Facile synthesis of Ni-doped SnO2 nanorods and their high gas sensitivity to isopropanol

In this work, pure SnO₂ and Ni-doped SnO₂ nanorods were synthesized through a one-step template-free hydrothermal method and then used to detect isopropanol. Sensors fabricated with the Ni-doped SnO₂ nanocomposites showed the best gas sensing performance when the Ni doping amount was 1.5 mol.%. The response reached 250 at 225 °C, which was approximately 8.3 times higher than that of the pure SnO₂ nanorods. The limit of detection for isopropanol was as low as 10 ppb at the optimum working temperature. In addition, it also displayed good selectivity and excellent reproducibility. It is believed that the enhanced isopropanol sensing behavior benefit from the increased oxygen defects and larger specific surface area by Ni doping.     

Cathodoluminescence study of SnO2 powders aimed for gas sensor applications

In this paper we report on cathodoluminescence (CL) spectra of SnO₂ powders, synthesized using the wet chemical route. The analysis of influence of the modes of calcination (T_an-450–800 °C), and doping by both Pd and Pt (0.01–10.0 wt.%) on CL spectra was made. It was found that the measurement of CL spectra could be an effective research method of nanostructured metal oxides, aimed for gas sensor applications. It was established that in nanocrystalline SnO₂ the same system of energy levels, associated with radiative recombination, as in single crystalline and polycrystalline SnO₂, is retained. It was found that doping by both Pd and Pt modifies the structural properties of SnO₂ grains. Also, there is an optimum doping; near 0.1–0.2 wt.%, at which a maximum intensity of cathodoluminescence is reached. It was concluded that for low concentrations of both Pd and Pt additives in SnO₂ an improvement of the material's crystal structure is promoted, and is associated with a decrease in the non-radiating recombination rate.     

Porous SnO2 sputtered films with high H2 sensitivity at low operation temperature

Undoped and Pd-doped SnO₂ films were deposited at various substrate temperatures and discharge gas pressures using reactive magnetron sputtering. Structural factors of the films, such as crystallite size, grain size, and film density, were systematically investigated. The main objectives of this study are to clarify the operation temperature dependence of the H₂ sensitivity of these films as well as to clarify the dominant structural factor in the determination of the sensitivity. The operation temperature at which the sensitivity defined by (R_a−R_g)/R_g, where R_a and R_g are the resistances before and after exposure to H₂, showed a maximum decreased with decreasing film density. The highest sensitivity of 4470 was obtained for a Pd-doped film with the lowest density of 3.1 g/cm³ at 100 °C. It was found that the sensitivity correlated with film density rather than with crystallite size and grain size. The high sensitivity of a Pd-doped porous film at a low temperature was discussed in relation to the Schottky-barrier-limited transport as well as the chemical and electronic effects of Pd.     

SnO2/NiO复合半导体纳米纤维的制备及气敏性能研究

采用静电纺丝技术结合化学沉淀法和高温煅烧处理, 制备了具有不同Sn含量的SnO₂/NiO复合半导体纳米纤维。采用扫描电子显微镜(SEM), X射线衍射仪(XRD)和能量色散X射线光谱仪(EDS)对样品的形貌, 结构以及各元素含量进行表征。以乙醇为目标气体, 探究SnO₂/NiO纳米纤维的气体传感性质, 以及Sn含量对复合纳米纤维气敏性能的影响。研究结果表明, SnO₂/NiO复合纳米纤维具有三维网状结构, SnO₂复合对NiO纳米纤维的气敏性能具有明显的增强作用。随着SnO₂含量的增加, 复合纤维对乙醇气体的响应灵敏度增强, 其中响应最高的复合纳米纤维在最佳工作温度160 ℃条件下对体积分数为100×10^-6乙醇气体的响应灵敏度为13.4, 是NiO纳米纤维最大响应灵敏度的8.38倍。与市面常见的乙醇气体传感器MQ-3相比, SnO₂/NiO复合纳米纤维的最佳工作温度更低, 响应灵敏度更高, 具有一定的实际应用价值。     

一维Pt/SnO2纳米纤维的制备及NOx气敏性研究

为了制备出室温条件下对NO_x气体具有更高灵敏度和更快响应的传感器纳米材料并研究其气敏性能, 本研究通过高压静电纺丝法制备出一维Pt/SnO₂中空纳米纤维。采用XRD、SEM、TEM等表征手段对其结构和形貌进行研究, 同时进行了NO_x的气敏性能测试并予以探讨。研究结果表明: Pt/SnO₂纳米材料是一维中空管状及类似管状结构; 当Pt掺杂量为0.3wt%、NO_x浓度为9.7×10^-5 (V/V)时, NOx响应最快为11.33 s, 灵敏度最高可达109.6%; 当Pt掺杂量为0.5wt%时, 对NO_x检测限最低浓度可达2.91×10^-6 (V/V)。     

High sensitivity ozone sensors for environmental monitoringproduced using laser ablated nanocrystalline metal oxides

A series of gas sensors produced using the laser ablated nanocrystalline metal oxides. SnO₂, In₂O₃ , and WO₃ have been studied. Devices were tested with a view to their potential use as ozone detectors. Initially, fabrication procedures and compositions were optimized. The investigation then focused on parameters important for environmental monitoring applications including sensitivity, selectivity, and response time. High sensitivities to ppb ozone levels were observed particularly in the case of devices produced using SnO₂ and In₂O₃. Good selectivity was also observed for all optimized materials together with fast response times. These latter characteristics were particularly good for devices produced using WO₃     

Sensitivity enhancement for H2 gas detection using a SnO2–Ag2O–PdOx nanocrystalline system

Thick film H₂ sensors were fabricated using SnO₂ loaded with Ag₂O and PdO_x. The composition that gave highest sensitivity for H₂ was in the wt.% ratio of SnO₂:Ag₂O:PdO_x as 93:5:2. The nano-crystalline powders of SnO₂–Ag₂O–PdO_x composites synthesized by sol–gel method were screen printed on alumina substrates. Fabricated sensors were tested against gases like H₂, CH₄, C₃H₈, C₂H₅OH and SO₂. The composite material was found sensitive against H₂ at the working temperature 125 °C, with minor interference of other gases. H₂ gas as low as 100 ppm can be detected by the present fabricated sensors. It was found that the sensors based on SnO₂–Ag₂O–PdO_x nanocrystalline system exhibited high performance, high selectivity and very short response time to H₂ at ppm level. These characteristics make the sensor to be a promising candidate for detecting low concentrations of H₂.     

SnO/SnO2 heterojunction: an alternative candidate for sensing NO2 with fast response at room temperature

The SnO₂-based family is a traditional but important gas-sensitive material. However, the requirement for high working temperature limits its practical application. Much work has been done to explore ways to improve its gas-sensing performance at room temperature (RT). For this report, SnO₂, SnO, and SnO/SnO₂ heterojunction was successfully synthesized by a facile hydrothermal combined with subsequent calcination. Pure SnO₂ requires a high operating temperature (145 °C), while SnO/SnO₂ heterojunction exhibits an excellent performance for sensing NO₂ at RT. Moreover, SnO/SnO₂ exhibits a fast response, of 32 s, to 50 ppm NO₂ at RT (27 °C), which is much faster than that of SnO (139 s). The superior sensing properties of SnO/SnO₂ heterojunction are attributed to the unique hierarchical structures, large number of adsorption sites, and enhanced electron transport. Our results show that SnO/SnO₂ heterojunction can be used as a promising high-performance NO₂ sensitive material at RT.     

异质复合结构纳米纤维SnO2/ZnO的制备及其气敏特性研究

采用静电纺丝法制备了多级中空结构的SnO₂纳米纤维, 然后将SnO₂纳米纤维置于90℃乙酸锌溶液中, 恒温水浴条件下, 在SnO₂纳米纤维上生长了ZnO纳米球, 形成了异质结构的SnO₂/ZnO复合纳米纤维。分别通过XRD、SEM、EDX和XPS等表征手段对异质复合纳米纤维SnO₂/ZnO材料的结构、形貌及元素含量进行了表征分析。异质结构的SnO₂/ZnO复合纳米纤维保持了SnO₂纳米纤维多级中空的纤维结构, SnO₂纳米纤维长度约为300 nm, 依附于SnO₂纤维表面的SnO₂纳米颗粒生长的ZnO纳米球直径为250~300 nm。采用静态气体测试系统对异质复合纳米纤维SnO₂/ZnO气敏元件的气敏性能进行了测试。测试结果表明: 异质复合纳米纤维SnO₂/ZnO气敏元件在最佳工作温度350℃下, 对(0.5~100)×10^-6丙酮具有优异的响应灵敏度、较好的选择性和长期稳定性。异质复合纳米纤维SnO₂/ZnO中存在于ZnO纳米球与SnO₂纳米颗粒间的N-N同型异质结导致复合材料晶界势垒高度的降低, 改善了电子与空穴的输运特性, 促使SnO₂/ZnO异质复合纳米纤维的吸附能力大大增强, 从而改善了SnO₂/ZnO元件的丙酮敏感特性。     

陶瓷微球新型直接滴定成型工艺研究

以平均粒径为0.1~0.5μm的SnO₂粉为原料,通过凝胶注模成型制备SnO₂浆料,并使用滴定针筒将浆料直接滴定于旋转的金属基超疏水表面,使SnO₂液滴在不同条件下的旋转金属基超疏水表面固化成球。研究了液滴尺寸、成型时间、固含量等因素对微球成型的影响规律,结果表明:直接滴定成型的SnO₂陶瓷微球的球形度十分理想,球形度大于常规滴定成型法,并且可成型出直径0.1~0.5 mm的陶瓷微球;微球的球形度随固含量的增加而增大,随液滴尺寸的增加而减小,随固化时间的增加而减小;当液滴尺寸调整为0.05 mm时,使用凝胶注模工艺优化后的固含量为80%的SnO₂粉浆,在60℃时干燥固化30 min,该条件下获得的SnO₂陶瓷微球具有最高球形度,可达到99.5%;微球球坯烧结前后的表面微观组织结构较为均匀,烧结后可保持完整的球体形状。      

Au修饰SnO2复合纳米材料的制备和气敏性能

以氯金酸和乙酰丙酮氯化锡为主要材料,通过一步水热法制备了SnO₂和Au修饰的SnO₂（Au/SnO₂）纳米粒子.使用TEM、EDS、XRD和XPS等手段对样品的形貌、组成及结构进行表征,研究了两种材料对乙醇的气敏性能.结果表明,两种纳米颗粒的尺寸都比较均一,平均直径约为9-12 nm;SnO₂为四方金红石结构,Au为面心立方结构;在Au/SnO₂样品中,Au与SnO₂的重量比为2.6%,Au元素主要以Au⁰的价态存在并含有少量的Au³⁺价态;与纯SnO₂纳米粒子相比,Au修饰可显著提高气敏元件对乙醇响应的灵敏度和选择性。     

The preparation and gas sensitivity study of polythiophene/SnO2 composites

Nanocomposites of SnO₂ and polythiophene (PTP) were synthesized by the in situ chemical oxidative polymerization method. These nanocomposites were characterized by FTIR, transmission electron microscope (TEM), X-ray diffraction (XRD) and thermogravimetric and differential thermal analysis (TG–DTA) techniques, which proved the polymerization of thiophene monomer and the strong interaction between polythiophene and SnO₂. The composites were used for gas sensing to methanol (MeOH), ethanol (EtOH), acetone, and NO_x at different working temperature. It was found that PTP/SnO₂ materials with different PTP mass percent (1%, 5%, 10%, 20% and 30%) could detect NO_x with very higher selectivity and sensitivity at much lower working temperature than the reported SnO₂. The PTP/SnO₂ nanocomposites responded to NO_x at concentration as low as 10 ppm. PTP/SnO₂ composite containing 5 mass% PTP showed the highest sensitivity at room temperature. The sensing mechanism of PTP/SnO₂ nanocomposites to NO_x was presumed to be the effects of p–n heterojunction between PTP and SnO₂.     

Pd掺杂量对有机无机杂化SiO2膜H2/CO2分离性能和水热稳定性能的影响

以1,2-二(三乙氧基硅基)乙烷(BTESE)为前驱体、PdCl₂为钯源, 制备Pd掺杂有机无机杂化SiO₂(POS)溶胶, 涂膜后在水蒸气氛围中煅烧, 制备得到POS膜。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、N₂吸附-脱附和透射电子显微镜(TEM)对POS粉体的微观结构进行表征。考察了钯/硅摩尔比(n(Pd/Si)=0.1、0.5和1)对POS膜的气体分离性能与水热稳定性能的影响。结果表明: 随着Pd掺杂量的增加, POS膜的H₂渗透率逐渐增大, H₂/CO₂的理想选择性逐渐下降。经100 kPa水蒸气处理180 h后, 采用n (Pd/Si)=1制备的POS膜的H₂渗透率达到1.62× 10^-7 mol·m^-2·s^-1·Pa^-1, H₂/CO₂理想分离因子达到13.6, 表明该膜具有较好的H₂渗透性能、H₂/CO₂分离性能和水热稳定性能。     

SnO2修饰石墨毡电极的制备及其性能表征

采用H₂O₂对石墨毡（GF）进行预处理,然后在其表面电沉积Sn,最后在120℃烘箱氧化24 h制备出SnO₂修饰的石墨毡电极。通过扫描电镜（SEM）对SnO₂修饰前后的石墨毡表面形貌进行表征,采用循环伏安法研究了SnO₂修饰后石墨毡电极的电化学性能。结果表明：SnO₂能够均匀地包覆在石墨毡表面;SnO₂修饰石墨毡后V⁴⁺/V⁵⁺电对的氧化峰的峰电流由0.0538 A增加到0.0708 A,与未处理石墨毡相比增加了31.5%,反应峰出峰持续时间提高,说明SnO₂对V⁴⁺/V⁵⁺电对电极过程具有一定的催化作用。析氧电位由1.382 V增加到了1.517 V,使电极在VOSO₄溶液中的电化学窗口变宽。     

Sub-parts-per-billion level detection of dimethyl methyl phosphonate (DMMP) by quantum cascade laser photoacoustic spectroscopy

The need for the detection of chemical warfare agents (CWAs) is no longer confined to battlefield environments because of at least one confirmed terrorist attack, the Tokyo Subway [Emerg. Infect. Dis. 5, 513 (1999)] in 1995, and a suspected, i.e., a false-alarm of a CWA in the Russell Senate Office Building [Washington Post, 9 February 2006, p. B01]. Therefore, detection of CWAs with high sensitivity and low false-alarm rates is considered an important priority for ensuring public safety. We report a minimum detection level for a CWA simulant, dimethyl methyl phosphonate (DMMP), of <0.5 ppb (parts in 10(9)) by use of a widely tunable external grating cavity quantum cascade laser and photoacoustic spectroscopy. With interferents present in Santa Monica, California street air, we demonstrate a false-alarm rate of 1:10(6) at a detection threshold of 1.6 ppb.     

Comparison of the electrochemical behavior of CeO2–SnO2 and CeO2–TiO2 electrodes produced by the Pechini method

CeO₂–SnO₂ and CeO₂–TiO₂ thin films were prepared by the Pechini method and their characteristics were compared, using a fractional factorial design to quantify the effect of five preparation variables. It was observed that CeO₂–SnO₂ electrodes show a greater electrochemical response than the CeO₂–TiO₂ films. The best intercalation charge densities were 18.11 and 9.91 mC/cm² for CeO₂–SnO₂ and CeO₂–TiO₂, respectively. Both films were optically inactive with transparencies, in most cases, higher than 90%.     

Excimer laser deposition and characteristics of tin oxide thin films

ArF excimer laser assisted chemical vapor deposition of tin oxide thin films on Si was obtained using SnCl₄ and O₂ as precursors. Experimental measurements revealed that the deposition rate increases with incident laser energy density. The composition, structure and ultraviolet-to-visible spectra of the thin films were investigated by means of XPS, SEM, XRD and a UV–Vis techniques. It was shown that SnO₂ and SnOCl₂ coexisted in the thin films, and SnOCl₂ was almost completely converted into SnO₂ after annealing. The SnO₂ thin films deposited at room temperature were amorphous in structure and the grain size of the films became larger after annealing. The transmittance of the SnO₂ thin films is above 90%, the absorption edge is 355 nm and the energy gap is 3.49 eV.     

SnO2-Fe2O3复合材料应用于碳纳米管集流体对锂离子电池性能的影响

水热合成法制备纳米SnO₂-Fe₂O₃复合材料,以SnO₂-Fe₂O₃为活性物质,多壁碳纳米管（MWCNTs）导电纸代替传统铜箔作为负极集流体制作锂离子电池。采用XRD、SEM进行表征,结果显示,SnO₂-Fe₂O₃均匀嵌入到MWCNTs构建的三维导电网络的空隙中。电化学测试结果表明,SnO₂-Fe₂O₃/MWCNTs导电纸作为负极电极能够显著提高锂离子电池的循坏和倍率性能。在100 mA/g电流密度下循环30次,SnO₂-Fe₂O₃/MWCNTs导电纸电池比容量达到1 088 mAh/g,而在200 mA/g电流密度下循环200次后,SnO₂-Fe₂O₃/MWCNTs导电纸比容量能稳定保持在898 mAh/g,表现出良好的循环性能,逐渐增大充放电电流,电池的比容量有所下降但其库伦效率仍然保持在96%以上,而在高倍率（1 600 mA/g）下进行充放电时,SnO₂-Fe₂O₃/MWCNTs导电纸比容量仍然能够保持在547 mAh/g,之后再将电流密度降到100 mA/g,比容量重新回到1 000 mAh/g,SnO₂-Fe₂O₃/MWCNTs导电纸表现出十分优异的电化学性能。      

锂离子电池负极材料PAN-ACF/SnO2的研究

以聚丙烯腈基活性碳纤维(PAN-ACF)和SnCl₂为原料, 采用溶胶-凝胶法制备PAN-ACF/SnO₂复合材料并将其用作锂离子电池负极材料。采用X射线衍射仪(XRD)分析材料的组成及晶体结构; 用扫描电镜(SEM)观察样品形貌; 用热失重分析(TGA)对复合材料中SnO₂的含量进行测定; 用恒流充放电、交流阻抗(EIS)和循环伏安(CV)对复合材料作为锂离子电池负极材料的电化学性能进行表征。结果表明, SnO₂的含量对产物的形貌、结构和电化学性能有重要的影响。所制得的PAN-ACF/SnO₂复合材料中SnO₂ 的晶格常数a=0.4739 nm和c=0.3181 nm, 为四方金红石结构。PAN-ACF表面在多次充放电过程中未发生明显变化。该复合材料用作锂离子电池负极材料时, 在电流密度为50 mA/g的条件下, SnO₂含量为41.9%的复合材料首次放电高达1824 mAh/g, 20次后容量仍保持在450 mAh/g左右并趋于稳定, 呈现出良好的循环性能。     

SnO2退火温度对钙钛矿太阳能电池性能的影响

电子传输层是钙钛矿太阳能电池的关键部分, 起到阻挡空穴、传输电子和减少电子空穴复合的作用。本研究采用低温溶液法制备SnO₂薄膜作为钙钛矿电池的电子传输层, 研究SnO₂的退火温度对电子传输层微观形貌、物理性能以及钙钛矿太阳能电池性能的影响。结果表明: 当退火温度为60、90、120和240 ℃时, SnO₂薄膜表面存在较多的孔隙; 而退火温度为150、180和210 ℃时, 薄膜表面孔隙较少。在实验温度下, 制备的SnO₂薄膜为四方相, FTO玻璃上涂覆SnO₂薄膜后其透过率要优于空白FTO玻璃的透过率。当SnO₂退火温度为180 ℃时, 薄膜的电子迁移率最高, 钙钛矿电池具有最佳的传输电阻和复合电阻, 所得电池的性能最优, 其光电转换效率为17.28%, 开路电压为1.09 V, 短路电流为20.91 mA/cm², 填充因子为75.91%。