固体聚合物电解质电导率式湿度传感器

1 引言。湿度传感器(HS)作为重要的化学传感器,在仓储、过程控制及气象等方面有着广泛的应用。目前HS普遍存在稳定性和可靠性不够理想、耐湿性能差、抗干扰能力不强的缺点,故制约了它的应用和发展。因此,探索新的高精度、高可靠性、长寿命的感湿材料,研究各类新型传感器具有重要意义。Nation膜是一种全氟磺酸质子交换膜,带有磺酸基团,可以吸附空气中的水分,吸附量与空气中的水含量存在一定的定量关系,因而可以作为HS的感湿材料。本实验利用燃料电池用的耐腐蚀碳纸为电极,将Nation转换为锂离子型,制备了以Nation为感湿材料的HS,在相对湿度为10％-97％范围内,电导率的对数与相对湿度(RH)之间具有良好的线性响应。     

P2O5掺杂的磷钨酸常温电解质

以磷钨酸(PWA)为基质,加入适量的P2O5,制备了P2O5/PWA电解质. 采用交流阻抗谱方法研究了不同质量分数P2O5电解质的导电性能及相对湿度对电导率的影响. 结果表明,质量分数为7%的P2O5/PWA电解质,室温电导率达到0.045 S/cm;相对湿度在20%～70%范围内电解质的电导率变化不大;在40 ℃下长时间放置,电解质的质量损失小于2%,表明其常温保水性好.     

基于CsPbBr3量子点的湿度传感器的制备及其在微裂纹检测中的应用

采用简单的溶液路线结合乙酰丙酮铁(AAI)改性技术,制备了分散性良好、尺寸均匀的钙钛矿型CsPbBr₃-Fe量子点(QDs),通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及光致发光(PL)光谱对材料进行表征。并通过旋涂法构筑基于钙钛矿QDs的电阻式湿度传感器。湿敏特性测量结果表明：该湿度传感器在10%~100%的相对湿度(RH)的检测范围内具有良好的线性、快速响应特性;在70% RH时传感器的灵敏度为1.1,响应时间为33 s,恢复时间为38 s。此外,我们运用有限元方法模拟了管道微裂缝的泄漏行为,通过模拟不同流速、压力下的流速场和压力场分布,验证了利用湿度传感器检测泄漏点位置的可行性。     

一次性唾液α-淀粉酶生物传感器的研制

基于丝网印刷技术在PVC薄膜上制备了一次性碳电极,用Nafion固定二茂铁(Fc)作为电子介体,将α-糖苷酶和葡萄糖氧化酶(GOD)滴加于二茂铁修饰的电极上,滴加明胶晾干,戊二醛间接交联固定制成一次性唾液α-淀粉酶生物传感器,用计时电流法测定对α-淀粉酶的响应.实验结果表明,该传感器响应电流与α-淀粉酶活性在60～840 U/L之间呈现良好的线性关系,检出限为17 U/L.该生物传感器响应时间短,达到95%稳态响应时间不超过30 s,具有良好的一致性、准确性和稳定性.探讨了pH、缓冲液、温度及其它干扰物质等对该传感器的影响.该传感器可用于唾液α-淀粉酶浓度的快速、准确检测.     

基于CsPbBr3量子点的湿度传感器的制备及其在微裂纹检测中的应用

采用简单的溶液路线结合乙酰丙酮铁(AAI)改性技术，制备了分散性良好、尺寸均匀的钙钛矿型CsPbBr₃-Fe量子点(QDs)，通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及光致发光(PL)光谱对材料进行表征。并通过旋涂法构筑基于钙钛矿QDs的电阻式湿度传感器。湿敏特性测量结果表明：该湿度传感器在10%~100%的相对湿度(RH)的检测范围内具有良好的线性、快速响应特性；在70% RH时传感器的灵敏度为1.1，响应时间为33 s，恢复时间为38 s。此外，我们运用有限元方法模拟了管道微裂缝的泄漏行为，通过模拟不同流速、压力下的流速场和压力场分布，验证了利用湿度传感器检测泄漏点位置的可行性。     

TiO2-SnO2纳米晶膜紫外光照下对臭氧气敏性能的研究

以低温水热法制备了TiO2-SnO2复合纳米晶粒,采用提拉法涂敷于带有金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臭氧传感器。采用X射线衍射仪、热场发射扫描电子显微镜、能量色散X射线谱仪和紫外-可见光谱能谱仪,表征了TiO2-SnO2纳米晶粒的晶体结构和微观形貌。采用紫外-可见吸收光谱法和电化学方法,讨论了TiO2-SnO2纳米晶粒对臭氧敏感机理与光电化学特性。在气体传感器静态测试系统上,采用XEDWS-60A型气敏元件分析仪测试了紫外光下臭氧传感器敏感特性、动态响应、抗干扰和稳定性。结果表明,以Ti与Sn摩尔比为6的TiO2-SnO2纳米晶粒为敏感薄膜的臭氧传感器,在相对湿度为40%和温度为25℃条件下,臭氧浓度为0.1~1.8μg/L时,有、无紫外光照射的臭氧传感器线性度分别为97.5%和78.5%,动态响应分别为2和9 s,恢复时间分别为5.5和15 s。此传感器对CO、NOx、甲醛、丙酮、丁醇和甲醇等气体具有良好的抗干扰性能。在汽车上连续使用12个月后,响应衰减了4.7%,响应正常时间为8.5个月。     

ZrOCl2掺杂对磷硅酸盐凝胶质子导电性能的影响

采用溶胶-凝胶技术研究了ZrOCl₂·8H₂O掺杂对磷硅酸盐凝胶质子导电性能的影响. 结果表明, 掺杂ZrOCl₂·8H₂O能提高磷硅酸盐凝胶的质子电导率, 并且掺杂质量分数为0.97%时质子电导率达到最大值(σ₁₃₀=2.38 S/m). 掺杂样品在相对湿度为40%条件下放置30 d后, 未发生H₃PO₄渗出现象, 其质子传导性能基本不变. 核磁共振谱结果表明, 掺杂ZrOCl₂减少了磷硅酸盐凝胶结构中自由磷酸的形成, 提高了与四面体之间的化学结合力.     

基于CuO-Co3O4的催化燃烧型一氧化碳传感器

采用共沉淀法制备了CuO-Co3O4复合材料,并以其为催化剂,负温度系数热敏电阻(NTCT)为加热电阻,制备了一种催化燃烧型CO传感器,该传感器对CO的定量限为0.034 9 mg.L-1。利用X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)对复合材料的物相和表面形貌进行表征。当CuO-Co3O4的煅烧温度为400℃时,传感器对CO的灵敏度最高。在桥电压为9 V,CO的浓度为0.034 9~0.582 mg.L-1时,传感器的响应信号与CO浓度之间呈现良好的线性关系,线性相关系数为0.979。90%的响应和恢复时间分别为24 s和68 s。     

基于纳米CuO敏感材料的电流型NO2传感器研究

采用浸渍技术在多孔的氧化钇稳定的氧化锆(YSZ)中制备了纳米CuO敏感材料,并以其为敏感电极,YSZ为固体电解质,制备了一种新型的电流型NO2传感器。采用X射线衍射仪和扫描电子显微镜表征了NO2传感器的相组成和微观形貌,应用IM6e型电化学工作站测试了其气敏性能。结果表明,CuO颗粒粒径约为100 nm,且与基体结合紧密。在500～600℃时,传感器对NO2表现出良好的敏感性。在极化电压为-300 mV,NO2体积分数为0～5.0×10-4时,传感器的响应电流值与NO2浓度之间呈良好的线性关系。在被测气体总流量为400 cm3/min时,传感器信号90%的响应和恢复时间均为50 s。传感器响应信号在测试时间内具有良好的稳定性。共存气体O2和CO2对传感器的敏感性几乎没有影响。     

盐酸普萘洛尔分子印迹电化学传感器的制备与研究

以盐酸普萘洛尔为目标模板分子,通过电聚合多巴胺,在多壁碳纳米管修饰的玻碳电极表面制备了对目标分子有特异响应的分子印迹电化学传感器.利用扫描电子显微镜、循环伏安法和差示脉冲伏安法对此传感器的表面形貌及性能进行了表征,并且优化了检测条件,研究了印迹传感器对模板分子及其结构类似物的选择性响应.结果表明:此传感器具有较好的选择性响应,而且碳纳米管的存在显著提高了传感器的灵敏度.盐酸普萘洛尔的浓度在0.20～100 μmol/L范围内与峰电流呈良好的线性关系;检出限为2.53×10-8 mol/L(S/N=3).此传感器还具有良好的稳定性和重现性.     

In vitro and short-term in vivo characteristics of a Kel-F thin film modified glucose sensor.

A new outer layer composition, consisting of polytetrafluoroethylene (PTFE), Kel-F oil, and Nafion, is suggested to minimize the detrimental effect of dissolved oxygen and to extend the linear response range of a glucose oxidase(GOx)-based sensor using nonconducting polymer. The morphology of Kel-F/PTFE/Kel-F/Nafion polymeric laminate was followed during fabrication by SEM. When Kel-F film was formed on the PTFE outer layer, the linear response was extended to 21 mM, at a sensitivity of 2.8 +/- 0.8 nA/mM mm2. We demonstrate that a sensor without Kel-F/PTFE/Kel-F/Nafion outer layer is relatively oxygen dependent, whereas by comparison a sensor with Kel-F/PTFE/Kel-F/Nafion outer layer is oxygen independent. The current of such a glucose sensor implanted in the subcutaneous tissue stabilized within 60 min, and the lag between blood glucose changes and sensor output was within 1 min. The in vivo characteristics of the glucose sensor described show great promise for one-point in vivo calibration.     

Development of dimethyl sulfoxide biosensor using a mediator immobilized enzyme electrode

A mediator immobilized dimethyl sulfoxide (DMSO) sensor using DMSO reductase (DMSO-R) was constructed. Methyl viologen (MV) was used as a mediator and immobilized on a glassy carbon (GC) electrode with Nafion polymer. DMSO-R from Rhodobacter sphaeroides f. sp. denitrificans was retained by a dialysis film on the modified GC electrode. The amperometric signal in response to DMSO was observed. The linear range of the calibration curve for DMSO was between 0 and 600 microM. The response time was within 100 s and the relative standard deviation was 4% at 200 microM DMSO (n = 4). To eliminate the background noise derived from oxygen in samples, the glucose oxidase-catalase retained DMSO sensor was also examined.     

Effects of Humidity,Temperature and Bismuth Electrodeposition on Electroanalytical Performances of Nafion‐coated Printed Electrodes for Cd2+ and Pb2+ Detection

The synergistic use of Nafion polymeric membrane and in situ electrodeposited bismuth film is a worthwhile strategy to develop electrochemical sensors for the detection of Cd²⁺ and Pb²⁺. However, Nafion thin films morphological and conductivity properties have a strong dependence on the environmental conditions, such as relative humidity and temperature, while the bismuth in situ electroplating can affect the repeatability of measurements. With the aim to overcome these drawbacks, the effects of the storage environmental conditions were investigated to improve the morphological stability and electroanalytical performances of Nafion film‐based sensor for the detection of Cd²⁺ and Pb²⁺. Nafion‐coated graphite‐based screen‐printed electrodes were stored at different humidity and temperature conditions and characterised by using square wave anodic stripping voltammetry, cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscopy. Significant differences were observed at the varying of humidity conditions, with an enhancement of sensor electrochemical performances at lower humidity. Furthermore, different approaches for bismuth in situ electrodeposition on Nafion‐coated screen‐printed electrodes were compared by using overlap or removal approach. This study disclosed considerable differences in the electrochemical performances and morphology of the resulting bismuth‐sensor, obtaining an enhancement of the working stability for the removal approach.     

正交设计法优化PEMFC催化层的最佳配比

利用正交实验设计法优选PEMFC电极催化层制备的最佳条件.实验证实亲水电极(催化层中不含PTFE)性能优于疏水电极.在该工艺条件下,当Nafion的含量为1.4mg·cm-2,Pt含量为0.4mg·cm-2时,以常压的H2和空气分别作为燃料气和氧化剂,电池的最高功率可达到0.37W·cm-2.研究表明,提高Pt/C中的Pt含量将是提高催化剂性能的有效途径.     

N,N-双(二硫代羧基)二乙烯三胺乙基聚合物的合成及其吸附性能

以二乙烯三胺与二硫化碳反应生成中间体[N,N-双(二硫代羧基)二乙烯三胺],进而与1,2-二氯乙烷聚合生成N,N-双(二硫代羧基)二乙烯三胺乙基聚合物,用红外光谱确认了中间体和聚合物的结构.测定了聚合物对一部分重金属离子的吸附性能.结果表明,聚合物能定量地吸附某些重金属离子,对Ag+、Cu2+等离子有较高的吸附容量.     

含氮磷酸锂薄膜在空气中的稳定性

利用射频(RF)磁控溅射方法制备了含氮磷酸锂(LiPON)薄膜. 采用SEM、XRD、XPS等技术以及交流阻抗法和电位线性扫描法, 研究了空气湿度对LiPON薄膜形貌、组成和性能的影响. 结果表明, LiPON薄膜在湿度为40%的空气环境中放置24 h后, 将发生明显的水解反应, 使LiPON薄膜表面形貌变得疏松、局部突起; PH3和NH3的产生, 使薄膜中磷元素和氮元素含量减少, 而Li2CO3的生成, 则使薄膜中碳元素和氧元素含量有明显的增加. LiPON电解质薄膜形貌和组成的变化, 造成了薄膜电化学性能的严重恶化.     

Renewable liquid film-based electrochemical sensor for gaseous hydroperoxides

Electrochemical sensors for hydroperoxides based on thin flowing films were investigated. The sensor is composed of two segments of Nafion tubing put on a silver wire. A small portion of the silver wire is exposed and is chloridized to function as the reference electrode. One Nafion segment has a Pt-wire coil wrapped on it to function as the counter electrode and the other has a similar Pt-Rh wire coil that functions as the working electrode. A collection solution flows as a thin film on the sensor surface and also functions as the collection medium. Hydrogen peroxide and cumene hydroperoxide were examined as test compounds. The former can be oxidatively determined with a Pt-Rh electrode over a large range (ppb-ppm) without any significant influence of relative humidity. By using a technique to stop the liquid flow, the sensitivity can be further improved. Cumene hydroperoxide, an industrially important hydroperoxide, can be determined easily with a relative precision of better than 5% in the vapor phase over simulated process reaction mixtures containing percentage levels of the analyte by reduction on a Pd electrode. The sensor is simple and inexpensive to fabricate and requires only a suitably equipped personal computer for operation.     

An improved polymer electrolyte-based amperometric hydrogen sensor

An improved polymer electrolyte membrane (PEM) fuel cell-based amperometric hydrogen sensor that operates at room temperature has been developed. The electrolyte used in the sensor is a PVA/H₃PO₄ blend, which is a proton-conducting solid polymer electrolyte. A thin film of palladium is used as the anode and platinum supported on carbon as the cathode. The sensor functions as a fuel cell, H₂/Pd//PVA-H₃PO₄//Pt/O₂, and the short-circuit current is found to be linearly related to the hydrogen concentration. The basic principle, details of assembly, response behaviour of the sensor and its application are discussed.     

Preparation of Nafion/PTFE/Zr(HPO4)2 composite membranes by direct impregnation method

The viscosities of as received 5.1 wt.% Nafion solutions (EW = 1100, Du Pont Co) blended with various concentrations of ZrOCl₂ were studied. We show the solution viscosity decreases as the wt. ratio of [ZrOCl₂]/[Nafion] is increased from 0.0 to 0.03, then the viscosity does not change significantly as the wt. ratio of [ZrOCl₂]/[Nafion] is increased from 0.03 to 0.16, and then the viscosity increases dramatically as the wt. ratio of [ZrOCl₂]/[Nafion] is increased above 0.16. Four Nafion solutions consisting of 5.1 wt.% Nafion and ZrOCl₂ with [ZrOCl₂]/[Nafion] wt. ratios of 0.019–0.24 were used with porous poly(tetrafluoroethylene) (PTFE) film to prepare zirconium hydrogenphosphate (ZrP) hybridized Nafion/PTFE (NF–ZrP) composite membranes by direct impregnating porous PTFE in Nafion/ZrOCl₂ solutions. The influence of [ZrOCl₂]/[Nafion] wt. ratio of Nafion/ZrOCl₂ solution on the membrane morphology of NF–ZrP and polyelectrolyte membrane fuel cell (PEMFC) performance at temperatures of 110–130 °C with relative humidity of 51.7–28.8% RH was investigated.     

丙烯酸水溶液聚合法制备PTFE/PAA/Nafion膜及其性能

采用廉价的多孔聚四氟乙烯(PTFE)膜作为基底, 用少量的Nafion与PTFE膜复合可制备低成本的质子膜. 但疏水性的PTFE膜与亲水性的Nafion膜结合性不佳. 基于此, 本文对疏水性的PTFE膜材料表面进行设计, 先采用丙烯酸对疏水性的PTFE膜表面进行亲水性改性, 再喷涂亲水性Nafion膜, 完成低成本PTFE/PAA/Nafion膜的制备. 实验结果表明, 改性前的PTFE膜材料水接触角为150°, 改性后的膜接触角变为55.6°, 亲水性大幅上升, 膜的机械强度和尺寸稳定性(断裂强度为25.2 MPa, 80 ℃下的溶胀率为11.9%)均优于Nafion117膜, 而 Nafion用量则节省了60%. PTFE/PAA/Nafion膜具有高质子导通率(80 ℃下达到131.9 mS/cm), 接近于Nafion117膜, 最大功率密度可以达到404.2 mW/cm².