Low temperature H_2S sensor based on copper oxide/tin dioxide thick film

Nanostructured tin dioxide (SnO2) powders were prepared by a sol-gel dialytic process and and the doping of CuO on it was completed by a deposition-precipitation method.The thick film sensors were fabricated from the CuO/SnO2 polycrystalline powders.Sensing behavior of the sensor was investigated with various gases including CO,H2,NH3,hexane,acetone,ethanol,methanol and H2S in air.The as-synthesized gas sensor had much better response to H2S than to other gases.At the same time,the CuO/SnO2 sensor had enough sensitivity,together with fast response and recovery,to distinguish H2S from those gases at 160 and 210 ?C.Therefore,it might have promising applications in the future.     

二氧化锡中空微球用于快速灵敏检测硫化氢

以氨基酚醛树脂球作模板,通过一种简单的模板法制备了具有中空微球(HMS)结构的二氧化锡;将其涂覆于氧化铝陶瓷管金电极表面,制得一种新型薄膜式硫化氢传感器.采用X射线衍射(XRD)及透射电子显微镜(TEM)表征了材料的微观结构和形貌,并考察了二氧化锡中空微球(Sn O2HMS)的气敏性能.结果表明,二氧化锡中空微球对硫化氢气体表现出良好的气敏特性.在最佳工作温度(200℃)下,所制作的传感器对142.6 mg/m3硫化氢的响应值高达97.13%,响应时间为22 s.该传感器对硫化氢的响应线性范围为0.2852~142.6 mg/m3,相关系数为0.9931,检出限达到0.1549 mg/m3,且几乎不受环境湿度和温度的影响,具有良好的重现性和选择性.对养殖场中硫化氢气体连续监测10个月后,传感器响应信号衰减了5.4%,表明该传感器具有长期稳定的使用寿命,可实现远程监测的实际应用.     

基于SnO2-CuO纳米纤维的薄膜型H2-S传感器研究

采用同轴静电纺丝技术制备了SnO2-CuO复合纳米纤维,采用提拉法将SnO2-CuO纳米纤维涂覆于印有梳状Au电极的氧化铝陶瓷管表面形成敏感薄膜,设计了一种新型薄膜式H2 S传感器。采用 X 射线衍射、扫描电子显微镜和X-射线光电子能谱( XPS)表征SnO2-CuO纳米纤维的相组成和微观形貌,分析了敏感薄膜成分配比和厚度对硫化氢敏感机理和电化学特性。采用WS-30A型气敏元件分析仪测试了H2 S传感器敏感特性、温度特性、湿度特性、动态响应、抗干扰特性和稳定性。结果表明,以C50纳米纤维为敏感薄膜(膜厚为70 nm)的H2 S传感器,在温度为25℃, H2 S气体浓度为10~60 mg/L时,传感器线性度和灵敏度分别为92.3％和98.2％,响应最大值为1080,承受的最大相对湿度为95％,动态响应和恢复时间分别为4和12 s。此传感器对CO, NO2, SO2, NH3, CO2, CH4和H2等有害气体具有较好的抗干扰性。在矿井中连续使用12月后,响应衰减了9.2％,响应正常时间为10.9月。     

A comparative study of CuO/TiO_2-SnO_2,Cut/Tit_2 and CuO/SnO_2 catalysts for low-temperature CO oxidation

Nanometer SnO2 particles were synthesized by sol-gel dialytic processes and used as a support to prepare CuO supported catalysts via a deposition-precipitation method. The samples were characterized by means of TG-DTA, XRD, H2-TPR and XPS. The catalytic activity of the CuO/TiO2-SnO2 catalysts was markedly depended on the loading of CuO, and the optimum CuO loading was 8 wt.% (T100 = 80 ◦C). The CuO/TiO2-SnO2 catalysts exhibited much higher catalytic activity than the CuO/TiO2 and CuO/SnO2 catalysts. H2-TPR result indicated that a large amount of CuO formed the active site for CO oxidation in 8 wt.% CuO/TiO2-SnO2 catalyst.     

热解法制备纳米SnO2及其气敏性能研究

作为一种n型金属氧化物半导体，SnO2由于具有寿命长、灵敏度高和成本低等特点而一直是电阻式气敏传感器研究的热点．由于SnO2材料的气敏效应是晶粒表面控制型的，因此，SnO2的传感性能对其粒径和比表面积的大小有很强的依赖性．改进SnO2制备方法，提高其气敏效应一直是气敏传感器研究的热点．目前，文献报道的方法大多是以SnCl4为原料制备SnO2，而以其它锡盐为原料的研究则很少。本文以SnC2O4为原料，通过低温直接热解SnC2O4制得SnO2．所得产物具有粒径小、分布均匀和比表面积大的特点，且具有良好的酒敏特性，该产物的红外吸收出现明显的红移现象。     

Nanocrystalline In2O3-based H2S sensors operable at low temperatures

Nanocrystalline In(2)O(3)-based solid solutions, with different concentration of Co, with cubic structure were successfully prepared by a simple route. The as-prepared materials were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The indirect heating structure sensors based on pure and doped In(2)O(3) as sensitive materials were fabricated on an alumna tube with Au electrodes and gas-sensing properties of the sensor elements were measured as a function of concentration of dopant, operating temperature and concentrations of the test gases. The results showed that In(2)O(3) had high response towards H(2)S gas at an operating temperature 150 degrees C, while 2.5 wt.% Co-doped In(2)O(3) sensor exhibited enhance response and selectivity to H(2)S at rather lower operating temperature. Incorporation of platinum further improved the response, selectivity and response time towards H(2)S. Platinum incorporated 2.5 wt.% Co-doped In(2)O(3) (Pt: 0.5 wt.%) was able to detect 10-100 ppm of H(2)S in air at an operating temperature of 100 degrees C. The selectivity of the sensor elements for H(2)S against liquefied petroleum gas (LPG), NH(3) and H(2) gases was studied. The improved gas-sensing properties can mainly be attributed to the selectivity to oxidation of H(2)S and noble metal additive sensitization.     

(Sn,Sb)O2-x基纳米结构厚膜材料气敏特性及机理

对采用水热合成技术所形成的纳米(Sn,Sb)O2 x晶粒结构、厚膜材料的气敏特性及其机理进行了研究,并采用XRD、TEM手段对纳米尺度的（Sn、Sb)O2 x晶粒的结构与表面效应及晶粒形态进行了表征.结果表明,当掺杂Sb5＋的浓度（摩尔分数xSb5＋)为（2.9～5.8)×10－6时,（Sn、Sb)O2 x纳米晶粒表面的电子缺陷浓度增大,增强了对气体的吸附能力,从而提高了对可燃性气体的灵敏度.同时可使晶粒保持短柱状的形态特征,对其灵敏度有一定的控制作用.     

基于叶片状氧化铜纳米材料的无酶葡萄糖传感电极

将Nafion交联剂与纳米材料修饰至玻碳电极基底制备一种无酶葡萄糖传感器,通过循环伏安曲线、时间-电流曲线检测该电极电化学特性. 氧化铜纳米复合膜具有高比表面积和多活性点位的优点. 实验结果表明,氧化铜纳米电极对葡萄糖的检测线性响应范围0.01 ~ 0.3 mmol·L^-1,灵敏度1783.58 μA·L·mmol^-1·cm^-2,检测限0.80 μmol·L^-1 (S/N=3),稳定性较好,能抵抗抗坏血酸、多巴胺和尿酸干扰.     

Distinction of gases with a semiconductor sensor depending on the scanning profile of a cyclic temperature

A gas-sensing system based on a dynamic nonlinear response is reported to improve the selectivity in the sensor response toward sample gases. A cyclic temperature composed of fundamental and second harmonics was applied to a SnO(2) semiconductor gas sensor and the resulting conductance of the sensor was analyzed by fast Fourier transformation (FFT). The dynamic nonlinear responses to the gas species were further characterized depending on the scanning profile of the temperature. These characteristic sensor responses under the application of second-harmonic perturbation were theoretically considered based on a reaction-diffusion model for the semiconductor surface.     

Gas Sensing Properties of Co3O4-loaded SnO2 to Ethanol and Acetone

A series of Co3O4-loaded SnO2 nanocomposite thick films were prepared by grinding, screen-printing and sintering at 700 ±C for 3 h. XRD data showed the nanocomposite thick films were rutile structure of SnO2 and cubic Co3O4. The composite films were found to exhibit good response to alcohol and acetone at 300 ±C. The film went through a sharp sensitivity maximum at 5 mol%CoO4=3 with a change in Co3O4 content. At 300 ±C, the maximum sensor response to alcohol and acetone, each 1000 ppm in air, was 301 and 235, respectively, which was about 7 and 5 times as large as that of the pure SnO2 respectively. The selectivity to alcohol and acetone over H2 and CO also was promoted by the addition of Co3O4 to SnO2. The mechanism of such strong promotion of sensor response (electronic sensitization) is discussed.     

Simple self-assembly of 3D laminated CuO/SnO2 hybrid for the detection of triethylamine

Tin dioxide is important gas sensor material and has wide applications in the detection of toxic gases and volatile organic compounds. Here, we synthesized a 3D laminated structural CuO/SnO₂ material possessing p-n heterostructures. The morphology and structure were characterized by XRD, SEM, TEM and XPS techniques and the sensing properties were investigated for the detection of triethylamine (TEA). The results indicate that 3D laminated CuO/SnO₂ material, assembled by lamellae consisting of ordered nanoparticles, exhibit an enhanced sensing performance compared with SnO₂, and notably, CuO/SnO₂ with size less than 1 μm has obvious high selectivity in the detection of 100 ppm TEA. Particularly, it has a high response and stability to 1 and 5 ppm TEA (S is 8 and 33), and that is higher than SnO₂ material, suggesting 3D laminated CuO/SnO₂ is an effective candidate material served as sensor platform to detect low-concentration amines.     

氧化镍-铁酸锌复合薄膜/锡掺杂玻璃光波导传感元件的制备及其对硫化氢气体的气敏性

用溶胶-凝胶法制成了NiO掺杂的ZnFe2O4溶胶,并用浸渍提拉法将其固定在锡掺杂玻璃光波导表面,研制了NiO-ZnFe2O4复合薄膜/锡掺杂玻璃光波导气敏元件,并对无机有毒气体进行了检测。 实验结果表明,在室温下,该传感元件对H2S气体具有一定的选择性响应,而对相同浓度的其它无机气体的响应相对较小,能够检测到1.0×10-9（体积比）的H2S气体,其响应和恢复时间分别是6和8 s。 该元件具有灵敏度高、响应-恢复快、可逆性和重复性好、容易制备,在室温下便于操作等特点。     

一维Ga2O3/SnO2纳米纤维的制备及其气敏性能

通过静电纺丝法制备了一维Ga2O3/SnO2纳米纤维,采用X射线衍射(XRD)、扫描电镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)等方法对材料进行了表征,测试了不同Ga2O3质量分数(0、40%、50%、60%、70%、100%)的Ga2O3/SnO2纳米纤维(650℃,5 h)对应元件对三甲胺、丙酮、乙醛、乙酸、氨气、乙醇、甲醛7种气体的气敏性能。结果表明:在室温(25℃)时,60%(w/w)Ga2O3-40%(w/w)SnO2纳米纤维对三甲胺气体具有较高的灵敏度和较短的响应/恢复时间。对1000μL·L^-1三甲胺的灵敏度达到51;检出限达到0.8μL·L^-1,其灵敏度为1.3。     

CuO/TiO2/γ-Al2O3催化剂表征及对NO+CO反应性能研究

采用色谱-微反流动法反应装置考察了w%CuO/15%TiO₂/γ-Al₂O₃催化剂对NO+CO的反应活性;催化剂经空气氛或氢气氛预处理后,NO转化率达100%的反应温度分别是325和275 ℃;XRD仅能检测到γ-Al₂O₃晶相,负载15%CuO后可以检测到微弱的CuO晶相;H₂-TPR能检测到2个CuO的还原峰(α和β峰),将其归属于高度分散的CuO分别在裸露的γ-Al₂O₃和TiO₂/γ-Al₂O₃载体上的还原;原位红外分析结果表明催化剂经空气氛或氢气氛预处理后,吸附NO+CO反应气后,反应的中间产物N₂O出现的温度分别为200和150 ℃。     

金属有机化学气相沉积法制备SnO2/MCM-41半导体传感器及其性能研究

采用金属有机化学气相沉积(MOCVD)法制备了SnO2/MCM-41半导体传感器, 考察了沉积时间和沉积温度对SnO2/MCM-41半导体传感器的SnO2沉积量、比表面积和孔径的影响; 研究发现, 随着SnO2沉积量的增加, 孔径有规律地下降, 说明SnO2较均匀地沉积在介孔分子筛MCM-41的孔道之中. SnO2/MCM-41半导体传感器对CO和H2具有较高的传感性能, 其传感性能的大小与CO和H2的浓度成正比.     

Gas sensor array based on metal-decorated carbon nanotubes

Here we demonstrate design, fabrication, and testing of electronic sensor array based on single-walled carbon nanotubes (SWNTs). Multiple sensor elements consisting of isolated networks of SWNTs were integrated into Si chips by chemical vapor deposition (CVD) and photolithography processes. For chemical selectivity, SWNTs were decorated with metal nanoparticles. The differences in catalytic activity of 18 catalytic metals for detection of H(2), CH(4), CO, and H(2)S gases were observed. Furthermore, a sensor array was fabricated by site-selective electroplating of Pd, Pt, Rh, and Au metals on isolated SWNT networks located on a single chip. The resulting electronic sensor array, which was comprised of several functional SWNT network sensors, was exposed to a randomized series of toxic/combustible gases. Electronic responses of all sensor elements were recorded and the sensor array data was analyzed using pattern-recognition analysis tools. Applications of these small-size, low-power, electronic sensor arrays are in the detection and identification of toxic/combustible gases for personal safety and air pollution monitoring.     

Photocatalytic storing of O2 as H2O2 mediated by high surface area CuO. Evidence for a reductive-oxidative interfacial mechanism

CuO powders with a high specific surface area are shown to be able to produce H(2)O(2) in aqueous solution under simulated light irradiation. The highest rate of peroxide production was observed under mild experimental conditions using O(2) and a large surface area photocatalyst CuO irradiated with a solar simulator having light intensities between 60 and 90 mW/cm(2). The CuO employed had a specific surface area (SSA) of 64.8-70.1 m(2)/g and was prepared in a tubular furnace by controlled thermal decomposition of precipitated copper oxalate. The CuO particles produced were 1 mum cubes with primary particles around 15 nm. No peroxide was produced under the same conditions with commercial CuO, with SSA 200 times lower. The CuO synthesized during this work was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), specific surface area [Brunauer-Emmett-Teller (BET)], porosity, and X-ray photoelectron spectroscopy (XPS). From XPS, it was observed that only Cu(II) was present in the unused and used CuO. This indicates that the redox transient species involving other Cu oxidation states disappear very fast during the reaction, regenerating Cu(II) during H(2)O(2) production. Diverse experiments provided some evidence for the possible interfacial reaction mechanism leading to H(2)O(2), following the initial step of O(2)(-)(.) formation on the CuO surface under irradiation with photons, with energies exceeding the band gap of CuO. A photocatalyzed degradation of a concentrated 4-chlorophenol (4-CP) solution was observed under solar-simulated light in the presence of CuO.     

SnO2纳米晶的水热合成及其气敏特性

SnO2 nanocrystal with different crystalline sizes were prepared with SnCl2 2H2O and H2O2 raw materials by a hydrothermal process. The synthesized powders at different reaction temperatures were characterized by means of powder X-ray diffraction, transmission electron microscope, specific surface area and gas sensitivity measurements. The results revealed that the pure SnO2 nanocrystallites synthesized at 120 ℃ have high specific surface area （210.3 m2/g）, and show a high sensitivity to C2H5OH gas. Both traits are beneficial in gas-sensitive detection application.     

Hydrothermal Synthesis and Primary Gas Sensing Properties of CuO Nanosheets

Uniformity nanosheets of CuO were prepared by a mild hydrothermal synthesis method. Phase analysis was carried out using x-ray diffraction (XRD) and the result confirmed the CuO nanosheets as a single phase. The field-emission scanning electron microscopy (FE-SEM) was used to observe the morphology of CuO nanosheets while the gas sensing properties of these unique CuO nanosheets were tested at a static state system. The results show that the CuO has uniformity nanosheets, and the gas sensing property show that the CuO nanosheets gas sensor has a stable gas response and the same gas sensitivity trend to tested gases. This method may be suitable for larger-scale production of these CuO nanosheets for practical applications.     

纳米氧化铜修饰的苯巴比妥分子印迹传感器的制备及其电化学性能

为了改善分子印迹传感器的灵敏度,在四丁基高氯酸铵的支持电解质溶液中,以甲基丙烯酸为功能单体,马来松香丙烯酸乙二醇酯为交联剂在纳米氧化铜修饰过的玻碳电极上电聚合了一种苯巴比妥(PB)识别性能的分子印迹传感膜.采用循环伏安(CV)法、差分脉冲伏安(DPV)法及交流阻抗(EIS)法对这种纳米氧化铜修饰过的印迹及非印迹电极的电化学性能进行了研究,结果显示纳米氧化铜修饰过的印迹及非印迹电极的电化学性能完全不同.X射线衍射(XRD)证实纳米粒子为氧化铜.采用扫描电镜(SEM)对纳米氧化铜修饰过的印迹传感器的形貌进行分析,发现纳米氧化铜分散在电极表面,改善了修饰印迹传感器的识别点.差分脉冲伏安法(DPV)表明苯巴比妥的浓度在1.0×10-8-1.8×10-4mol·L-1范围内呈现良好的线性关系(线性相关系数R=0.9994);检出限2.3×10-9mol·L-1(信噪比(S/N)=3).研究结果表明纳米氧化铜修饰过的印迹传感器具有较高灵敏度及选择性.此印迹传感器能用于实际样品中苯巴比妥的检测,加标回收率在95.0%-102.5%.