Highly Selective and Reversible Detection of Simulated Breath Hydrogen Sulfide Using Fe-Doped CuO Hollow Spheres: Enhanced Surface Redox Reaction by Multi-Valent Catalysts.

The precise and reversible detection of hydrogen sulfide (H2 S) at high humidity condition, a malodorous and harmful volatile sulfur compound, is essential for the self-assessment of oral diseases, halitosis, and asthma. However, the selective and reversible detection of trace concentrations of H2 S (≈0.1 ppm) in high humidity conditions (exhaled breath) is challenging because of irreversible H2 S adsorption/desorption at the surface of chemiresistors. The study reports the synthesis of Fe-doped CuO hollow spheres as H2 S gas-sensing materials via spray pyrolysis. 4 at.% of Fe-doped CuO hollow spheres exhibit high selectivity (response ratio ≥ 34.4) over interference gas (ethanol, 1 ppm) and reversible sensing characteristics (100% recovery) to 0.1 ppm of H2 S under high humidity (relative humidity 80%) at 175 °C. The effect of multi-valent transition metal ion doping into CuO on sensor reversibility is confirmed through the enhancement of recovery kinetics by doping 4 at.% of Ti- or Nb ions into CuO sensors. Mechanistic details of these excellent H2 S sensing characteristics are also investigated by analyzing the redox reactions and the catalytic activity change of the Fe-doped CuO sensing materials. The selective and reversible detection of H2 S using the Fe-doped CuO sensor suggested in this work opens a new possibility for halitosis self-monitoring.

Highly Selective and Sensitive Detection of Breath Isoprene by Tailored Gas Reforming: A Synergistic Combination of Macroporous WO3 Spheres and Au Catalysts.

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 WO3 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.

Exclusive and ultrasensitive detection of formaldehyde at room temperature using a flexible and monolithic chemiresistive sensor.

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 TiO2 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 TiO2 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 TiO2 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.

A Transparent Nanopatterned Chemiresistor: Visible-Light Plasmonic Sensor for Trace-Level NO2 Detection at Room Temperature.

The highly selective detection of trace gases using transparent sensors at room temperature remains challenging. Herein, transparent nanopatterned chemiresistors composed of aligned 1D Au-SnO2 nanofibers, which can detect toxic NO2 gas at room temperature under visible light illumination is reported. Ten straight Au-SnO2 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 NO2 , and its detection limit is as low as 6 ppb. The unique room-temperature NO2 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.

General Strategy for Designing Highly Selective Gas-Sensing Nanoreactors: Morphological Control of SnO2 Hollow Spheres and Configurational Tuning of Au Catalysts.

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-SnO2 nanoreactors by loading Au nanoclusters on the inner surface of SnO2 hollow shells using the layer-by-layer assembly technique. The results revealed that the sensor based on SnO2 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 SnO2 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.

Extremely selective detection of ppb levels of indoor xylene using CoCr2O4 hollow spheres activated by Pt doping.

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.

Dual Role of Multiroom-Structured Sn-Doped NiO Microspheres for Ultrasensitive and Highly Selective Detection of Xylene.

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.

Toward breath analysis on a chip for disease diagnosis using semiconductor-based chemiresistors: recent progress and future perspectives.

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 NH3 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 H2S, 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.

Highly Selective Xylene Sensor Based on NiO/NiMoO4 Nanocomposite Hierarchical Spheres for Indoor Air Monitoring.

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/NiMoO4 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/NiMoO4 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, C2H5OH, CH3COCH3, HCHO, CO, trimethylamine, and NH3. 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/NiMoO4 nanocomposite hierarchical spheres is discussed in relation to the catalytic promotion of the xylene-sensing reaction by synergistic combination between NiO and NiMoO4, 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.

A New Strategy for Humidity Independent Oxide Chemiresistors: Dynamic Self-Refreshing of In2 O3 Sensing Surface Assisted by Layer-by-Layer Coated CeO2 Nanoclusters.

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.

Kilogram-scale synthesis of Pd-loaded quintuple-shelled Co3O4 microreactors and their application to ultrasensitive and ultraselective detection of methylbenzenes.

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 with giant and ultraselective chemiresistivity to xylene and toluene.

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.

A new concept for obtaining SnO2 fiber-in-tube nanostructures with superior electrochemical properties.

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.

Honeycomb-like periodic porous LaFeO3 thin film chemiresistors with enhanced gas-sensing performances.

The use of composite materials and polynary compounds is a promising strategy to promote conductometric sensor performances. The perovskite oxides provide various compositional combinations between different oxides for tuning gas-sensing reaction and endowing rich oxygen deficiencies for preferable gas adsorption. Herein, a sacrificial colloidal template approach is exploited to fabricate crystalline ternary LaFeO3 perovskite porous thin films, by transferring a La(3+)-Fe(3+) hybrid solution-dipped template onto a substrate and sequent heat treatment. The honeycomb-like LaFeO3 film consisted of monolayer periodic pore (size: ∼ 500 nm) array can be successfully in situ synthesized in a homogeneous layout with a single phase of perovskite. This periodic porous LaFeO3 film with p-type semiconductivity exhibits a high gas response, fast response (∼4 s), trace detection capacity (50 ppb), and favorable ethanol selectivity from similar acetone. It exhibits enhanced sensing performances compared to those of a binary n-type Fe2O3 film and a nontemplated dense LaFeO3 film. In addition, a five-axe spiderweb diagram is introduced to make a feasible evaluation of the optimal practical work condition, comprehensively regarding the response/recovery rate, gas response, selectivity and operating temperature. The enhanced ethanol sensing mechanism of honeycomb-like LaFeO3 periodic porous film is also addressed. This novel and facile route to fabricate well-ordered porous LaFeO3 thin film can also be applied to many fields to obtain special performances, such as solar cells, ion conductors, gas separation, piezoelectricity, and self-powered sensing device system.

Design of highly sensitive and selective Au@NiO yolk-shell nanoreactors for gas sensor applications.

Au@NiO yolk-shell nanoparticles (NPs) were synthesized by simple solution route and applied for efficient gas sensor towards H2S gas. Carbon encapsulated Au (Au@C core-shell) NPs were synthesized by glucose-assisted hydrothermal method, whereas Au@NiO yolk-shell NPs were synthesized by precipitation method using Au@C core-shell NPs as a template. Sub-micrometer Au@NiO yolk-shell NPs were formed having 50-70 nm Au NPs at the periphery of NiO shell (10-20 nm), which was composed of 6-12 nm primary NiO particles. Au@NiO yolk-shell NPs showed higher response for H2S compared to other interfering gases (ethanol, p-xylene, NH3, CO and H2). The maximum response was 108.92 for 5 ppm of H2S gas at 300 °C, which was approximately 19 times higher than that for the interfering gases. The response of Au@NiO yolk-shell NPs to H2S was approximately 4 times higher than that of bare NiO hollow nanospheres. Improved performance of Au@NiO yolk-shell NPs was attributed to hollow spaces that allowed the accessibility of Au NPs to gas molecules. It was suggested that adsorption of H2S on Au NPs resulted in the formation of sulfide layer, which possibly lowered its work function, and therefore tuned the electron transfer from Au to NiO rather NiO to Au, which leaded to increase in resistance and therefore response.

Impedance spectroscopic analysis on effects of partial oxidation of TiN bottom electrode and microstructure of amorphous and crystalline HfO2 thin films on their bipolar resistive switching.

The electrical resistance switching (RS) properties of amorphous HfO2 (a-HfO2) and crystalline HfO2 (c-HfO2) thin films grown on a TiN substrate via atomic layer deposition were examined using DC current-voltage (I-V) sweep and AC impedance spectroscopic (IS) analyses. The rapid thermal annealing of the a-HfO2 film at 500 °C under a N2 atmosphere for 5 min crystallized the HfO2 film and induced an interfacial TiON barrier layer. The a-HfO2 sample showed fluent bipolar RS performance with a high on/off ratio (∼ 500), whereas the c-HfO2 sample showed a much lower on/off ratio (<∼ 10), but its switching uniformity was better than that of a-HfO2. Such critical differences can be mainly attributed to the absence and presence of the TiON barrier layer in the a-HfO2 and c-HfO2 samples, respectively. The AC IS especially enabled the resistance states of the HfO2/Pt interface and the HfO2/TiN interface to be separately examined during one complete switching cycle of each sample. Although the Pt/c-HfO2 interface has a Schottky barrier in the pristine state, it disappeared once the c-HfO2 was electroformed and was not recovered even after the reset step. In contrast, the Pt/a-HfO2 interface partly recovered the Schottky barrier after the reset.

One-pot synthesis of Pd-loaded SnO(2) yolk-shell nanostructures for ultraselective methyl benzene sensors.

A continuous, single-step, and large-scale preparation of Pd-catalyst-loaded SnO2 yolk-shell spheres is demonstrated. These nanostructures show an unusually high response and selectivity to methyl benzenes, such as xylene and toluene, with very low cross-responses to various interfering gases, making them suitable for precise monitoring of indoor air quality.

Electronic sensitization of the response to C2H5OH of p-type NiO nanofibers by Fe doping.

Pure and 0.18-13.2 at.% Fe-doped NiO nanofibers were prepared by electrospinning and their gas sensing characteristics and microstructural evolution were investigated. The responses ((Rg - Ra)/Ra, where Rg is the resistance in gas and Ra is the resistance in air) to 5 ppm C2H5OH, toluene, benzene, p-xylene, HCHO, CO, H2, and NH3 at 350-500 ° C were significantly enhanced by Fe doping of the NiO nanofibers, while the responses of pure NiO nanofibers to all the analyte gases were very low ((Rg - Ra)/Ra = 0.07-0.78). In particular, the response to 100 ppm C2H5OH was enhanced up to 217.86 times by doping of NiO nanofibers with 3.04 at.% Fe. The variation in the gas response was closely dependent upon changes in the base resistance of the sensors in air. The enhanced gas response of Fe-doped NiO nanofibers was explained in relation to electronic sensitization, that is, the increase in the chemoresistive variation due to the decrease in the hole concentration induced by Fe doping.

Ultraselective and sensitive detection of xylene and toluene for monitoring indoor air pollution using Cr-doped NiO hierarchical nanostructures.

Ultraselective and sensitive detection of xylene and toluene with minimum interferences of other indoor air pollutants such as benzene, ethanol, and formaldehyde is achieved using NiO hierarchical nanostructures doped with Cr. Pure and 1.15-2.56 at% Cr-doped NiO flower-like hierarchical nanostructures assembled from nanosheets are prepared by a simple solvothermal reaction and their gas sensing characteristics toward o-xylene and toluene gases are investigated. The 1.15 at% Cr-doped NiO hierarchical nanostructures show high responses to 5 ppm of o-xylene and toluene (ratio of resistance to gas and air = 11.61 and 7.81, respectively) and negligible cross-responses to 5 ppm of benzene, formaldehyde, ethanol, hydrogen, and carbon monoxide. However, pure NiO nanostructures show low responses to 5 ppm of o-xylene and toluene (ratio of resistance to gas and air = 2.01 and 1.14, respectively) and no selectivity toward any specific gas is observed. Significant enhancement of the response and selectivity to o-xylene and toluene is attributed to the decrease in the hole concentration in NiO and the catalytic oxidation of methyl groups by Cr doping.

Percutaneous vertebroplasty at C7 for the treatment of painful metastases -A case report-.

The cervical spine is a less common site for metastatic disease than is the thoracolumbar spine. Percutaneous vertebroplasty (PVP) in the cervical spine can be performed using an anteromedial or lateral approach. A 51-year-old woman with breast cancer had been experiencing severe weight-bearing neck pain for 2 months, even after undergoing radiation therapy. Imaging studies revealed an osteolytic compression fracture in the C7 vertebra. For performing PVP at C7 using the anteromedial approach, a needle was inserted from the left side of the patient's neck. The needle was advanced to the anterior 1/3 anterior 1/3 or 1/2 of the vertebral body by hammering, and approximately 2 ml of cement was injected. Immediately after the operation, the patient could move her neck without pain. In conclusion, PVP using an anterolateral approach may be an option for treating metastatic osteolytic vertebral lesions in the cervical spine for alleviating intractable axial neck pain.