The Role of NiO Doping in Reducing the Impact of Humidity on the Performance of SnO2‐Based Gas Sensors: Synthesis Strategies,and Phenomenological and Spectroscopic Studies

The humidity dependence of the gas‐sensing characteristics in SnO₂‐based sensors, one of the greatest obstacles in gas‐sensor applications, is reduced to a negligible level by NiO doping. In a dry atmosphere, undoped hierarchical SnO₂ nanostructures prepared by the self‐assembly of crystalline nanosheets show a high CO response and a rapid response speed. However, the gas response, response/recovery speeds, and resistance in air are deteriorated or changed significantly in a humid atmosphere. When hierarchical SnO₂ nanostructures are doped with 0.64–1.27 wt% NiO, all of the gas‐sensing characteristics remain similar, even after changing the atmosphere from a dry to wet one. According to diffuse‐reflectance Fourier transform IR measurements, it is found that the most of the water‐driven species are predominantly absorbed not by the SnO₂ but by the NiO, and thus the electrochemical interaction between the humidity and the SnO₂ sensor surface is totally blocked. NiO‐doped hierarchical SnO₂ sensors exhibit an exceptionally fast response speed (1.6 s), a fast recovery speed (2.8 s) and a superior gas response (R_a/R_g = 2.8 at 50 ppm CO (R_a: resistance in air, R_g: resistance in gas)) even in a 25% r.h. atmosphere. The doping of hierarchical SnO₂ nanostructures with NiO is a very‐promising approach to reduce the dependence of the gas‐sensing characteristics on humidity without sacrificing the high gas response, the ultrafast response and the ultrafast recovery.     

Low‐Temperature Growth of SnO2 Nanorod Arrays and Tunable n–p–n Sensing Response of a ZnO/SnO2 Heterojunction for Exclusive Hydrogen Sensors

Uniform SnO₂ nanorod arrays have been deposited at low temperature by plasma‐enhanced chemical vapor deposition (PECVD). ZnO surface modification is used to improve the selectivity of the SnO₂ nanorod sensor to H₂ gas. The ZnO‐modified SnO₂ nanorod sensor shows a normal n‐type response to 100 ppm CO, NH₃, and CH₄ reducing gas whereas it exhibits concentration‐dependent n–p–n transitions for its sensing response to H₂ gas. This abnormal sensing behavior can be explained by the formation of n‐ZnO/p‐Zn‐O‐Sn/n‐SnO₂ heterojunction structures. The gas sensors can be used in highly selective H₂ sensing and this study also opens up a general approach for tailoring the selectivity of gas sensors by surface modification.     

Thin‐Wall Assembled SnO2 Fibers Functionalized by Catalytic Pt Nanoparticles and their Superior Exhaled‐Breath‐Sensing Properties for the Diagnosis of Diabetes

Hierarchical SnO₂ fibers assembled from wrinkled thin tubes are synthesized by controlling the microphase separation between tin precursors and polymers, by varying flow rates during electrospinning and a subsequent heat treatment. The inner and outer SnO₂ tubes have a number of elongated open pores ranging from 10 nm to 500 nm in length along the fiber direction, enabling fast transport of gas molecules to the entire thin‐walled sensing layers. These features admit exhaled gases such as acetone and toluene, which are markers used for the diagnosis of diabetes and lung cancer. The open tubular structures facilitated the uniform coating of catalytic Pt nanoparticles onto the inner SnO₂ layers. Highly porous SnO₂ fibers synthesized at a high flow rate show five‐fold higher acetone responses than densely packed SnO₂ fibers synthesized at a low flow rate. Interestingly, thin‐wall assembled SnO₂ fibers functionalized by Pt particles exhibit a dramatically shortened gas response time compared to that of un‐doped SnO₂ fibers, even at low acetone concentrations. Moreover, Pt‐decorated SnO₂ fibers significantly enhance toluene response. These results demonstrate the novel and practical feasibility of thin‐wall assembled metal oxide based breath sensors for the accurate diagnosis of diabetes and potential detection of lung cancer.     

Optimal Doping for Enhanced SnO2 Sensitivity and Thermal Stability

Tin oxide nanocrystals (5–10 nm) doped with silica (0–15 wt %) were made by flame‐spray‐pyrolysis direct deposition onto the sensing electrodes and in situ stabilization by rapid flame annealing. Although increased SiO₂‐doping reduced the SnO₂ crystal and grain size, its sensing performance to ethanol vapor (0.1–50 ppm) exhibited an optimum with respect to SiO₂ content. The thermal stability and morphology of SiO₂‐doped SnO₂ nanoparticles were evaluated by sintering at 200–900 °C for 4–24 h in air. At low SiO₂ content, sintering of SnO₂ was prevented only partially resulting in small sinter necks (bottlenecks) between SnO₂ primary particles (smaller than twice the Debye length). This morphology drastically enhanced the sensitivity toward the analyte by maintaining a thermally stable high surface area and fully depleted connections at the primary particle necks. This enhancement is attributed mostly to the decreasing neck size of the SnO₂ SiO₂ heterojunctions rather than the decreasing SnO₂ crystallite and grain sizes with increasing SiO₂ doping. At high SiO₂ contents, SnO₂ sintering was inhibited as its grains were separated effectively by dielectric SiO₂; this resulted in isolated SnO₂ nanocrystals with drastically reduced sensitivity, thereby effectively being insulators.     

General Fabrication of Monolayer SnO2 Nanonets for High‐Performance Ultraviolet Photodetectors

A facile approach for the fabrication of monolayer SnO₂ nanonet is presented using polymer colloid monolayer nanofilms from oil–water interface self‐assembly as sacrificial templates. The hole size of the nanonets can be adjusted easily by the mean diameter of polymer colloidal spheres. This method can be extended to the fabrication of a series of monolayer nanonets of semiconducting oxides such as TiO₂, ZnO, and CeO₂. Furthermore, the first photoresponse nanodevice based on monolayer SnO₂ nanonet is fabricated. This device presents ultrahigh photocurrent and sensitivity, excellent stability, and reproducibility.     

Rational Design of Highly Porous SnO2 Nanotubes Functionalized with Biomimetic Nanocatalysts for Direct Observation of Simulated Diabetes

1D metal‐oxide nanotube (NT) structures have attracted considerable attention for applications in chemical sensors due to their high surface area and unique chemical and physical properties. Moreover, bimodal pores, i.e., meso‐ and macro‐sized pores, which are formed on the shell of NTs, can further facilitate gas penetration into the sensing layers, leading to much improved sensing properties. However, thin‐walled NTs with bimodal pore distribution have been rarely fabricated due to the limitations of synthetic methods. Here, Ostwald ripening‐driven electrospinning combined with sacrificial templating route using polystyrene (PS) colloid and bioinspired protein is firstly proposed for producing both bi‐modal pores and catalyst‐loaded thin‐walled SnO₂ NTs. Homogeneous catalyst loading on porous SnO₂ NTs is achieved by the protein cage that contains catalysts and PS colloids and protein shells are thermally decomposed during calcination of electrospun fibers, resulting in the creation of dual‐sized pores on NTs. Pt catalyst decorated porous SnO₂ NTs (Pt‐PS_SnO₂ NTs) show exceptionally high acetone gas response, superior selectivity against other interfering gases, and very low limit of detection (10 ppb) to simulated diabetic acetone molecules. More importantly, sensor arrays assembled with developed porous SnO₂ NTs enable the direct distinction between the simulated diabetic breath and normal breath from healthy people.     

Heterogeneous,Porous 2D Oxide Sheets via Rapid Galvanic Replacement: Toward Superior HCHO Sensing Application

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/CoO_x) is suggested through a 2D oxide exfoliation approach combined with a fast galvanic replacement reaction (GRR). The ultrathin (<5 nm) layered CoO_x NSs are simply prepared by ion‐exchange exfoliation and a subsequent GRR process that induces a rapid phase transition from p‐type CoO_x to n‐type SnO₂ metal oxides (<10 min). The controlled GRR process enables the creation of heterogeneous SnO₂/CoO_x 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/CoO_x NSs exhibit an unparalleled HCHO‐sensing performance (R_air/R_gas > 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.     

Highly Selective SAM–Nanowire Hybrid NO2 Sensor: Insight into Charge Transfer Dynamics and Alignment of Frontier Molecular Orbitals

Organic–inorganic hybrid gas sensors can offer outstanding performance in terms of selectivity and sensitivity towards single gas species. The enormous variety of organic functionalities enables novel flexibility of active sensor surfaces compared to commonly used pure inorganic materials, but goes along with an increase of system complexity that usually hinders a predictable sensor design. In this work, an ultra‐selective NO₂ sensor is realized based on self‐assembled monolayer (SAM)‐modified semiconductor nanowires (NWs). The crucial chemical and electronic parameters for an effective interaction between the sensor and different gas species are identified using density functional theory simulations. The theoretical findings are consistent with the experimentally observed extraordinary selectivity and sensitivity of the amine‐terminated SnO₂ NW towards NO₂. The energetic position of the SAM–gas frontier orbitals with respect to the NW Fermi level is the key to ensure or impede an efficient charge transfer between the NW and the gas. As this condition strongly depends on the gas species and the sensor system, these insights into the charge transfer mechanisms can have a substantial impact on the development of highly selective hybrid gas sensors.     

Growth of Aligned Square‐Shaped SnO2 Tube Arrays

Tin dioxide (SnO₂) box beams, or tubes with square or rectangular cross‐sections, are synthesized on quartz substrates using a combustion chemical vapor deposition (CVD) method in an open atmosphere at 850 °C to 1150 °C. The cross‐sectional width of the as‐synthesized SnO₂ tubules is tunable from 50 nm to sub‐micrometer depending on synthesis temperature. Each tubule is found to be a single crystal of rutile structure with four {110} peripheral surfaces and &#60;001&#62; growth direction. Although several growth patterns are observed for different samples, the basic growth mechanism is believed to be a self‐catalyzed, direct vapor–solid (VS) process, where most new material is incorporated into the bottom parts of the existing SnO₂ tubules through surface diffusion. The tubes are readily aligned in the direction perpendicular to the substrate surface to form tube arrays. These well‐aligned SnO₂ tubule arrays with tunable tube size could be the building blocks or templates for fabrication of functional nanodevices, especially those relevant to energy storage and conversion such as nanobatteries, nanofuel cells, and nanosensors. A gas sensor based on a single SnO₂ nanotubes demonstrated extremely high sensitivity to ethanol vapor.     

Direct Conversion of Single‐Layer SnO Nanoplates to Multi‐Layer SnO2 Nanoplates with Enhanced Ethanol Sensing Properties

Direct conversion of single‐layer SnO nanoplates to multi‐layer SnO₂ nanoplates is achieved by annealing in an O₂ ambient at 700 °C. For 50 ppm ethanol, the sensitivities of the multi‐layer SnO₂ nanoplates are more than double that of single‐layer SnO₂ nanoplates, which are also formed from the single‐layer SnO. The higher sensitivity of the multi‐layer nanoplates is attributed to their larger surface/volume ratio. The facile fabrication of interconnected multi‐layer SnO₂ nanoplates at low temperature directly on a Si substrate and sensing chip without the aid of catalysts offers vast advantages over competing methods for the fabrication of high‐sensitivity SnO₂ sensors.     

1D Tellurium Nanostructures: Photothermally Assisted Morphology‐Controlled Synthesis and Applications in Preparing Functional Nanoscale Materials

A facile visible‐light‐assisted solution‐phase approach has been successfully developed to synthesize trigonal Te 1D nanostructures. By varying the relative amount of H₂TeO₃ and water‐soluble polymers, wirelike, beltlike, tubular Te, and Te nanoparticle‐joined 1D aggregates, as well as a novel thorny 1D assembly of Te nanothreads can be synthesized on a large scale. The diameter of the Te nanowires can be modulated by controlling the nucleation and growth process through modulation of the pH value of the reaction mixture. It is believed that the light irradiation and thermal effect play a significant role in this photothermally assisted technique. We have shown that the Te nanowires can be used as a template to prepare Pt–Te nanochains, where the composition of Pt in the Pt–Te 1D products can be modulated by adjusting the ratio of the Te nanowires and Pt salts. Preliminary optical investigations reveal that blue–violet emission of Te nanowires can be enhanced by the formation of defects or dislocations in the Te region through the galvanic replacement reaction between Te nanowires and H₂PtCl₆. In addition, we demonstrate that Te 1D nanostructures can be utilized to prepare Te at carbon‐rich nanocables and carbonaceous nanotubes. Te–Pt at carbon‐rich nanocables can also be fabricated using Te–Pt nanochains as the template. These Pt–Te nanochains and carbonaceous nanostructures are expected to find wide applications in electrochemistry, catalysis, fuel cells, sensors, and other fields. Furthermore, the successful preparation of Te 1D nanostructures with abundant shapes, Pt–Te nanochains, and their carbonaceous composite nanomaterials will offer great opportunities to explore the dependence of novel properties of nanomaterials on their morphology and composition, regulate the photoconductivity of semiconductors, and also be essential for the manufacture of potential optoelectronic devices.     

Ultrasensitive and Highly Selective Gas Sensors Based on Electrospun SnO2 Nanofibers Modified by Pd Loading

This work presents a new route to suppress grain growth and tune the sensitivity and selectivity of nanocrystalline SnO₂ fibers. Unloaded and Pd‐loaded SnO₂ nanofiber mats are synthesized by electrospinning followed by hot‐pressing at 80 °C and calcination at 450 or 600 °C. The chemical composition and microstructure evolution as a function of Pd‐loading and calcination temperature are examined using EDS, XPS, XRD, SEM, and HRTEM. Highly porous fibrillar morphology with nanocrystalline fibers comprising SnO₂ crystallites decorated with tiny PdO crystallites is observed. The grain size of the SnO₂ crystallites in the layers that are calcined at 600 °C decreases with increasing Pd concentration from about 15 nm in the unloaded specimen to about 7 nm in the 40 mol% Pd‐loaded specimen, indicating that Pd‐loading could effectively suppress the SnO₂ grain growth during the calcination step. The Pd‐loaded SnO₂ sensors have 4 orders of magnitude higher resistivity and exhibit significantly enhanced sensitivity to H₂ and lower sensitivity to NO₂ compared to their unloaded counterparts. These observations are attributed to enhanced electron depletion at the surface of the PdO‐decorated SnO₂ crystallites and catalytic effect of PdO in promoting the oxidation of H₂ into H₂O. These phenomena appear to have a much larger effect on the sensitivity of the Pd‐loaded sensors than the reduction in grain size.     

Piezoelectric‐Effect‐Enhanced Full‐Spectrum Photoelectrocatalysis in p–n Heterojunction

Photoelectrochemical (PEC) water splitting offers a promising strategy for converting solar energy to chemical fuels. Herein, a piezoelectric‐effect–enhanced full‐spectrum photoelectrocatalysis with multilayered coaxial titanium dioxide/barium titanate/silver oxide (TiO₂/BTO/Ag₂O) nanorod array as the photoanode is reported. The vertically grown nanorods ensure good electron conductivity, which enables fast transport of the photogenerated electrons. Significantly, the insertion of a piezoelectric BaTiO₃ (BTO) nanolayer at the p‐type Ag₂O and n‐type TiO₂ interface created a polar charge‐stabilized electrical field. It maintains a sustainable driving force that attract the holes of TiO₂ and the electrons of Ag₂O, resulting in greatly increased separation and inhibited recombination of the photogenerated carriers. Furthermore, Ag₂O as a narrow bandgap semiconductor has a high ultraviolet–visible–near infrared (UV–vis–NIR) photoelectrocatalytic activity. The TiO₂/BTO/Ag₂O, after poling, successfully achieves a prominent photocurrent density, as high as 1.8 mA cm^?2 at 0.8 V versus Ag/Cl, which is about 2.6 times the TiO₂ nanorod photoanode. It is the first time that piezoelectric BaTiO₃ is used for tuning the interface of p‐type and n‐type photoelectrocatalyst. With the enhanced light harvesting, efficient photogenerated electron–hole pairs' separation, and rapid charge transfer at the photoanode, an excellent photoelectrocatalytic activity is realized.     

Gas Sensors: Ultrasensitive and Highly Selective Gas Sensors Based on Electrospun SnO2 Nanofibers Modified by Pd Loading (Adv. Funct. Mater. 24/2010)

This work presents a new route to suppress grain growth and tune the sensitivity and selectivity of nanocrystalline SnO₂ fibers. Unloaded and Pd‐loaded SnO₂ nanofiber mats are synthesized by electrospinning followed by hot‐pressing at 80 °C and calcination at 450 or 600 °C. The chemical composition and microstructure evolution as a function of Pd‐loading and calcination temperature are examined using EDS, XPS, XRD, SEM, and HRTEM. Highly porous fibrillar morphology with nanocrystalline fibers comprising SnO₂ crystallites decorated with tiny PdO crystallites is observed. The grain size of the SnO₂ crystallites in the layers that are calcined at 600 °C decreases with increasing Pd concentration from about 15 nm in the unloaded specimen to about 7 nm in the 40 mol% Pd‐loaded specimen, indicating that Pd‐loading could effectively suppress the SnO₂ grain growth during the calcination step. The Pd‐loaded SnO₂ sensors have 4 orders of magnitude higher resistivity and exhibit significantly enhanced sensitivity to H₂ and lower sensitivity to NO₂ compared to their unloaded counterparts. These observations are attributed to enhanced electron depletion at the surface of the PdO‐decorated SnO₂ crystallites and catalytic effect of PdO in promoting the oxidation of H₂ into H₂O. These phenomena appear to have a much larger effect on the sensitivity of the Pd‐loaded sensors than the reduction in grain size.     

Cu2O Nanocrystal‐Templated Growth of Cu2S Nanocages with Encapsulated Au Nanoparticles and In‐Situ Transmission X‐ray Microscopy Study

Cubic and octahedral Cu₂O nanocrystals and Au–Cu₂O core–shell heterostructures are used as sacrificial templates for the growth of Cu₂S nanocages and Au–Cu₂S core–cage structures. A rapid sulfidation process involving a surface reaction of Cu₂O nanocrystals with Na₂S, followed by etching of the Cu₂O cores with HCl solution for ≈5 sec, results in the fabrication of Cu₂S cages with a wall thickness of 10–20 nm. Transmission electron microscopy characterization reveals the formation of crystalline walls and the presence of ultrasmall pores with sizes of 1 nm or less. Formation of Cu₂O–Cu₂S core–shell structures and their conversion into Cu₂S cages is verified by UV–vis absorption spectroscopy. X‐ray photoelectron spectra further confirm the composition of the cages as Cu₂S. The entire hollowing process via the Kirkendall effect is recorded using in‐situ transmission X‐ray microscopy. After shell formation, continuous ionic diffusion removes the interior Cu₂O. Intermediate structures with remaining central Cu₂O portions and bridging arms to the surrounding cages are observed. The nanocages are also shown to allow molecular transport: anthracene and pyrene penetration into the cages leads to enhanced fluorescence quenching immediately upon adsorption onto the surfaces of the encapsulated gold nanocrystals.     

Engineering of Facets,Band Structure,and Gas‐Sensing Properties of Hierarchical Sn2+‐Doped SnO2 Nanostructures

Hierarchical SnO₂ nanoflowers, assembled from single‐crystalline SnO₂ nanosheets with high‐index (11$ \bar 3 $ ) and (10$ \bar 2 $ ) facets exposed, are prepared via a hydrothermal method using sodium fluoride as the morphology controlling agent. Formation of the 3D hierarchical architecture comprising of SnO₂ nanosheets takes place via Ostwald ripening mechanism, with the growth orientation regulated by the adsorbate fluorine species. The use of Sn(II) precursor results in simultaneous Sn²⁺ self‐doping of SnO₂ nanoflowers with tunable oxygen vacancy bandgap states. The latter further results in the shifting of semiconductor Fermi levels and extended absorption in the visible spectral range. With increased density of states of Sn²⁺‐doped SnO₂ selective facets, this gives rise to enhanced interfacial charge transfer, that is, high sensing response, and selectivity towards oxidizing NO₂ gas. The better gas sensing performance over (10$ \bar 2 $ ) compared to (11$ \bar 3 $ ) faceted SnO₂ nanostructures is elucidated by surface energetic calculations and Bader analyses. This work highlights the possibility of simultaneous engineering of surface energetics and electronic properties of SnO₂ based materials.     

Pd-Doped Tin-Oxide-Based Thick-Film Sensor Array for Detection of H2, CH4, and CO

In the present work, a palladium (Pd)-doped tin oxide (SnO₂) thick-film sensor array has been developed by using solid state reaction-derived pure SnO₂ powders (starting with two initial tin precursors: SnCl₂·2H₂O and SnCl₄·5H₂O). The crystal structure of the powders and the morphology of the thick films have been characterized by using x-ray diffraction and field-emission scanning electron microscopy, respectively. Initially, the sensitivity of all the sensors of the array was studied for hydrogen (H₂), methane (CH₄), and carbon monoxide gas, followed by detailed analysis of the transient response of a 1 wt.% Pd-doped SnO₂ sensor prepared by using SnCl₄·5H₂O as a starting tin precursor, as it possessed better sensitivity for all the test gases. It is found that this sensor exhibits fast response and recovery times (1 min and 3.05 min) along with good repeatability for test gases; however, for CH₄ gas, it shows very much longer response and recovery times. The high response towards H₂ gas has been correlated well with the smallest crystallite size (18 nm) as well as the porous structure of the thick-film surface.     

Preparation and gas sensitivity of WO3 hollow microspheres and SnO2 doped heterojunction sensors

Dispersed tungsten trioxide (WO₃) microsphere aggregates were prepared by chemical reduction with hydrazine hydrate in a glycol–water system, and the composites of WO₃/tin oxide (SnO₂) with different SnO₂ weight fractions were prepared by microwave refluxing. The products were characterized by x-ray diffraction, field emission scanning electron microscopy, thermogravimetric-differential thermal analysis, Fourier transform infrared spectroscopy, and the Brunauer–Emmett–Teller method. The gas-sensing characteristics based on the composites were investigated by a stationary-state gas distribution method. The results show that the noncompact WO₃ microspheres with hollow structure were obtained. The phase composition and the morphology of WO₃ were changed by SnO₂ doping. The heterojunction structure was formed between WO₃ and SnO₂, and the heterojunction sensors have high sensitivity to H₂S, NO_X, and xylene at relatively lower operating temperature, especially the sensor doped by 3% SnO₂ operating just at 90 °C for H₂S gas.     

One‐Dimensional Hierarchical Structures Composed of Novel Metal Oxide Nanosheets on a Carbon Nanotube Backbone and Their Lithium‐Storage Properties

Some facile solution methods are developed to directly grow anatase TiO₂ nanosheets with exposed (001) facets and SnO₂ nanosheets onto a carbon nanotube backbone for the first time. TiO₂ nanosheets can also be grown on SnO₂@CNT coaxial nanocables. An electrochemical investigation shows that these unique one‐dimensional hierarchical nanostructures exhibit significantly enhanced lithium‐storage properties under different testing conditions by comparison to the pure metal oxide counterparts, and evidently suggests that improved electrochemical properties of TiO₂ and SnO₂ can be achieved through proper design of the nanostructure and chemical composition.     

The Effect of Morphological Modification on the Electrochemical Properties of SnO2 Nanomaterials

The electrochemical performances of 1D SnO₂ nanomaterials, nanotubes, nanowires, and nanopowders, are compared to define the most favorable morphology when SnO₂ nanomaterials are adopted as the electrode material for lithium‐ion batteries. Changes in the morphology of SnO₂ are closely related with its electrochemical performance. Some SnO₂ nanomaterials feature not only an increased energy density but also enhanced Li⁺ transfer. The correlation between the morphological characteristics and the electrochemical properties of SnO₂ nanomaterials is discussed. The interesting electrochemical results obtained here on SnO₂ nanomaterials indicate the possibility of designing and fabricating attractive nanostructured materials for lithium‐ion batteries.