Gas‐Sensing Properties of Needle‐Shaped Ni‐Doped SnO2 Nanocrystals Prepared by a Simple Sol–Gel Chemical Precipitation Method

The preparation of needle‐shaped SnO₂ nanocrystals doped with different concentration of nickel by a simple sol–gel chemical precipitation method is demonstrated. By varying the Ni‐dopant concentration from 0 to 5 wt %, the phase purity and morphology of the SnO₂ nanocrystals are significantly changed. Powder XRD results reveal that the SnO₂ doped with a nickel concentration of up to 1 wt % shows a single crystalline tetragonal rutile phase, whereas a slight change in the crystallite structure is observed for samples with nickel above 1 wt %. High resolution scanning electron microscopy (HRSEM) results reveal the change in morphology of the materials from spherical, for SnO₂, to very fine needle‐like nanocrystals, for Ni‐doped SnO₂, annealed at different temperatures. The gas sensing properties of the SnO₂ nanocrystals are significantly enhanced after the nickel doping.     

Synthesis,characterization, and biosensing application of ZnO/SnO2 heterostructured nanomaterials

In this work, zinc oxide/tin oxide (ZnO/SnO₂) heterostructured nanomaterials were synthesized by hydrothermal method. Transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction measurements revealed that the product was composed of ZnO nanowires and SnO₂ nanobranches. The novel ZnO/SnO₂ heterostructured nanocrystals were for the first time used as a supporting matrix to explore a novel immobilization and biosensing platform of redox proteins. UV–visible absorption investigation indicated that hemoglobin (Hb) intercalated well in the ZnO/SnO₂ heterostructured nanocrystals retained its native structure. Comparative experiments have confirmed that the ZnO/SnO₂-based biosensor not only had enhanced direct electron transfer capacity but also displayed excellent electrocatalytic properties such as higher sensitivity and wider linear range to the detection of hydrogen peroxide in comparison with the ZnO- and SnO₂-based biosensors.     

Conductivity of SnO<Subscript>2</Subscript>-In<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocrystalline composite films

The conductivity of films consisting of a mixture of SnO₂ and In₂O₃ nanocrystals at 200–500°C was studied. Based on the experimental data, it was assumed that in films containing less than 20 wt % In₂O₃, the current flows along SnO₂ nanocrystals. A model of conductivity in these films is presented; it includes an electron transfer from In₂O₃ to SnO₂, which forms positively charged In₂O₃ nanocrystals that contact the negatively charged SnO₂ nanocrystals. In the presence of In₂O₃ nanocrystals, the activation energy of the electron transfer between SnO₂ nanocrystals decreased substantially because of a decrease in the barrier of electron transfer between SnO₂ crystals under the action of the negative charge. As a result, a percolation cluster of charged SnO₂ crystals formed. At high contents of In₂O₃ (over 20 wt %), the conductivity increased dramatically. The curve of the temperature dependence of conductivity changed because of the appearance of a percolation cluster of In₂O₃ nanocrystals, in which the current passed. The conductivity of a mixed film of this kind differed from that of the nanocrystalline film of pure In₂O₃.     

溶胶-凝胶法可控制备氧化锡纳米晶包覆碳纳米管

采用溶胶-凝胶法制备了氧化锡纳米晶包覆的碳纳米管。自由Sn4+离子从稳定的Sn柠檬酸配合物中缓慢释放出来,迁移到碳纳米管上,并在碳纳米管上沉积形成了SnO2纳米晶,沉积过程完全为异相成核方式,在碳纳米管外并没有发现单独的SnO2纳米晶。这种溶胶-凝胶方法还可以用来制备无氯离子污染的、低团聚的纯SnO2纳米晶。     

One-pot template-free synthesis, formation mechanism, and lithium ions storage property of hollow SnO2 microspheres

In this work, we report a facile one-pot template-free approach to prepare hollow rutile SnO₂ microspheres using SnCl₄ as the precursor in a condensed H₂SO₄–EtOH mixed solvent. The formation mechanism of the hollow microspheres was proposed on the basis of characterizations. First, the controlled hydrolysis and condensation of SnCl₄ to SnO₂ nanocrystals was realized by the formation of water via catalytic dehydration of EtOH in the presence of condensed H₂SO₄. These SnO₂ nanocrystals rapidly aggregated to form microspheres in order to minimize their surface energies. Then, Ostwald ripening mechanism governed the subsequent growth and recrystallization of the nanocrystals to form the hollow structure. The resulting hollow SnO₂ microspheres exhibited better cycle performance than the pristine SnO₂ nanoparticles when used as anode materials in lithium ion batteries.     

Influence of Size and Shape on the Photocatalytic Properties of SnO2 Nanocrystals

Tuning the functional properties of nanocrystals is an important issue in nanoscience. Here, we are able to tune the photocatalytic properties of SnO₂ nanocrystals by controlling their size and shape. A structural analysis was carried out by using X‐ray diffraction (XRD)/Rietveld and transmission electron microscopy (TEM). The results reveal that the number of oxygen‐related defects varies upon changing the size and shape of the nanocrystals, which eventually influences their photocatalytic properties. Time‐resolved spectroscopic studies of the carrier relaxation dynamics of the SnO₂ nanocrystals further confirm that the electron–hole recombination process is controlled by oxygen/defect states, which can be tuned by changing the shape and size of the materials. The degradation of dyes (90 %) in the presence of SnO₂ nanoparticles under UV light is comparable to that (88 %) in the presence of standard TiO₂ Degussa P‐25 (P25) powders. The photocatalytic activity of the nanoparticles is significantly higher than those of nanorods and nanospheres because the effective charge separation in the SnO₂ nanoparticles is controlled by defect states leading to enhanced photocatalytic properties. The size‐ and shape‐dependent photocatalytic properties of SnO₂ nanocrystals make these materials interesting candidates for photocatalytic applications.     

Eu<Superscript>3+</Superscript>-fluorescence properties in nano-crystallized SnO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

Fluorescence and spectral hole burning properties of Eu³⁺ ions were studied in nanocrystals-precipitated SnO₂-SiO₂ glasses. The glasses were prepared to contain various amount of Eu₂O₃ using the sol-gel method, in which SnO₂ nanocrystals were precipitated by heating in air. In the glasses containing Eu₂O₃ less than 1%, the Eu³⁺ ions were preferentially doped in the SnO₂ nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons and holes excited in SnO₂ crystals. The SnO₂ nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence intensities of the Eu³⁺ ions. With the increasing Eu₂O₃ concentration, the amount of SnO₂ nanocrystals decreased and the Sn⁴⁺ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities and the hole depth to decrease.     

Enhanced gas sensing by assembling Pd nanoparticles onto the surface of SnO2 nanowires

SnO₂ nanowires with an average 0.6 μm in length and about 25 nm in diameter were prepared by a hydrothermal method. The sensors were fabricated using SnO₂ nanowires assembled with Pd nanocrystals. The sensing properties of the sensors such as selectivity, response-recovery time and stability were tested at 290 °C. After assembling Pd nanocrystals onto the surface of SnO₂ nanowires, the gas sensing properties of the sensors toward H₂S were improved. The sensors based on Pd nanoparticle@SnO₂ nanowires exhibit high stability owing to stable single crystal structure. The mechanism of promoting sensing properties with Pd nanoparticles is discussed.     

Synthesis,Characterization and Photocatalytic Activity of Mg‐Impregnated ZnO–SnO2 Coupled Nanoparticles

ZnO–SnO₂ nanoparticles were prepared by coprecipitation method; then Mg, with different molar ratios and calcination temperatures, was loaded on the coupled nanoparticles by impregnation method. The synthesized nanoparticles were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), and Brunauer–Emmett–Teller (BET) techniques. Based on XRD results, the ZnO–SnO₂ and Mg/ZnO–SnO₂ nanoparticles were made of ZnO and SnO₂ nanocrystallites. According to DRS spectra, the band gap energy value of 3.13 and 3.18 eV were obtained for ZnO–SnO₂ and Mg/ZnO–SnO₂ nanoparticles, respectively. BET analysis revealed a Type III isotherm with a microporous structure and surface area of 32.051 and 49.065 m² g^?1 for ZnO–SnO₂ and Mg/ZnO–SnO₂, respectively. Also, the spherical shape of nanocrystallites was deduced from TEM and FESEM images. The photocatalytic performance of pure ZnO–SnO₂ and Mg/ZnO–SnO₂ was analyzed in the photocatalytic removal of methyl orange (MO). The results indicated that Mg/ZnO–SnO₂ exhibited superior photocatalytic activity to bare ZnO–SnO₂ photocatalyst due to high surface area, increased MO adsorption and larger band gap energy. Maximum photocatalytic activity of Mg/ZnO–SnO₂ nanoparticles was obtained with 0.8 mol% Mg and calcination temperature of 350°C.     

Polymer‐Templated Formation of Polydopamine‐Coated SnO2 Nanocrystals: Anodes for Cyclable Lithium‐Ion Batteries

Well‐controlled nanostructures and a high fraction of Sn/Li₂O interface are critical to enhance the coulombic efficiency and cyclic performance of SnO₂‐based electrodes for lithium‐ion batteries (LIBs). Polydopamine (PDA)‐coated SnO₂ nanocrystals, composed of hundreds of PDA‐coated “corn‐like” SnO₂ nanoparticles (diameter ca. 5 nm) decorated along a “cob”, addressed the irreversibility issue of SnO₂‐based electrodes. The PDA‐coated SnO₂ were crafted by capitalizing on rationally designed bottlebrush‐like hydroxypropyl cellulose‐graft‐poly (acrylic acid) (HPC‐g ‐PAA) as a template and was coated with PDA to construct a passivating solid‐electrolyte interphase (SEI) layer. In combination, the corn‐like nanostructure and the protective PDA coating contributed to a PDA‐coated SnO₂ electrode with excellent rate capability, superior long‐term stability over 300 cycles, and high Sn→SnO₂ reversibility.     

Effect of SnO2 Nanocrystals on the Emission of Eu3+ Ions in Silica Matrix

Silica xerogels containing Eu³⁺ ions and SnO₂ nanocrystals were prepared in the sol‐gel process, and characterized by x‐ray diffraction (XRD) and photoluminescence spectra. Under the excitation at 393 nm, characteristic emission of Eu³⁺ ions at 614 nm was enhanced with increasing amount of SnO₂ nanocrystals. Moreover, when the Eu³⁺/SnO₂ co‐doped samples were excited at 345 nm, corresponding to the sideband of SnO₂ nanocrystals, the emission of Eu³⁺ ions at 614 nm was clearly observed, while no emission of Eu³⁺ ions for the Eu³⁺‐doped sample. It may be ascribed to the energy transfer from SnO₂ conduction band to Eu³⁺ conduction band. Further experimental results suggest that the energy transfer may be achieved through surface transition state.     

Solid‐State Electrochemiluminescence of F‐doped SnO2 Nanocrystals and Its Sensing Application

Electrochemiluminescence (ECL) behaviors and mechanisms of fluorine‐doped tin oxide (F‐SnO₂) semiconductor nanocrystals (NCs) were firstly investigated in both of nonaqueous and aqueous solutions via potential scanning or pulsing. Furthermore, the ECL of F‐SnO₂ was applied successfully to detect dopamine based on the quenching effect.     

Preparation and formaldehyde sensitive properties of N-GQDs/SnO2 nanocomposite

Graphene quantum dots (GQDs) have both the properties of graphene and semiconductor quantum dots, and exhibit stronger quantum confinement effect and boundary effect than graphene. In addition, the band gap of GQDs will transform to non-zero from 0 eV of graphene by surface functionalization, which can be dispersed in common solvents and compounded with solid materials. In this work, the SnO₂ nanosheets were prepared by hydrothermal method. As the sensitizer, nitrogen-doped graphene quantum dots (N-GQDs) were prepared and composited with SnO₂ nanosheets. Sensing performance of pristine SnO₂ and N-GQDs/SnO₂ were investigated with HCHO as the target gas. The response (R_a/R_g) of 0.1% N-GQDs/SnO₂ was 256 for 100 ppm HCHO at 60 °C, which was about 2.2 times higher than pristine SnO₂ nanosheet. In addition, the material also had excellent selectivity and low operation temperature. The high sensitivity of N-GQDs/SnO₂ was attributed to the increase of active sites on materials surface and the electrical regulation of N-GQDs. This research is helpful to develop new HCHO gas sensor and expand the application field of GQDs.     

Band gap tuning in nanocomposite ZrO2–SnO2 thin film achieved through sol–gel co-deposition method

Transparent SnO₂, nanocomposite ZrO₂–SnO₂ and ZrO₂ thin films were prepared by sol–gel dip-coating technique. X-ray diffraction (XRD) spectra showed a mixture of three phases: tetragonal ZrO₂ and SnO₂ and orthorhombic ZrSnO₄. X-ray photoelectron spectroscopy (XPS) gave Zr 3d, Sn 3d and O 1s spectra of the nanocomposite ZrO₂–SnO₂ thin film which revealed the presence of oxygen vacancies in the nanocomposite ZrO₂–SnO₂ thin film. Scanning electron microscopy (SEM) observations showed that microstructure of the nanocomposite ZrO₂–SnO₂ thin film consists of uniform dispersion of isolated SnO₂ particles in ZrO₂ matrix. The band gap for the ZrO₂ was estimated to be 5.51 eV and that for the nanocomposite ZrO₂–SnO₂ film was 4.9 eV. These films demonstrated the tailoring of band gap values which can be directly employed in tuning the band gap by simply changing the relative concentration of zirconium and tin elements. Photoluminescence (PL) spectra revealed an intense emission peak at 424 nm in the nanocomposite ZrO₂–SnO₂ film which indicate the presence of oxygen vacancies in ZrSnO₄.     

Photocatalytic Degradation of Glyphosate in Water by N‐Doped SnO2/TiO2 Thin‐Film‐Coated Glass Fibers

Photocatalytic degradation of glyphosate contaminated in water was investigated. The N‐doped SnO₂/TiO₂ films were prepared via sol–gel method, and coated on glass fibers by dipping method. The effects of nitrogen doping on coating morphology, physical properties and glyphosate degradation rates were experimentally determined. Main variable was the concentration of nitrogen doping in range 0–40 mol%. Nitrogen doping results in shifting the absorption wavelengths and narrowing the band gap energy those lead to enhancement of photocatalytic performance. The near optimal 20N/SnO₂/TiO₂ composite thin film exhibited about two‐ and four‐folds of glyphosate degradation rates compared to the undoped SnO₂/TiO₂ and TiO₂ films when photocatalytic treatment were performed under UV and solar irradiations, respectively, due to its narrowest band gap energy (optical absorption wavelength shifting to visible light region) and smallest crystallite size influenced by N‐doping.     

Theoretical study on the stability and electronic property of Ag2SnO3

Bulk crystal properties of Ag₂SnO₃ were investigated with the advantage of density functional theory. The whole structure has layered feature: hexagonal metallic planes formed by Ag atoms and distorted octahedrons of SnO₆ clusters are configured alternatively along c axis of hexagonal cell. The cohesive energy is about ?2.792 eV/atom, which is less than SnO₂. The Debye temperature of Ag₂SnO₃ is about 231.6 K, and the bulk and shear moduli are 62.13 and 20.63 GPa, respectively. Band structure and DOS show the compound has a small pseudo-band gap value of 1.0 eV and so may be a semiconductor. When checking the PDOS intensity at the Fermi surface of Ag atoms, a weak metallic character can be seen. The distortion mechanism becomes less effective to reduce the total orbital energy both in SnO₂ and in Ag₂SnO₃ and as a result the bond lengths of Sn–O are intended to be isotropy.     

Metal-free indoline dye sensitized solar cells based on nanocrystalline Zn2SnO4

Zn₂SnO₄ nanocrystals were synthesized and first used as the electrode materials for the metal-free indoline dyes sensitized solar cells (DSSCs). The highest efficiency of 3.08% was achieved for a D131 DSSC. This might be attributed to the fact that the D131 dye has a greater positive oxidation potential, which can lead to rapid dye regeneration, avoiding the geminate charge recombination between oxidized dye molecules and injected electrons in the Zn₂SnO₄ film. The efficiency can be improved significantly using a mixture solution of D131 and N719 dyes for which an efficiency of 3.6% was obtained.     

SnO2纳米棒的生长过程、发光性能及光催化活性

在柠檬酸的调控下,采用水热法合成SnO_2纳米棒。利用高分辨透射电子显微镜、X射线衍射、傅里叶变换红外光谱、Brunauer-Emmett-Teller氮吸附、紫外可见漫反射光谱和光致发光光谱研究了SnO_2样品在生长过程中的结构特征。结果表明,SnO_2纳米晶体的生长可进一步分为2个阶段:早期SnO_2纳米晶遵循定向附着模式生长,而后期采取Ostwald熟化模式沿[001]方向缓慢生长。SnO_2纳米粒子在不同阶段的光致发光性能和光催化活性显示:在晶体的生长过程中,这2种性能变化趋势几乎相似,即生长前期性能迅速增加,随后性能逐渐降低。     

Photoelectrochemical study of electrodeposited TiO<Subscript>2</Subscript> thin films onto F:SnO<Subscript>2</Subscript> substrates

TiO₂ thin films have been effectively fused onto F:SnO₂ (FTO) substrates via the electrodeposition method. The influence of deposition temperature on the synthesis of F:SnO₂ substrates and relative information of as-deposited and annealed TiO₂ thin films have been studied. Novel TiO₂ microspheres are detected on F:SnO₂ substrates at an optimized electrodeposition potential. Raman bands approve the creation of single-anatase-phase TiO₂. The optimized deposition surroundings show a decrease in the band gap of F:SnO₂ substrates and TiO₂ thin films. The determined photoelectrochemical properties of annealed TiO₂ thin films indicate a fill factor of 51% and power conversion efficiency of 0.15% for application in solar cells.     

Facile Mechanochemical Synthesis of Nano SnO2/Graphene Composite from Coarse Metallic Sn and Graphite Oxide: An Outstanding Anode Material for Lithium‐Ion Batteries

A facile method for the large‐scale synthesis of SnO₂ nanocrystal/graphene composites by using coarse metallic Sn particles and cheap graphite oxide (GO) as raw materials is demonstrated. This method uses simple ball milling to realize a mechanochemical reaction between Sn particles and GO. After the reaction, the initial coarse Sn particles with sizes of 3–30 μm are converted to SnO₂ nanocrystals (approximately 4 nm) while GO is reduced to graphene. Composite with different grinding times (1 h 20 min, 2 h 20 min or 8 h 20 min, abbreviated to 1, 2 or 8 h below) and raw material ratios (Sn:GO, 1:2, 1:1, 2:1, w/w) are investigated by X‐ray diffraction, X‐ray photoelectron spectroscopy, field‐emission scanning electron microscopy and transmission electron microscopy. The as‐prepared SnO₂/graphene composite with a grinding time of 8 h and raw material ratio of 1:1 forms micrometer‐sized architected chips composed of composite sheets, and demonstrates a high tap density of 1.53 g cm^?3. By using such composites as anode material for LIBs, a high specific capacity of 891 mA h g^?1 is achieved even after 50 cycles at 100 mA g^?1.