Synthesis and characterization of monodisperse hollow SnO<Subscript>2</Subscript> microspheres and their enhanced sensing properties to ethanol

The monodisperse hollow SnO₂ (H-SnO₂) microspheres were successfully synthesized by the ion exchange method using sulfonated PS microspheres as a template. The structure and morphology were characterized by X-ray diffraction, transmission electron microscopy and high-resolution transmission electron microscopy, which confirms the hollow structure of the products. The H-SnO₂ microspheres are composed of numerous SnO₂ nanoparticles with a shell thickness of about 13 nm. The monodisperse H-SnO₂ microspheres have a high specific surface area of 55.54 m²/g, which improves the gas sensing properties toward ethanol. Gas-sensing measurement results indicate that H-SnO₂ microspheres exhibit an excellent sensitivity (103.1) toward 200 ppm ethanol at 260 °C, which is much higher than that (65.8) of SnO₂ nanoparticles.     

Ultrafine SnO2 nanoparticles as a high performance anode material for lithium ion battery

In this paper, the ultrafine tin oxides (SnO₂) nanoparticles are fabricated by a facile microwave hydrothermal method with the mean size of only 14 nm. Phase compositions and microstructures of the as-prepared nanoparticles have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that the ultrafine SnO₂ nanoparticles are obtained to be the pure rutile-structural phase with the good dispersibility. Galvanostatic cycling and cyclic voltammetry results indicate that the first discharge capacity of the ultrafine SnO₂ electrode is 1196.63  mAh g⁻¹, and the reversible capacity could retain 272.63 mAh g⁻¹ at 100 mA g⁻¹ after 50 cycles for lithium ion batteries (LIBs). The excellent electrochemical performance of the SnO₂ anode for LIBs is attributed to its ultrafine nanostructure for providing active sites during lithium insertion/extraction processes. Pulverization and agglomeration of the active materials are effectively reduced by the microwave hydrothermal method.     

Facile synthesis and superior anodic performance of ultrafine SnO2-containing nanocomposites

Ultrafine SnO₂-containing nanocomposites were synthesized from glucose/SnCl₂ acid solution under hydrothermal environment. The content of SnO₂ in the nanocomposites could be adjusted by changing the mass ratio of SnCl₂ to glucose in the initial solution. The crystalline structure and morphology of the as-synthesized nanocomposites have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The results revealed that the nanocomposites were composed of highly dispersing SnO₂ nanoparticles with the sizes of only a few nanometers (3–5 nm). Electrochemical tests demonstrated that the electrochemical performances were strongly dependent on the content of SnO₂ in the nanocomposites. The nanocomposites containing 75 wt.% SnO₂ exhibited an outstanding reversible capacity of 610 mAh/g and high capacity retention after 200 cycles. The extraordinary performance should originate from the very small size of SnO₂ nanoparticles and carbon precursor matrix derived from glucose which can confer the ability to accommodate the volume changes and prevent the agglomeration of Sn particles during charge/discharge process.     

A facile route to carbon-coated SnO2 nanoparticles combined with a new binder for enhanced cyclability of Li-ion rechargeable batteries

Carbon-coated SnO₂ nanoparticles were prepared by a novel facile route using commercial SnO₂ nanoparticles treated with concentrated sulfuric acid in the presence of sucrose at room temperature and ambient pressure. The key features of this method are the simple procedure, low energy consumption, and inexpensive and non-toxic source materials. As-prepared core/shell nanoparticles were characterized by X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDX), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The electrochemical measurements showed that the carbon-coated SnO₂ nanoparticles with 10% carbon and using carboxymethyl cellulose (CMC) as a binder displayed the best electrochemical performance with the highest specific capacity of 502 mAh g⁻¹ after 50 cycles at a current density of 100 mA g⁻¹. In addition, owing to the water solvability of CMC, the usage of CMC as binder makes the whole electrode fabrication process cheaper and more environmental friendly.     

Preparation and characterization of tin oxide,SnO2 nanoparticles decorated graphene

SnO₂ nanoparticles/graphene (SnO₂/GP) nanocomposite was synthesized by a facile microwave method. The X-ray diffraction (XRD) pattern of the nanocomposite corresponded to the diffraction peak typical of graphene and the rutile phase of SnO₂ with tetragonal structure. The field emission scanning electron microscope (FESEM) images revealed that the graphene sheets were dotted with SnO₂ nanoparticles with an average size of 10 nm. The X-ray photoelectron spectroscopy (XPS) analysis indicated that the development of SnO₂/GP resulted from the removal of the oxygenous groups on graphene oxide (GO) by Sn²⁺ ions. The nanocomposite modified glassy carbon electrode (GCE) showed excellent enhancement of electrochemical performance when interacting with mercury(II) ions in potassium chloride supporting electrolyte. The current was increased by more than tenfold, suggesting its potential to be used as a mercury(II) sensor.     

Free-standing single-walled carbon nanotube/SnO2 anode paper for flexible lithium-ion batteries

Free-standing single-walled carbon nanotube/SnO₂ (SWCNT/SnO₂) anode paper was prepared by vacuum filtration of SWCNT/SnO₂ hybrid material which was synthesized by the polyol method. From field emission scanning electron microscopy and transmission electron microscopy, the CNTs form a three-dimensional nanoporous network, in which ultra-fine SnO₂ nanoparticles, which had crystallite sizes of less than 5 nm, were distributed, predominately as groups of nanoparticles on the surfaces of single walled CNT bundles. Electrochemical measurements demonstrated that the anode paper with 34 wt.% SnO₂ had excellent cyclic retention, with the high specific capacity of 454 mAh g^?1 beyond 100 cycles at a current density of 25 mA g^?1, much higher than that of the corresponding pristine CNT paper. The SWCNTs could act as a flexible mechanical support for strain release, offering an efficient electrically conducting channel, while the nanosized SnO₂ provides the high capacity. The SWCNT/SnO₂ flexible electrodes can be bent to extremely small radii of curvature and still function well, despite a marginal decrease in the conductivity of the cell. The electrochemical response is maintained in the initial and further cycling process. Such capabilities demonstrate that this model hold great promise for applications requiring flexible and bendable Li-ion batteries.     

Nonaqueous and template-free synthesis of Sb doped SnO2 microspheres and their application to lithium-ion battery anode

Antimony doped SnO₂ (ATO) microspheres composed of ATO nanoparticles were prepared by using a hydrothermal process in a nonaqueous and template-free solution from the inorganic precursors (SnCl₄ and Sb(OC₂H₅)₃). The physical properties of the as-synthesized samples were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption isotherms, and X-ray photoelectron spectrum (XPS). The resulting particles were highly crystalline ATO microspheres in the diameter range of 3-10 μm and with many pores. The as-prepared samples were used as negative materials for lithium-ion battery, whose charge-discharge properties, cyclic voltammetry, and cycle performance were examined. The results showed that a high initial discharge capacity of 1981 mAh g⁻¹ and a charge capacity of 957 mAh g⁻¹ in a potential range of 0.005-3.0 V was achieved, which suggests that tin oxide-based materials work as high capacity anodes for lithium-ion rechargeable batteries. The cycle performance is improved because the conducting ATO nanoparticles can also perform as a better matrix for lithium-ion battery anode.     

Facile synthesis of graphitic carbons decorated with SnO2 nanoparticles and their application as high capacity lithium-ion battery anodes

A facile and potentially scalable synthesis route to obtain SnO₂–carbon composites was developed. SnO₂ nanoparticles were deposited on the surface of two types of graphitic carbon: (a) commercial porous graphite (HG) and (b) graphitic carbon nanostructures. The synthesis procedure consists of two simple steps: (i) room temperature formation/deposition of SnO₂ nanocrystals and (ii) thermal treatment at 350 °C to generate SnO₂ nanoparticles (size ~3.5 nm) over the carbon surface. The electrochemical performance of the graphitic carbons and the SnO₂–carbon composites as anode materials in Li-ion rechargeable batteries was investigated. In all cases, tape casting electrode fabrication allowed almost full active material utilization. Good cyclabilities were achieved, with HG and HG–SnO₂ showing capacities of 356 and 545 mAh g⁻¹, respectively after 50 cycles.     

Raman spectra,photoluminescence and ferromagnetism of pure,Co and Fe doped SnO2 nanoparticles

The pure and transition metal (Co and Fe = 3 and 5 mol%) doped SnO₂ nanoparticles have been synthesized by a chemical route using polyvinyl alcohol as surfactant. These nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman, Fourier transform infrared (FTIR) spectroscopy, photoluminescence (PL) and magnetic measurements. The XRD patterns show that all the samples have tetragonal rutile structure without any extra phase and the value of average particle size using FWHM lies within 12–29 nm is also confirmed by TEM. FTIR spectrum has been used to confirm the formation of SnO bond. Raman spectroscopy shows the intensity loss of classical cassiterite SnO₂ vibration lines which is an indication of significant structural modifications. From PL, an intense blue luminescence centered at a wavelength ～530 nm is observed in the prepared SnO₂ nanoparticles, which is different from the yellow-red light emission observed in SnO₂ nanostructures prepared by other methods. The strong blue luminescence from the as-grown SnO₂ nanoparticles is attributed to oxygen-related defects that have been introduced during the growth process. These Co and Fe-doped SnO₂ nanoparticles exhibit room temperature ferromagnetism and the value of their magnetic moment and phase transition temperature are sensitive to their size and stoichiometric ratio.     

Continuous microwave flow synthesis (CMFS) of nano-sized tin oxide: Effect of precursor concentration

Tin oxide (SnO₂) nanoparticles exhibit an intense luminescent behavior under UV-light in contrast to the bulk tin oxide and therefore have become focus of many investigations. SnO₂ nano-agglomerates were successfully prepared by continuous microwave flow synthesis (CMFS) method using tin chloride pentahydrate as a tin precursor. The effect of concentration of reacting species on the degree of crystallinity, particle size, lattice parameters, morphology, and photocatalytic behavior was probed. Structural and morphological features of the resulting SnO₂ nano-structures were examined by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Brunar Emmett Tellar (BET), Transmission electron microscopy (TEM) and ultra-violet (UV/Visible) spectroscopy. From the XRD spectra the crystal structure of the synthesized product was confirmed as phase pure tetragonal cassiterite type with particle size of 4.43 nm. TEM images further confirmed the formation of highly agglomerated nanoparticles, whereas the change in concentration had no appreciable effect on the particle morphology. BET surface area measurements confirmed that the surface area of the SnO₂ nanoparticles decreased with increase in Sn precursor concentration. The optical band gap values of SnO₂ nanoparticles were calculated to be 3.19 eV, which is a red-shift compared with that of the bulk SnO₂ (3.6 eV). The nano-agglomerates were efficient catalyst for the photodegradation of methylene blue (MB) dye. Our results indicate that the synthesized SnO₂ nanoparticles can have potential applications in liquid photovoltaic, photocatalysis and sensors.     

Synthesis of layered hierarchical porous SnO<Subscript>2</Subscript> for enhancing gas sensing performance

Layered hierarchical porous SnO₂ (LHP-SnO₂) have been synthesized by a two-step method, in which pure SnO₂ nanoparticles(NPs) with the diameter about 3.2 nm were prepared firstly through a hydro-thermal method, and then LHP-SnO₂ were prepared by utilizing polystyrene (PS) microspheres as a template and SnO₂ NPs as a precursor. The as-prepared sample consisted of porous SnO₂ layers, in which each layer presents a three-dimensional random arrangement of macropores with average pore diameter of about 260 nm. The Nitrogen adsorption–desorption analysis implied that the sample was characterized with large surface area of 140.67 m²/g and extensive micropores and mesopores structure. Compared with pure SnO₂ NPs, the LHP-SnO₂ exhibited an obvious improvement in gas sensing properties. These results indicate that the layered hierarchical porous structure possess potential application in sensing materials.     

High reversible capacity of SnO2/graphene nanocomposite as an anode material for lithium-ion batteries

A gas–liquid interfacial synthesis approach has been developed to prepare SnO₂/graphene nanocomposite. The as-prepared nanocomposite was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller measurements. Field emission scanning electron microscopy and transmission electron microscopy observation revealed the homogeneous distribution of SnO₂ nanoparticles (2–6 nm in size) on graphene matrix. The electrochemical performances were evaluated by using coin-type cells versus metallic lithium. The SnO₂/graphene nanocomposite prepared by the gas–liquid interface reaction exhibits a high reversible specific capacity of 1304 mAh g⁻¹ at a current density of 100 mA g⁻¹ and excellent rate capability, even at a high current density of 1000 mA g⁻¹, the reversible capacity was still as high as 748 mAh g⁻¹. The electrochemical test results show that the SnO₂/graphene nanocomposite prepared by the gas–liquid interfacial synthesis approach is a promising anode material for lithium-ion batteries.     

Ultrahigh Active Pd Nanocatalyst Supported on Core-Sheath Conducting Polymer/Metal Oxide Composite Nanorods

Abstract  

A facile and aqueous-phase method based on the electron transfer reduction process for fabricating core-sheath structured polyaniline (PANI)/SnO₂ composite nanorods supported Pd nanocatalyst has been demonstrated. The Pd nanoparticles synthesized by this strategy have a small size of smaller than 3.0 nm. The well dispersed Pd nanoparticles with small sizes supported on core-sheath PANI/SnO₂ composite nanorods exhibited an ultrahigh catalytic activity during the catalytic reduction of p-nitrophenol into p-aminophenol by NaBH₄ in aqueous solution. The kinetic apparent rate constant (k_app) reach to be about 26.9 × 10⁻³ s⁻¹. It is believed that this method could be extended to cover many kinds of other functional composite nanomaterials where the active component is expected to bring in new features and applications.     

Stability and thermal conductivity of nanofluids of tin dioxide synthesized via microwave-induced combustion route

SnO₂ nanofluids were prepared by dispersing tin dioxide nanoparticles in deionized (DI) water as a base fluid. 4–5 nm tin dioxide crystals were synthesized via chloride solution combustion synthesis (CSCS) using SnCl₄ and sorbitol as a novel precursor and the fuel, respectively. Ammonium nitrate was also used as the combustion aid. The molar ratio of sorbitol plus ammonium nitrate to SnCl₄ was set at unity; whereas, the molar ratio of sorbitol-to-ammonium nitrate divided by that of stoichiometric value (Φ) was varied in the range of 0.5–1.4 in order to find the optimum values of specific surface area for the CSCS technique. Transition electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD), and Brunauer–Emmet–Teller (BET) techniques were employed for the characterization of the nanoparticles. Since SnO₂ nanoparticles form clusters within fluids, the fluids were ultrasonicated to improve the dispersion and stability of the nanoparticles. The colloidal stability of the SnO₂ nanofluids was quantitatively characterized by UV–vis spectrophotometric measurements. The results of the UV–vis experiments indicate higher dispersion together with enhanced stability for the nanofluid prepared by SnO₂ nanoparticles synthesized at Φ = 1.0. After 500 h sedimentation time, the relative concentration of the nanofluid with the highest stability is remained at around 77% of the initial concentration of the fluid.A transient hot-wire apparatus was used to measure the thermal conductivities of the nanofluids. In addition, the effects of pH and temperature on the thermal conductivity were also investigated. At 353 K, for the nanofluid prepared by SnO₂ nanoparticles synthesized at Φ = 1.0 at a weight fraction of 0.024%, thermal conductivity is enhanced up to about 8.7%, with an optimal pH = 8.     

Preparation and electrochemical performance of SnO2@carbon nanotube core–shell structure composites as anode material for lithium-ion batteries

Carbon nanotube-encapsulated SnO₂ (SnO₂@CNT) core–shell composite anode materials are prepared by chemical activation of carbon nanotubes (CNTs) and wet chemical filling. The results of X-ray diffraction and transmission electron microscopy measurements indicate that SnO₂ is filled into the interior hollow core of CNTs and exists as small nanoparticles with diameter of about 6 nm. The SnO₂@CNT composites exhibit enhanced electrochemical performance at various current densities when used as the anode material for lithium-ion batteries. At 0.2 mA cm^?2 (0.1C), the sample containing wt. 65% of SnO₂ displays a reversible specific capacity of 829.5 mAh g^?1 and maintains 627.8 mAh g^?1 after 50 cycles. When the current density is 1.0, 2.0, and 4.0 mA cm^?2 (about 0.5, 1.0, and 2.0C), the composite electrode still exhibits capacity retention of 563, 507 and 380 mAh g^?1, respectively. The capacity retention of our SnO₂@CNT composites is much higher than previously reported values for a SnO₂/CNT composite with the same filling yield. The excellent lithium storage and rate capacity performance of SnO₂@CNT core–shell composites make it a promising anode material for lithium-ion batteries.     

Synthesis of SnO2@MnO2@graphite nanosheet with high reversibility and stable structure as a high-performance anode material for lithium-ion batteries

In this study, SnO₂@MnO₂@graphite (SMG) anode material is prepared via a facile ball-milling approach combined with hydrothermal treatment. SnO₂ and MnO₂ nanoparticles are evenly dispersed on numerous sheet-like graphite. MnO₂ can not only play a catalytic role for facilitating the conversion reaction of Sn/Li₂O to SnO₂, but also as a barrier to impede the coarsening of Sn in the composite. Meanwhile, graphite nanosheets could serve as an ideal volume expansion buffer and good electron conductor. Consequently, the SMG anode delivers superior reversible capacity of 1048.5 mAhg⁻¹, ideal rate capability of 522.2 mAhg⁻¹ at 5.0 A g^-1 and stable long-life cyclic performance of 814.8 mAhg⁻¹ at 1.0 A g^-1 after 1000 cycles. This result indicates that the incorporation of MnO₂, graphite nanosheet and SnO₂ have a great potential in enhancing the performance of SnO₂-based anode for battery applications.     

Highly sensitive acetone sensor based on Eu-doped SnO2 electrospun nanofibers

In this study, a series of undoped and Eu-doped SnO₂ nanofibers were synthesized via a simple electrospinning technique and subsequent calcination treatment. Field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were carefully used to characterize the morphologies, structures and chemical compositions of these samples. The results reveal that the as-prepared nanofibers are composed of crystallite grains with an average size of about 10 nm and Eu³⁺ ions are successfully doped into the SnO₂ lattice. Compared with pure SnO₂ nanofibers, Eu-doped SnO₂ nanofibers demonstrate significantly enhanced sensing characteristics (e.g., large response value, short response/recovery time and outstanding selectivity) toward acetone vapor, especially, the optimal sensor based on 2 mol% Eu-doped SnO₂ nanofibers shows the highest response (32.2 for 100 ppm), which is two times higher than that of the pure SnO₂ sensor at an operating temperature of 280 °C. In addition, the sensor exhibits a good sensitivity to acetone in sub-ppm concentrations and the detection limit could extend down to 0.3 ppm, making it a potential candidate for the breath diagnosis of diabetes.     

Graphene-supported SnO2 nanoparticles prepared by a solvothermal approach for an enhanced electrochemical performance in lithium-ion batteries

SnO₂ nanoparticles were dispersed on graphene nanosheets through a solvothermal approach using ethylene glycol as the solvent. The uniform distribution of SnO₂ nanoparticles on graphene nanosheets has been confirmed by scanning electron microscopy and transmission electron microscopy. The particle size of SnO₂ was determined to be around 5 nm. The as-synthesized SnO₂/graphene nanocomposite exhibited an enhanced electrochemical performance in lithium-ion batteries, compared with bare graphene nanosheets and bare SnO₂ nanoparticles. The SnO₂/graphene nanocomposite electrode delivered a reversible lithium storage capacity of 830 mAh g⁻¹ and a stable cyclability up to 100 cycles. The excellent electrochemical properties of this graphene-supported nanocomposite could be attributed to the insertion of nanoparticles between graphene nanolayers and the optimized nanoparticles distribution on graphene nanosheets.     

A novel carbon microspheres@SnO2/reduced graphene composite as anode for lithium-ion batteries with superior cycle stability

Many advantages made SnO₂ a potential anode for lithium-ion batteries, but huge volume expansion during cycling seriously impeded its practical application. Here, a novel double-carbon structure with low graphene weight proportion was successfully prepared using a facile hydrothermal method to enhance the long-cycle stability of SnO₂ as anodes for lithium-ion batteries. In this structure, SnO₂ nanoparticles were formed around the surface of the carbon microspheres (CMS), and the reduced graphene (GR) shuttled through the outer layer. As anodes for lithium-ion batteries, the SnO₂ protected by dual carbon (CMS@SnO₂/GR) exhibited outstanding cycle performance with an initial reversible capacity of 789.5 mAh g^-1 and the reversible capacity retention rate of 68.6% after 350 cycles at 200 mA g^-1. The abundance free space among CMS, nano-scale, and the excellent flexibility of graphene were all contributed to alleviating the volume variation of CMS@SnO₂/GR during the lithiation and delithiation.     

Solvothermal preparation and gas sensing properties of hierarchical pore structure SnO2 produced using grapefruit peel as a bio-template

Hierarchical pore structure nano-sized SnO₂ was synthesized using a solvothermal method with SnCl₄ as the raw material and grapefruit peel as the bio-template. The products were characterized by powder X-ray diffraction, high resolution scanning electron microscopy, transmission electron microscopy and nitrogen adsorption/desorption measurements. The results show that the SnO₂ prepared from the grapefruit peel bio-template consists of many large size (5–20 µm) interconnected pores with a honeycomb structure and nanosized pores (9.46 nm) on the walls of the large pores. The as-prepared SnO₂ presented a high specific surface area of 42.98 m²/g and the average crystallite size was about 10±0.5 nm. The gas sensing performance of the prepared material toward several volatile organic compounds was investigated. The results show that the hierarchical pore structure nano-sized SnO₂ was highly sensitive and selective to n-butanol, indicating that this material may be a promising candidate for future development as a n-butanol gas sensor.