful tool for designing highly selective and sensitive oxide semiconductor gas sensors.

Semiconductor gas sensors using metal oxides, carbon nanotubes, graphene-based materials, and metal chalcogenides have been reviewed from the viewpoint of the sensitive, selective, and reliable detection of exhaled biomarker gases, and perspectives/strategies to realize breath analysis on a chip for disease diagnosis are discussed based on the concurrent design of high-performance sensing materials and miniaturized pretreatment components. Carbon-based sensing materials that show relatively high responses to NO and NH 3 at low or mildly raised temperatures can be applied to the diagnosis of asthma and renal disease. Halitosis can be diagnosed by employing sensing or additive materials such as CuO and Mo that have high chemical affinities for H 2 S, while catalyst-loaded metal oxide nanostructure sensors or their arrays have been used to diagnose diabetes via the selective detection of acetone or by pattern recognition of sensor signals. For the ultimate miniaturization of a breath-analysis system into a tiny chip, preconditioning that includes preconcentration, dehumidification, and flow sensing needs to be either improved through the design of gas/moisture adsorbents or removed/simplified through the design of highly sensitive sensing materials that are less impervious to interference from humidity and temperature. Moreover, an abundant sensing library needs to be provided for the diagnosis of diseases (e.g. lung cancer) that are associated with multiple biomarker gases and for finding new methods to diagnose other diseases. For this aim, p-type oxide semiconductors with high catalytic activities, as well as combinatorial approaches, can be considered for the development of sensing materials that detect less-reactive large molecules, and high-throughput screening, respectively. Selectivity for a specific biomarker gas will simplify the system further. Breath analysis on a tiny chip using semiconductor chemiresistors with ultralow power consumption that is connected to the 'Internet of Things' will pave new roads for disease diagnosis and patient monitoring.

NiO/NiWO 4 composite yolk-shell spheres with a nanoscale NiO outer layer were prepared using one-pot ultrasonic spray pyrolysis and their gas sensing characteristics were studied. The NiO/NiWO 4 yolk-shell spheres exhibited an extremely high response to 5 ppm p-xylene (ratio of resistance to gas and air = 343.5) and negligible cross-responses to 5 ppm ethanol, ammonia, carbon monoxide, hydrogen, and benzene, whereas pure NiO yolk-shell spheres showed very low responses and selectivity to all the analyte gases. The detection limit for p-xylene was as low as 22.7 ppb. This ultrasensitive and selective detection of p-xylene is attributed to a synergistic catalytic effect between NiO and NiWO 4 , high gas accessibility with large specific surface area, and increased chemiresistive variation due to the formation of a heterojunction. The NiO/NiWO 4 yolk-shell spheres with a thin NiO outer layer can be used to detect subppm-level p-xylene in a highly sensitive and selective manner for monitoring indoor air pollution.

Herein, the fabrication and characterization of highly sensitive and selective ethanol gas sensor based on CuO nanodisks is reported. The CuO nanodisks were synthesized by facile hydrothermal process and detailed characterization revealed the well-crystallinity, high-purity and high density growth of the prepared material. To fabricate the ethanol gas sensor, the prepared nanodisks were coated on alumina substrate. The fabricated sensor exhibited high-sensitivity and the recorded gas response (resistance-ratio), response time (τ res) and recovery time (τ recov) were 6.2, 119 and 35 s, respectively for 100 ppm of C₂H₅OH at 300 °C. Further, the fabricated sensor shows high selectivity towards ethanol gas compared to H₂ and CO gases.

Xylene is a hazardous volatile organic compound, which should be measured precisely for monitoring of indoor air quality. The selective detection of ppm-level xylene using oxide semiconductor chemiresistors, however, remains a challenging issue. In this study, NiO/NiMoO 4 nanocomposite hierarchical spheres assembled from nanosheets were prepared by hydrothermal reaction, and the potential of sensors composed of these nanocomposites to selectively detect xylene gas was investigated. The sensors based on the NiO/NiMoO 4 nanocomposite hierarchical spheres exhibited high responses (maximum resistance ratio =101.5) to 5 ppm p-xylene with low cross-responses (resistance ratios <30) to 5 ppm toluene, benzene, C 2 H 5 OH, CH 3 COCH 3 , HCHO, CO, trimethylamine, and NH 3 . In contrast, a sensor based on pure NiO hierarchical spheres exhibited negligibly low responses to all 9 analyte gases. The gas-sensing mechanism underlying the high selectivity and response to xylene in the NiO/NiMoO 4 nanocomposite hierarchical spheres is discussed in relation to the catalytic promotion of the xylene-sensing reaction by synergistic combination between NiO and NiMoO 4 , gas-accessible hierarchical morphology, and electronic sensitization by Mo addition. Highly selective detection of xylene can pave the road toward a new solution for precise monitoring of indoor air pollution.

Strategies for the enhancement of gas sensing properties, and specifically the improvement of gas selectivity of metal oxide semiconductor nanowire (NW) networks grown by chemical vapor deposition and thermal evaporation, are reviewed. Highly crystalline NWs grown by vapor-phase routes have various advantages, and thus have been applied in the field of gas sensors over the years. In particular, n -type NWs such as SnO₂, ZnO, and In₂O₃ are widely studied because of their simple synthetic preparation and high gas response. However, due to their usually high responses to C₂H₅OH and NO₂, the selective detection of other harmful and toxic gases using oxide NWs remains a challenging issue. Various strategies-such as doping/loading of noble metals, decorating/doping of catalytic metal oxides, and the formation of core-shell structures-have been explored to enhance gas selectivity and sensitivity, and are discussed herein. Additional methods such as the transformation of n -type into p -type NWs and the formation of catalyst-doped hierarchical structures by branch growth have also proven to be promising for the enhancement of gas selectivity. Accordingly, the physicochemical modification of oxide NWs via various methods provides new strategies to achieve the selective detection of a specific gas, and after further investigations, this approach could pave a new way in the field of NW-based semiconductor-type gas sensors., Competing Interests: The authors declare no conflict of interest.

Vertically ordered hematite nanotubes are considered to be promising photoactive materials for high-performance water-splitting photoanodes. However, the synthesis of hematite nanotubes directly on conducting substrates such as fluorine-doped tin oxide (FTO)/glass is difficult to be achieved because of the poor adhesion between hematite nanotubes and FTO/glass. Here, we report the synthesis of hematite nanotubes directly on FTO/glass substrate and high-performance photoelectrochemical properties of the nanotubes with NiFe cocatalysts. The hematite nanotubes are synthesized by a simple electrochemical anodization method. The adhesion of the hematite nanotubes to the FTO/glass substrate is drastically improved by dipping them in nonpolar cyclohexane prior to postannealing. Bare hematite nanotubes show a photocurrent density of 1.3 mA/cm(2) at 1.23 V vs a reversible hydrogen electrode, while hematite nanotubes with electrodeposited NiFe cocatalysts exhibit 2.1 mA/cm(2) at 1.23 V which is the highest photocurrent density reported for hematite nanotubes-based photoanodes for solar water splitting. Our work provides an efficient platform to obtain high-performance water-splitting photoanodes utilizing earth-abundant hematite and noble-metal-free cocatalysts.

The humidity dependence of the gas sensing characteristics of metal oxide semiconductors has been one of the greatest obstacles for gas sensor applications during the last five decades because ambient humidity dynamically changes with the environmental conditions. Herein, a new and novel strategy is reported to eliminate the humidity dependence of the gas sensing characteristics of oxide chemiresistors via dynamic self-refreshing of the sensing surface affected by water vapor chemisorption. The sensor resistance and gas response of pure In2 O3 hollow spheres significantly change and deteriorate in humid atmospheres. In contrast, the humidity dependence becomes negligible when an optimal concentration of CeO2 nanoclusters is uniformly loaded onto In2 O3 hollow spheres via layer-by-layer (LBL) assembly. Moreover, In2 O3 sensors LBL-coated with CeO2 nanoclusters show fast response/recovery, low detection limit (500 ppb), and high selectivity to acetone even in highly humid conditions (relative humidity 80%). The mechanism underlying the dynamic refreshing of the In2 O3 sensing surfaces regardless of humidity variation is investigated in relation to the role of CeO2 and the chemical interaction among CeO2 , In2 O3 , and water vapor. This strategy can be widely used to design high performance gas sensors including disease diagnosis via breath analysis and pollutant monitoring., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

SnSe nanoplates with thin and uniform morphology are prepared by one-pot spray pyrolysis, and are examined as anode materials for Na-ion batteries. During the spray pyrolysis process, metallic Se and Sn are prepared from SeO2 and SnO2, respectively, under a reducing atmosphere. Metallic Sn and metalloid Se, with melting points of 232 and 221 °C, respectively, form a melted Sn-Se mixture, which reacts exothermally to form SnSe nanocrystals. Several of these nanocrystals are grown simultaneously forming a micron-sized powder. Complete elimination of the excess amount of metalloid Se, by forming H2Se gas, results in aggregation-free SnSe nanoplates. The aspect ratio of these nanoplates is as high as 11.3. The discharge capacities for the SnSe nanoplates, prepared from spray solutions containing 100, 400, and 800% of the stoichiometric SeO2 content needed to form SnSe, are 407, 558, and 211 mA h g(-1), respectively, after 50 cycles at a constant current density of 0.3 A g(-1); their capacity retentions calculated from the second cycle onwards are 77, 100, and 60%, respectively. The phase pure SnSe nanoplates with a high aspect ratio show good cycling and rate performances for Na-ion storage.

Monolayers of periodic porous Co3 O4 inverse opal (IO) thin films for gas-sensor applications were prepared by transferring cobalt-solution-dipped polystyrene (PS) monolayers onto sensor substrates and subsequent removal of the PS template by heat treatment. Monolayer Co3 O4 IO thin films having periodic pores (d≈500 nm) showed a high response of 112.9 to 5 ppm C2 H5 OH at 200 °C with low cross-responses to other interfering gases. Moreover, the selective detection of xylene and methyl benzenes (xylene+toluene) could be achieved simply by tuning the sensor temperature to 250 and 275 °C, respectively, so that multiple gases can be detected with a single chemiresistor. Unprecedentedly high ethanol response and temperature-modulated control of selectivity with respect to ethanol, xylene, and methyl benzenes were attributed to the highly chemiresistive IO nanoarchitecture and to the tuned catalytic promotion of different gas-sensing reactions, respectively. These well-ordered porous nanostructures could have potential in the field of high-performance gas sensors based on p-type oxide semiconductors., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Co3O4 hollow spheres prepared by ultrasonic spray pyrolysis were converted into Co3O4-SnO2 core-shell hollow spheres by galvanic replacement with subsequent calcination at 450 °C for 2 h for gas sensor applications. Gas selectivity of the obtained spheres can be controlled by varying the amount of SnO2 shells (14.6, 24.3, and 43.3 at. %) and sensor temperatures. Co3O4 sensors possess an ability to selectively detect ethanol at 275 °C. When the amount of SnO2 shells was increased to 14.6 and 24.3 at. %, highly selective detection of xylene and methylbenzenes (xylene + toluene) was achieved at 275 and 300 °C, respectively. Good selectivity of Co3O4 hollow spheres to ethanol can be explained by a catalytic activity of Co3O4; whereas high selectivity of Co3O4-SnO2 core-shell hollow spheres to methylbenzenes is attributed to a synergistic effect of catalytic SnO2 and Co3O4 and promotion of gas sensing reactions by a pore-size control of microreactors.

The Kirkendall effect and Ostwald ripening were successfully combined to prepare uniquely structured NiO aggregates. In particular, a NiO-C composite powder was first prepared using a one-pot spray pyrolysis, which was followed by a two-step post-treatment process. This resulted in the formation of micron-sized spherical and hollow-structured NiO aggregates through a synergetic effect that occurred between nanoscale Kirkendall diffusion and Ostwald ripening. The discharge capacity of the spherical and hollow-structured NiO aggregates at the 500(th) cycle was 1118 mA h g(-1) and their capacity retention, which was measured from the second cycle, was nearly 100%. However, the discharge capacities of the solid NiO aggregates and hollow NiO shells were 631 and 150 mA h g(-1), respectively, at the 500(th) cycle and their capacity retentions, which were measured from the second cycle, were 63 and 14%, respectively. As such, the spherical and hollow-structured NiO aggregates, which were formed through the synergetic effect of nanoscale Kirkendall diffusion and Ostwald ripening, have high structural stability during cycling and have excellent lithium storage properties.

Metal oxide-carbon nanotube (CNT) composite microspheres with a novel structure were fabricated using a one-step spray pyrolysis process. Metal oxide-CNT composite microspheres with a uniform distribution of void nanospheres were prepared from a colloidal spray solution containing CNTs, metal salts, and polystyrene (PS) nanobeads. Perforated SnO2-CNT composite microspheres with a uniform distribution of void nanospheres showed excellent lithium storage properties as anode materials for lithium-ion batteries. Bare SnO2 microspheres and SnO2-CNT composite microspheres with perforated and filled structures had a discharge capacity of 450, 1108, and 590 mA h g(-1) for the 250th cycle at a current density of 1.5 A g(-1), and the corresponding capacity retention compared to the second cycle was 41, 98, and 55%, respectively. The synergetic combination of void nanospheres and flexible CNTs improved the electrochemical properties of SnO2. This effective and innovative strategy could be used for the preparation of perforated metal oxide-CNT composites with complex elemental compositions for many applications.

A novel structure denoted a "hollow nanosphere aggregate" is synthesized by introducing nanoscale Kirkendall diffusion to the spray pyrolysis process. The hollow Fe2O3 nanosphere aggregates with spherical shape and micron size are synthesized as the first target material. A solid iron oxide-carbon composite powder that is prepared by a one-pot spray pyrolysis process is transformed into the hollow Fe2O3 nanosphere aggregates by sequential post-pyrolysis treatments under reducing and oxidizing atmospheres. The nanoscale Kirkendall diffusion plays a key role in the formation of the hollow Fe2O3 nanosphere aggregates with spherical shape and micron size. The unique structure of the hollow Fe2O3 nanosphere aggregates results in their superior electrochemical properties as an anode material for lithium ion batteries by improving the structural stability during cycling. The hollow metal oxide nanosphere aggregates with various compositions for wide applications including energy storage can be prepared by the simple fabrication method introduced in this study.

We report the kilogram-scale, simple, and cost-effective synthesis of Pd-loaded quintuple-shelled Co3O4 microreactors by spray drying of aqueous droplets containing cobalt nitrate, palladium nitrate, citric acid, and ethylene glycol and subsequent heat treatment. Highly viscous gel spheres containing Co and Pd salts were successfully converted into multi thin-shelled Co3O4 reactors uniformly loaded with Pd catalysts by the sequential combustion of carbon and decomposition of the metal salts from the outer to the inner regions during one-step heat treatment. The responses (resistance ratio) of the Pd-loaded quintuple-shelled Co3O4 microreactors to 5 ppm toluene and p-xylene were 30.8 and 64.2, respectively, and the selectivity values to toluene and p-xylene against ethanol interference (response ratio) were 14.5 and 30.1, respectively. The unprecedented high response and selectivity were attributed to the effective dissociation of less reactive methylbenzenes into more active smaller species assisted both by catalytic Co3O4 and Pd during the prolonged retention within the microreactors. Kilogram-scale preparation of noble metal-loaded multishelled microreactors and their unique gas-sensing characteristics based on a novel microreactor concept can pave a new way to design of high-performance gas sensors for practical applications.

Pure and palladium-loaded Co3O4 hollow hierarchical nanostructures consisting of nanosheets have been prepared by solvothermal self-assembly. The nanostructures exhibited an ultrahigh response and selectivity towards p-xylene and toluene. The responses (resistance ratio) of the palladium-loaded Co3O4 hollow hierarchical nanostructures to 5 ppm of p-xylene and toluene were as high as 361 and 305, respectively, whereas the selectivity values (response ratios) towards p-xylene and toluene over interference from ethanol were 18.1 and 16.1, respectively. We attributed the giant response and unprecedented high selectivity towards methylbenzenes to the abundant adsorption of oxygen by Co3O4, the high chemiresistive variation in the Co3O4 nanosheets (thickness≈11 nm), and the catalytic promotion of the specific gas-sensing reaction. The morphological design of the p-type Co3O4 nanostructures and loading of the palladium catalyst have paved a new way to monitoring the most representative indoor air pollutants in a highly selective, sensitive, and reliable manner., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Yolk-shell-structured Zn-Fe-S multicomponent sulfide materials with a 1:2 Zn/Fe molar ratio were prepared applying a sulfidation process to ZnFe2O4 yolk-shell powders. The Zn-Fe-S powders had mixed sphalerite (Zn,Fe)S and hexagonal FeS crystal structures. The discharge capacities of the Zn-Fe-S powders sulfidated at 350 °C at a constant current density of 500 mA g(-1) for the first, second, and fiftieth cycles were 1098, 912, and 913 mA h g(-1), respectively. The powders exhibited a high discharge capacity of 602 mA h g(-1) even at the high current density of 10 A g(-1). The synergistic effect of yolk-shell structure and multicomponent composition improved the electrochemical properties of Zn-Fe-S powders., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Tin oxide (SnO2 ) nanotubes with a fiber-in-tube structure have been prepared by electrospinning and the mechanism of their formation has been investigated. Tin oxide-carbon composite nanofibers with a filled structure were formed as an intermediate product, which were then transformed into SnO2 nanotubes with a fiber-in-tube structure during heat treatment at 500 °C. Nanofibers with a diameter of 85 nm were found to be located inside hollow nanotubes with an outer diameter of 260 nm. The prepared SnO2 nanotubes had well-developed mesopores. The discharge capacities of the SnO2 nanotubes at the 2nd and 300th cycles at a current density of 1 A g(-1) were measured as 720 and 640 mA h g(-1), respectively, and the corresponding capacity retention measured from the 2nd cycle was 88 %. The discharge capacities of the SnO2 nanotubes at incrementally increased current densities of 0.5, 1.5, 3, and 5 A g(-1) were 774, 711, 652, and 591 mA h g(-1), respectively. The SnO2 nanotubes with a fiber-in-tube structure showed superior cycling and rate performances compared to those of SnO2 nanopowder. The unique structure of the SnO2 nanotubes with a fiber@void@tube configuration improves their electrochemical properties by reducing the diffusion length of the lithium ions, and also imparts greater stability during electrochemical cycling., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)