镁杂质离子对钒电池电解液性能的影响研究

通过对含有不同浓度镁杂质离子的电解液进行循环伏安测试、黏度测试及热稳定性测试,考察镁离子对电解液电化学性能及稳定性的影响。结果表明,当电解液中镁杂质离子浓度超过0.96g/L时,电解液黏度从0.89mm2/s增大至0.95mm2/s,电解液中钒离子扩散系数从(2.06~3.33)×10-6 cm2/s降低至(1.30~2.11)×10-6 cm2/s,导致电极反应速率和电极反应可逆性降低;同时电解液中出现钒离子大量沉淀现象,电解液稳定性降低,严重影响钒电池的正常运行。     

缓蚀法改善镁基储氢电极充放电循环稳定性的研究

研究了不同种类缓蚀剂及不同处理方式对非晶态镁基储氢电极充放电循环稳定性的影响。实验结果表明,缓蚀剂可以改变镁基储氢电极表面与电解液之间的界面性质,在不显著降低电极最大初始容量的同时,改善了电极的循环稳定性。     

Tri-axial recording of event-related potentials during passive cognitive tasks in patients with Alzheimer''s disease

A novel dynamic mathematical microelectrode model (a model of solvent and solute kinetics in electrolyte-filled microelectrodes) was deduced from experimental observations made on standard (single-barrelled, 3.0 M KCl-filled, approximately 10 M[ohm]) electrodes using (a) electrodiffusion, electro-osmosis, and continuity equations that were placed into the constraints of electrode geometry, and (b) handbook/textbook parameter values, only. The model proved to be able to faithfully reproduce all observed electrochemical and electrical electrode properties, i.e. even those that constituted no part of the model's experimental basis. In theoretical tests, the model shows, for the standard electrode that (a) inside the electrode, any profiles in electrical potential and electrolyte concentration are occurring at the most distal part (approximately 50 microm) of the tip region, (b) asymmetrical shifts in electrolyte concentration just inside the electrode tip opening are the true cause of the electrode's current rectification, and (c) strong transelectrode currents are producing water flows across the electrode orifice that may affect the volume of smaller and medium-sized cells. In further tests, the model shows, among other things, for non-standard electrodes that (a) decreasing the electrode electrolyte concentration will give rise to marked decreases in electrolyte leakage from the electrode, but only very minor changes in tip potential, and (b) increasing the surface charge of the electrode glass (increases in zeta potential) and/or decreasing the electrode electrolyte concentration will produce increases in electro-osmotic water transport, which may be desirable for the intracellular injection of water-soluble (electro-neutral) substances.     

Application of Glass Sealant for SOFC

Glass and glass-ceramic materials were investigated as SOFC seals at 800 ～ 850 ℃. The material was based on the glass and glass-ceramic in the BaO-CaO-Al2O3-SiO2-La2O3-B2O3 system. The sealant has a minimum thermal expansion mismatch with yttria-stabilized zirconia (YSZ)electrolyte and Ni/gYSZ for the anode. The sealant has a superior stability during the process of operation in SOFC and can withstand thermal shock during the process of thermal cycling. The results show that the BaO-CaO-Al2O3-SiO2-La2O3-B2O3 system sealant can be used as sealing materials for SOFC.     

添加剂对镁还原渣泡沫玻璃性能的影响

以镁还原渣和废玻璃为主要原料来制备泡沫玻璃,在确定镁还原渣和废玻璃配比的前提下,通过正交试验研究发泡剂碳酸钠、稳泡剂六偏磷酸钠及助熔剂硼砂的掺量对泡沫玻璃性能的影响,并对不同发泡剂掺量下的泡沫玻璃进行密度、吸水率、力学性能等的检测及XRD物相分析。结果表明,镁还原渣泡沫玻璃中含有明显的CaSiO_3晶相结构,3种因素中发泡剂的影响最为显著,当发泡剂、稳泡剂和助熔剂的掺量分别为2.0%、3.0%和2.0%时,得到的泡沫玻璃性能最好,其表观密度为598kg/m~3,抗压强度为5.34 MPa,吸水率为0.43%。     

石墨烯-离子液体修饰玻碳电极同时测定矿石中铅和镉

将石墨烯(GR)滴涂在玻碳电极(GCE)上制备GR/GCE电极,采用循环伏安法将离子液体(1-辛基-3-甲基咪唑六氟磷酸盐)聚合在GR/GCE电极表面,制得新型OMIMPF_6/GR/GCE修饰电极。以0.1mol/L HAc-NaAc缓冲溶液(pH 4.5)为支持电解液,利用差分脉冲法研究了Pb~(2+)和Cd~(2+)在OMIMPF_6/GR/GCE电极上的电化学行为。结果表明,Pb~(2+)和Cd~(2+)在修饰电极上有较好的电化学行为,Pb~(2+)和Cd~(2+)的浓度分别在1.0×10~(-8)~4.2×10~(-5)mol/L和1.0×10~(-8)~6.0×10~(-5)mol/L范围内与峰电流呈良好的线性关系;Pb~(2+)和Cd~(2+)的检出限分别为1.0×10~(-9) mol/L和5.0×10~(-8)mol/L。实验方法用于矿石中铅和镉的测定,结果的相对标准偏差(RSD,n=6)为2.9%~4.4%;并与原子吸收光谱法对比,测定结果基本一致。     

ZnS/AuNPs/ITO修饰电极电化学发光法测定水中痕量铜

针对常规方法测定痕量铜有操作繁琐、灵敏度低等问题,建立了采用ZnS/AuNPs/氧化铟锡(ITO)玻璃电极电化学发光法测定痕量铜的新方法。在ITO玻璃表面,用电化学沉积法沉积AuNPs和ZnS,制备了ZnS/AuNPs/ITO电极。考察了该修饰电极的光、电化学行为,并对制备条件进行了优化。结果表明,Cu²⁺能够抑制以AuNPs为载体、ZnS为发光物质的修饰电极电化学发光,相对电化学发光值与Cu²⁺浓度的对数值在1×10^-11~5×10^-8 mol/L范围内呈线性关系,检出限为0.52×10^-11 mol/L。方法用于水样中痕量铜的测定,结果的相对标准偏差(RSD,n=6)不大于1.3%,回收率在97%~105%之间;并与电感耦合等离子体质谱法测定结果基本一致。     

微分脉冲阳极溶出伏安法测定水处理剂用铝酸钙中砷

采用活性面位于侧面的金电极作为工作电极,建立了微分脉冲阳极溶出伏安法测定水处理剂用铝酸钙中砷含量的检测方法。将水处理剂用铝酸钙粉用氯化铝溶液加热回流溶解,经过滤后,对滤液进行稀释,以18%(质量分数)盐酸为支持电解质,对样品稀释液进行微分脉冲扫描阳极溶出伏安法测定。结果表明,砷在金电极上于峰电位为+0.09V左右产生灵敏的溶出峰,该峰峰高与砷的质量浓度在0.5~10μg/L之间呈现良好的线性关系,相关系数为0.997 7,检出限为0.15μg/L。按照实验方法对水处理剂用铝酸钙样品进行测定,并采用电感耦合等离子体质谱法(ICP-MS)做方法对照,同时加入砷标准溶液进行加标回收试验,结果表明,两种方法的测定结果基本一致,且实验方法的加标回收率为90%~102%。对3个水处理剂用铝酸钙样品测定结果的相对标准偏差(RSD,n=6)为2.1%~3.3%。     

金属液中定硫传感器的稳定性

采用高温化学电池固体电解质的方法来测定碳饱和铁液中的硫含量。用ZrO2(Y2O3)作为定硫传感器的固体电解质，将Y2O3＋Y2O2S作为其辅助电极组成A型定硫传感器；或用ZrO2（Y2O3）＋Y2O2S直接作为固体电解质组成B型定硫传感器。其电池形式分别为：Mo,Cr2O3＋Cr|ZrO2(Y2O3)|Y2O3 Y2O2S|[S]Fe,Mo,Mo;Mo,Cr2O3 Cr|ZrO2(Y2O3) Y2O2S|[S]Fe,Mo。定硫实验结果表明，该定硫传感器所测电动势信号稳定，响应快，重现性好，持续时间长，准确度较高，是一种比较成功的定硫传感器。此外，还得到了在1583K下电动势与铁液中硫含量的关系。     

The thin electrolyte layer approach to corrosion testing of dental materials--characterization of the technique

An innovative technique for corrosion testing of metallic dental materials is introduced. The thin electrolyte layer technique (TET) simulates the physical characteristics of the oral environment by employing a still, thin layer of an electrolyte, in contrast to bulk electrolyte techniques (BET) which utilize relatively large quantities of fluid. Limiting current density tests on a platinum electrode revealed a lower surface oxygen content for TET. Borate buffer (pH 6.8) was employed as an electrolyte. The effect of lower oxygen content in TET on passivation and polarization characteristics of 316L SS in 0.9% saline was investigated. The results revealed differences in the polarization resistance and open circuit potential development with time, as well as in anodic and cathodic polarization behavior. Lower O2 concentration in TET was attributed to different electrolyte convection characteristics under both testing conditions. Additionally, use of the TET resulted in better data reproducibility. Overall, this investigation led to a deeper understanding of the electrochemical processes inherent in thin electrolytes such as those found in the oral environment.     

B2O3在镁电解质中阴极还原机理的研究

采用循环伏安法、方波伏安法和计时电位法以W丝为工作电极,研究了KCl-CaCl2-NaCl-MgCl2熔盐中B2O3的阴极电化学还原机理。研究结果表明:B2O3在W电极的还原反应是包含3电子的准可逆过程,且产物B不可溶;还原过程受扩散和电子转移步骤混合控制,并存在前行化学反应;前行化学反应的平衡常数、正向和逆向反应速率常数分别为K=1.22、k1=0.72 s-1、k-1=0.59 s-1。     

Ti-V基贮氢合金电极电化学性能的影响因素

研究了粉体粒度、导电镍粉及工作温度对合金电极Ti0.17Zr0.08V035Ni0.10Ni0.30放电性能的影响。结果表明：随着合金粒度的减小，放电容量有所增加，但放电容量随着循环数的增加而有所降低；而导电羰基镍粉含量的变化对合金电极的放电容量几乎没有影响。随着合金电极工作温度的增加，合金电极的循环稳定性、充、放电电压均有所降低。温度明显地影响Ti—V基贮氢合金电极中V在电介质溶液中的溶解。     

Physicochemical properties of a novel composite polymer electrolyte doped with vinyltrimethoxylsilane-modified nano-La2O3

Nano-La2O3 was modified with the vinyltrimethoxylsilane by hydrolysis and a novel poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) based composite polymer electrolyte doped with the modified nano-La2O3 was prepared by phase inversion method. The physicochemical properties were studied by SEM, FT-IR, XRD, TG and electrochemical methods. The results of FT-IR indicated that the nano-La2O3 was successfully modified with vinyltrimethoxylsilane. The XRD analysis showed that the incorporation of modified nano-La2O3 into the polymer electrolyte membranes could effectively reduce the crystallinity of PVDF-HFP, and the characterizations also suggested that thermal stability and electrochemical stability window could reach to 382°C and 5.1V, respectively; the reciprocal temperature dependence of ionic conductivity followed Vogel-Tamman-Fulcher (VTF) relation, ionic conductivity at room temperature was up to 3.5×10-3S/cm and lithium ions transference number was up to 0.42; the interfacial resistance increased at initial value about353Ω/cm2 and reached a steady value about 559Ω/cm2 after 5d storage at 30°C. The fabricated Li/As-prepared electrolytes/LiCoO2 coin cell showed excellent rate and cycle performances.     

线性扫描伏安法测定电镀铬槽液中铬和铁

以光谱纯石墨电极作为工作电极,采用三电极体系对镀铬槽液进行动电位极化扫描,利用电活性物质的质量浓度在石墨电极表面的还原峰与氧化峰电流值的变化关系,分别建立了线性扫描伏安法测定电镀铬槽液中Cr⁶⁺和Fe²⁺的方法。结果表明,在扫描速率为50~60 mV/s,酸度为pH 2.0,测试温度为20 ℃时,测定结果最佳。Cr⁶⁺在0.43 V(vs. 饱和甘汞电极,SCE)发生还原,Cr⁶⁺的质量浓度在2~14 g/L范围内,其质量浓度与还原峰峰电流呈线性,线性回归方程的相关系数R²=0.999;Fe²⁺在0.52 V(vs. 饱和甘汞电极,SCE)发生氧化,Fe²⁺的质量浓度在5~15 g/L范围内,其质量浓度与氧化峰峰电流呈线性,线性回归方程的相关系数R²=0.998。实验方法用于测定实际槽液中Cr⁶⁺和Fe²⁺,结果的相对标准偏差( RSD, n=10)在1.1%~1.3%之间。将按照实验方法对实际槽液中Cr⁶⁺和Fe²⁺的测定结果与硫酸亚铁铵滴定法测定Cr以及原子吸收光谱法测定Fe的结果进行比对,吻合性较好。     

Preparation and laser induced damage properties of rare earth doped BAS glass

Rare earth doped B2O3-Al2O3-SiO2 glass （RExBAS, x=5, 10, 20; RE=La, Sm） were prepared by solid state reaction method. Optical transmission spectra of such glass were characterized by ultraviolet spectrometers, and 1064 nm laser induced damage performance was investigated through the method of ＂1-on-1＂. The results indicated that there was a strong absorptive peak near 1064 nm in SmxBAS glass, the peak was enhanced with increasing x. While LaxBAS glass was transparent to 1064 nm laser, at the same time, the results of laser induced damage showed that the anti-laser induced damage performance of such glass was strengthened with the addition of rare earth oxide. Furthermore, the laser induced damage threshold （LIDT） of SmxBAS glass was significantly higher than that of LaxBAS glass. Consequently, Sm^3＋ doping was favor in the improvement of anti-laser induced damage performance for BAS glass.     

Fabrication and characterization of glucose sensors based on a microarray H2O2 electrode

A glucose sensor was recently developed by modifying an immobilized GOD (glucose oxidase) membrane and coating Nafion diffusion limiting membrane over an amperometric H2O2 MAE (microarray electrode), which was fabricated by using standard planar processing. The chip of the sensor is 2.5 mm by 15. The MAE is composed of an Ag/AgCl RE (reference electrode), a Pt CE (counter electrode) and two sets of Pt WE (working electrode), each set consists of five bands. Silicon nitride was chosen as the top insulator. Six MAEs different in both width and length of the band were examined and the MAE with the narrowest width (10 microns) of bands exhibits the best electrochemical performances. The glucose sensor based on the MAE B1-2 presents a linear range of 0.5-40 mM glucose at 37 degrees C with a 1/15 M phosphate buffer solution (pH = 7.0) as supporting electrolyte. The sensitivity, background current, response time, CV (coefficient of variation) and long-term stability of the sensor are 7.1 +/- 0.5 nA/mM, 2 +/- 0.5 nA, 30 s, 3.4% and 6 days respectively.     

壳聚糖-多壁碳纳米管修饰玻碳电极差分脉冲溶出伏安法测定痕量钯

将多壁碳纳米管(MWCNT)分散于壳聚糖（CTS）溶液中,修饰在玻碳电极（GCE）表面,制成了壳聚糖-多壁碳纳米管修饰玻碳电极(CTS-MWCNT-GCE)。利用差分脉冲溶出伏安法研究了钯在该电极上的溶出伏安特性,优化了试验条件,提出了一种测定痕量钯的新方法。试验发现,在0.1 mol/L乙酸钠-0.1 mol/L盐酸缓冲溶液（pH 4.10）中,钯于－400 mV处被富集在该修饰电极表面,在-300 mV～400 mV电位范围内,以100 mV/s的速率扫描,钯在135 mV（vs. SCE）处出现一灵敏的溶出峰,峰电流与钯的浓度在1.88×10-9～1.69×10-8 mol/L范围内呈良好的线性关系,检出限为3.10×10-10 mol/L。该修饰电极具有良好的稳定性和重复性,在含有1.0×10-9 mol/L钯的溶液中,连续11次测定,其相对标准偏差(RSD)为0.21 %。方法用于矿样中痕量钯的测定,测定结果同火焰原子吸收光谱法（FAAS）的测定结果基本一致。     

Effects of OP-41483.alpha-CD, a stable prostacyclin analog, on cultured endothelial cell dysfunction caused by 15(S)-hydroperoxy-5,8,11,13-eicosatetraenoic acid (15-HPETE) in vitro

We studied the effect of OP-41483.alpha-CD, a stable prostacyclin analog, on, 15-HPETE induced bovine endothelial cell dysfunction, which was assessed by measuring a number of endothelial cells attached to plastic plates. 15-HPETE decreased the number of attached endothelial cells in a concentration- and time-dependent manner. OP-41483.alpha-CD and PGI2 significantly inhibited 15-HPETE induced dysfunction of the cells at a concentration of more than 10(-9)M. Besides, DDA (10(-6) - 10(-4)M) an adenylate cyclase inhibitor, diminished the inhibitory effect of OP-41483.alpha-CD on 15-HPETE induced cell dysfunction in a concentration-dependent manner. Furthermore, OP-41483.alpha-CD increased cAMP levels in the endothelial cells in the range of 10(-10) to 10(-8)M in a dose-dependent manner. These data suggest that OP-41483.alpha-CD could exert an inhibitory action on 15-HPETE induced endothelial cell dysfunction via partly increasing its effect on the intracellular cAMP level.     

离子液体-石墨烯-二氧化锰复合材料修饰玻碳电极差分脉冲伏安法测定土壤中铅和镉

采用涂滴法将石墨烯(GR)-二氧化锰(MnO₂)分散液滴在玻碳电极(GCE),然后利用循环伏安法将离子液体(OMIMPF₆)聚合制备得OMIMPF₆/GR/MnO₂/GCE复合材料修饰玻碳电极,建立了差分脉冲伏安法测定土壤中铅和镉的方法。实验表明,以4μL 2mg/mL的石墨烯-二氧化锰混合物分散液涂滴,电聚合离子液体30圈所制备的修饰电极,在0.1mol/L的醋酸-醋酸钠缓冲溶液(pH4.5)的支持电解液中,Pb²⁺和Cd²⁺的氧化峰电流值相对较高。Pb²⁺和Cd²⁺的浓度均在5.0×10^-8~1.4×10^-5mol/L范围内呈良好线性关系,Pb²⁺和Cd²⁺检出限分别达到5.0×10^-10mol/L和4.0×10^-9mol/L。对含10μmol/L Pb²⁺和10μmol/L Cd²⁺的标准混合溶液平行测定9次和连续扫描30次,Pb²⁺和Cd²⁺峰电流值的相对标准偏差均分别小于1.3%和4.3%,说明该修饰电极具有良好的重现性、稳定性。采用建立的方法用于土壤中铅和镉的检测,测得结果与原子吸收光谱法(GB/T 17141—1997)基本一致,相对标准偏差(RSD,n=6)均小于5.3%,回收率在97%~105%之间。     

TBP与N1923协同萃取铜电解液中的砷锑铋

采用TBP和N1923协同萃取铜电解液中的砷、锑、铋,考察TBP和N1923的浓度、电解液酸度、相比、时间、反萃取相比等因素对萃取过程的影响。结果表明,当有机相组成为60%TBP+25%N1923+5%异辛醇+10%磺化煤油,萃取相比O/A=3时,砷、锑、铋的单级萃取率分别为58.01%、53.49%和68.97%。在反萃相比O/A=2时,用水反萃砷的单级反萃率为53.61%。在反萃液组成为反萃剂50g/L、硫酸1mol/L,在反萃相比O/A=2时,锑、铋的单级反萃率分别为58.63%和79.46%。