二氧化锡基气敏材料研究进展

在众多可应用于气敏传感器的金属氧化物材料中,SnO_2半导体是应用范围最为广泛的金属氧化物之一。现今对于SnO_2基气敏材料的性能改良主要通过两种手段:一是掺杂法,通过与不同的材料复合,制备复合金属氧化物;二是SnO_2纳米材料的制备,控制制备不同形貌的纳米材料。总结了SnO_2纳米材料的制备方法,以及不同材料掺杂形成的SnO_2基气敏材料,详细描述了各种复合材料的制备方法、形貌特点和气敏性能,并展望了未来SnO_2气敏材料的发展方向。     

含Mn中间层提高钛基SnO2电催化电极的稳定性

采用浸渍法和溶胶-凝胶法分别制备了含Mn中间层和SnO_2表面催化层,并结合高温热氧化工艺制备了Ti/SnO_2和Ti/MnOx/SnO_2电催化电极.采用SEM、EDS和XPS等方法对两种电极进行了表征,使用大电流加速寿命实验详细研究了涂层的表面形貌、元素组成和化学态对两种电极稳定性的影响.结果表明:Ti/MnOx/SnO_2电极的稳定性是Ti/SnO_2电极的4.8倍,涂层使电极的稳定性显著提高.致密的涂层和较多的晶格氧能有效减少或阻止阳极的腐蚀,是电极稳定性提高的主要原因.     

用Mssbauer谱研究Zn_2SnO_4的湿敏机理

本文用 Mssbauer 谱学方法,对半导体陶瓷 Zn_2SnO_4的湿敏机理做了分析,得出结论:Sn 原子对Zn_2SnO_4的湿敏机理是有贡献的,Zn_2SnO_4湿敏机理是电子离子混合型传导,作为湿敏机理分析方法,M(?)ssbauer 谱是比较合适的。     

不同压力下纳米 SnO_2材料的特性

用水热法制得了在室温大气环境下稳定的半导体 SnO_2纳米材料。用 X 射线粉晶衍射、透射电镜、高分辨电镜及 M(?)ssbauer 谱等研究了不同压力下的纳米 SnO_2的特性。随着压力增加,所有谱线都有明显展宽,其特性明显区别于一般的多晶 SnO_2。用残缺态的概念解释了实验结果。     

锑掺杂二氧化锡导电机理及制备方法研究现状

从二氧化锡的应用出发,总结了锑掺杂二氧化锡的导电机理和该材料湿相制备方法的研究现状。认为晶格的氧缺位、Sb~(5+)杂质在SnO_2禁带形成施主能级并向导带提供n型载流子是锑掺杂SnO_2导电的两种主要机理,将湿相制备超细锑掺杂SnO_2分为均相沉淀和非均相沉淀两个方案。最后列举了在制备锑掺杂SnO_2超细粉时存在的问题,并对今后工作提出了展望。     

SnO_2薄膜和气敏特性

应用射频溅射法制备SnO_2膜。对SnO_2膜进行了AES、ESCA理化学分析,结果表明:SnO_2膜的成分完全由SnO_2所组成,膜中并没有分离的Sn的成分。同时也对SnO_2膜进行了气敏特性测试分析,结果表明:SnO_2和Pd/SnO_2膜对CH_4、CO、H_2、NO_2、H_2S等气体均有明显的敏感特性,当SnO_2膜表面掺入几十(?)P_d后,对上述气体的敏感性有所增加,工作温度可降低到150℃左右,选择性也有不同程度的改善。     

SnO_2-Zn_2SnO_4与SrTiO_3压敏-电容双功能陶瓷电学性能对比研究

通过传统陶瓷制备工艺制备了SnO_2-Zn_2SnO_4陶瓷复合物,与某型号商用SrTiO_3压敏-电容双功能陶瓷对比了电学性能。结果显示,尽管二者的压敏电压均低于10V/mm,但SnO_2-Zn_2SnO_4陶瓷具有较为优越的电学非线性性质,其非线性系数达到7.6,漏电流仅为56μA/cm~2。40 Hz时,SnO_2-Zn_2SnO_4陶瓷的相对介电常数为2×10~4,低于SrTiO_3的9×10~4,同时,SnO_2-Zn_2SnO_4陶瓷的介电损耗要高于SrTiO_3,且随着频率的升高急剧降低。通过对比研究,SnO_2-Zn_2SnO_4陶瓷具有潜在的应用价值。     

Pd-X/SnO_2复合催化剂催化乙醇电氧化性能研究

采用溶剂热法制备了SnO_2纳米棒,以其为载体,采用溶剂热还原法制备Pd-X/SnO_2复合催化剂,通过X射线衍射(XRD)、扫描电镜(SEM)及X射线能谱仪(EDS)对复合催化剂进行表征,采用循环伏安法考察了Pd/SnO_2掺杂非贵金属Co、Zn、Fe和Sb复合催化剂对乙醇氧化电催化性能的影响。结果表明:SnO_2纳米棒呈针尖状,大小均匀,长度为600nm,平均直径约为100nm,Pd粒子高度分散在SnO_2纳米棒表面;在1mol/L KOH+1mol/L C_2H_5OH溶液中,制得的Pd-X(Co、Zn、Fe、Sb)复合催化剂对乙醇氧化均具有较好的催化活性,其中Pd-Zn/SnO_2催化剂表现了最佳的催化性能;当E=-0.2V时,Pd-Zn/SnO_2催化乙醇氧化的峰电流密度可达为30.7mA/cm~2。     

基于SnO_2/石墨烯的光催化及应变传感多功能涂层

利用喷涂法制备了兼具光催化性能和应变传感功能的SnO_2/石墨烯复合涂层。实验研究了石墨烯含量对涂层应变敏感性及SnO_2光催化性能的影响。石墨烯的引入能够有效地抑制SnO_2的团聚现象继而提高SnO_2/石墨烯复合涂层的光催化性能。此外,SnO_2/石墨烯复合涂层对应变展现出了良好的敏感性。     

β_2-SiW_(11)/PANI/SnO_2三元复合催化剂的制备及光催化性能

以杂多酸盐β_2-K_8SiW_(11)O_(39)·14H_2O为掺杂剂,采用固相法制备了β_2-SiW_(11)/PAIN/SnO_2三元复合催化剂,并用红外光谱、X-射线粉末衍射和扫描电子显微镜等手段对其进行了表征。以亚甲基蓝染料废水(8 mg/L)为探针反应,评价了其光催化性能,与一元催化剂SnO_2、β_2-SiW_(11)和二元催化剂/PAIN/SnO_2比较,三元催化剂β_2-SiW_(11)/PAIN/SnO_2表现出较高的光催化降解性能,经30W紫外灯照射120min后,其降解率为94.63%,光催化降解亚甲基蓝为一级动力学反应。     

Functionalization of selectively grown networked SnO2 nanowires with Pd nanodots by γ-ray radiolysis

γ-ray radiolysis is applied to synthesizing Pd nanodots on networked SnO(2) nanowires. The growth behavior of Pd nanodots is systematically investigated as a function of the precursor concentration, illumination intensity, and exposure time of the γ-rays. These factors greatly influence the growth behavior of the Pd nanodots. Selectively grown networked SnO(2) nanowires are uniformly functionalized with Pd nanodots by the radiolysis process. The NO(2) sensing characteristics of the Pd-functionalized SnO(2) nanowires are compared with those of bare SnO(2) nanowires. The results indicate that γ-ray radiolysis is an attractive means of functionalizing the surface of oxide nanowires with catalytic Pd nanodots. Moreover, the Pd-functionalization greatly enhances the sensitivity and response time in SnO(2) nanowire-based gas sensors.     

Fabrication and optical properties of mesoporous SnO2 nanowire arrays

Large-scale SnO2 mesoporous nanowires have been successfully synthesized by an improved sol-gel method within the nanochannels of porous anodic alumina templates. In this method, chloride of stannic and urea are used as precursors, chloride of stannic is acting as source of tin ions, and urea offers a basic medium through its hydrolysis. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and selected-area electron diffraction are used to characterize the SnO2 mesoporous nanowires. It is found that the as-prepared nanowires consist of SnO2 nanoparticles and pores. They can be indexed as rutile structures and diameters are about 50-70 nm. The growth mechanism of the mesoporous nanowires is also been discussed. The band gap of the as-prepared mesoporous nanowires is 3.735 eV, determined by UV/visible absorption spectral results. The SnO2 mesoporous nanowires show strong and stable photoluminescence with emission peak centered at 3.730 eV, which has never been reported in nanowires. It could be attributed to the exciton recombination.     

The structure and photoluminescence properties of Bi2O3-core/SnO2-shell nanowires

Bi2O3-core/SnO2-shell nanowires have been prepared by using a two-step process: thermal evaporation of Bi2O3 powders and sputtering of SnO2. The crystalline nature of the Bi2O3-core/SnO2-shell nanowires has been revealed by high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED). TEM analysis and X-ray diffraction (XRD) results indicate that the Bi2O3-core/SnO2-shell nanowires consist of pure tetragonal alpha-Bi2O3-phase momocrystalline cores and tetragonal SnO2-phase polycrystalline shells. The photoluminescence (PL) measurements show that Bi2O3 nanowires have a broad emission band centered at around 560 nm in the yellow-green region. On the other hand, the Bi2O3-core/SnO2-shell coaxial nanowires with the sputtering times of 4 and 8 min have a blue emission band centered at around 450 nm. In contrast, those with a sputtering time of 10 min have a broad emission band centered at approximately 550 nm again. The origin of this yellow-green emission from the core/shell nanowires, however, quite differs from that from Bi2O3 nanowires, i.e., it is not from the Bi2O3 cores but from the SnO2 shells.     

Improvement in sensing properties of SnO2 nanowires by functionalizing with Pt nanodots synthesized by gamma-ray radiolysis

Selectively-grown networked SnO2 nanowires were functionalized with Pt nanodots by the radiolysis process. NO2 sensing characteristics of Pt-functionalized SnO2 nanowires were compared with those of bare SnO2 nanowires. The results demonstrate that the Pt functionalization greatly enhances the sensitivity and response time in SnO2 nanowire-based gas sensors. The enhancement is likely to be associated with the spillover effect and/or easy dissociation of NO2 into more active chemical species by the catalytic effect of Pt.     

Ferromagnetism driven by oxygen vacancies in SnO2 nanowires

Room temperature ferromagnetism has been observed in SnO2 nanowires synthesized by a chemical vapor deposition using Au layers as catalyst. The nanowires are homogeneous and single-crystalline grown along the [101] direction, with diameters ranging from 25 to 100 nm and length greater than 20 microm. The special magnetization reaches 0.114 emu/g for the nanowires with diameter of approximately 25 nm and reduces with increasing diameters. Branched SnO2 nanowires were prepared via a two-step vapor-liquid-solid approach, and an enhanced magnetization was obtained. To the contrary, the nanowires annealed at 1300 degrees C in air were completely transformed into the particles and exhibit weakened magnetization. These results demonstrate that the ferromagnetic properties of the samples depend on the surface-to-volume ratio of nanowires. With a combined study of photoluminescence, our results reveal that the oxygen vacancies at the surface of nanowires contribute to the ferromagnetism of SnO2 nanowires. This argument is further confirmed by a sequential annealing in a rich-oxygen atmosphere, then in a low vacuum condition.     

The template-free synthesis of square-shaped SnO(2) nanowires: the temperature effect and acetone gas sensors

Square-shaped single-crystalline SnO(2) nanowires and their sphere-like hierarchical structures were synthesized successfully with a template-free hydrothermal approach. It was found that an intermediate phase-Na(2)Sn(OH)(6)-is first produced because it is slow to dissolve in ethanol/water media. The intermediate phase gradually decomposes and converts into SnO(2) at temperatures higher than 200?°C. The reaction temperature also affects the microstructure of SnO(2) nanomaterials. Uniform square-shaped SnO(2) nanowires, which form sphere-like hierarchical structures in 100% structure yield, can be produced at 285?°C on a large scale. The diameter of the nanowires shows a decrease accompanying the increase of the reaction temperature. The temperature effect could be a result of the faster and oriented growth of SnO(2) nanowires along their [Formula: see text] direction at higher temperature. Chemical sensors constructed with square-shaped SnO(2) nanowires exhibit excellent stability, good sensitivity and selectivity, as well as a quick response and short recovery times under exposure to acetone gas in practical applications.     

Fabrication of reliable semiconductor nanowires by controlling crystalline structure

One-dimensional SnO(2) nanomaterials with wide bandgap characteristics are attractive for flexible and/or transparent displays and high-performance nano-electronics. In this study, the crystallinity of SnO(2) nanowires was regulated by controlling their growth temperatures. Moreover, the correlation of the crystallinity of nanowires with optical and electrical characteristics was analyzed. When SnO(2) nanowires were grown at temperatures below 900?°C, they showed various growth directions and abnormal discontinuity in their crystal structures. On the other hand, most nanowires grown at 950?°C exhibited a regular growth trend in the direction of [100]. In addition, the low temperature photoluminescence measurement revealed that the higher growth temperatures of nanowires gradually decreased the 500 nm peak rather than the 620 nm peak. The former peak is derived from the surface defect related to the shallow energy level and affects nanowire surface states. Owing to crystallinity and defects, the threshold voltage range (maximum-minimum) of SnO(2) nanowire transistors was 1.5 V at 850?°C, 1.1 V at 900?°C, and 0.5 V at 950?°C, with dispersion characteristics dramatically decreased. This study successfully demonstrated the effects of nanowire crystallinity on optical and electrical characteristics. It also suggested that the optical and electrical characteristics of nanowire transistors could be regulated by controlling their growth temperatures in the course of producing SnO(2) nanowires.     

Preparation of SnO2 nanowires by solvent-free method using mesoporous silica template and their gas sensitive properties

In this paper, a facile method was presented to synthesize tin dioxide (SnO2) nanowires by solvent-free method using SnCl2 x 2H2O as precursor and mesoporous silica SBA-15 as the hard template. No solvent was used in the processing. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and N2 adsorption/desorption isotherms. The results indicated that SnO2 nanowires fabricated by this method have a diameter of about 8 nm and a relatively high surface area 73.0 m2/g. The gas sensing properties of SnO2 nanowires were measured. The response and recovery time of this sensor were 6 s and 12 s, respectively. With the concentration of toluene increasing, the response of the sensor doubled increase. Compared with bulk SnO2, SnO2 nanowires showed much higher response to toluene.     

Highly conductive coaxial SnO(2)-In(2)O(3) heterostructured nanowires for Li ion battery electrodes

Novel SnO(2)-In(2)O(3) heterostructured nanowires were produced via a thermal evaporation method, and their possible nucleation/growth mechanism is proposed. We found that the electronic conductivity of the individual SnO(2)-In(2)O(3) nanowires was 2 orders of magnitude better than that of the pure SnO(2) nanowires, due to the formation of Sn-doped In(2)O(3) caused by the incorporation of Sn into the In(2)O(3) lattice during the nucleation and growth of the In(2)O(3) shell nanostructures. This provides the SnO(2)-In(2)O(3) nanowires with an outstanding lithium storage capacity, making them suitable for promising Li ion battery electrodes.     

Synthesis of Zn2SnO4 nanowires and their photoluminescence properties

Single-crystalline Zn2SnO4 nanowires were successfully synthesized on a photoresist-coated Si substrate using a facile chemical vapor deposition method. The growth of the nanowires followed a self-catalytic vapor-liquid-solid process. During annealing, the photoresist was carbonized into a complex glassy and graphite carbon structure. The immiscibility between the carbon layer and the in-situ formed Zn2SnO4 was a prime factor in the formation of the one-dimensional Zn2SnO4 nanowires. A broad blue-red emission band centered at 490.4 nm was observed in the photoluminescence spectrum of these nanowires, and it was related to the oxygen vacancies in these nanowires.