基于二氧化硅球腔阵列的葡萄糖传感器研究

在二氧化硅球腔阵列电极上,通过电沉积普鲁士蓝和直接吸附葡萄糖氧化酶,制备了一种新型葡萄糖生物传感器。该传感器对酶催化反应产物过氧化氢的选择性催化还原特性可实现对葡萄糖的检测,实验结果表明,传感器的最佳工作电位是－0．3V,测试溶液的最佳pH值为6．0。在选定的工作条件下,传感器的线性范围为2．49×10-5－2．42×10-3mol／L,检测极限值为7．2×10-6mol／L（S／N=3）,米氏常数为1．136mmol／L。该方法制备的生物传感器能有效降低干扰,具有潜在的应用价值。     

热分解法制备的Ti/SnO2+Sb2O3/PbO2电极性质研究

研究了热分解法制备的Ti／SnO2 Sb2O3／PbO2电极性能以及该电极在硫酸溶液中作阳极使用的电化学特性．ESEM实验结果表明，所制备的锡锑中间层表面致密有序，能有效阻止新生态氧向基体扩散，延缓了绝缘的TiO2层生成．循环伏安曲线表明在析氧过程中，电极表面的组成会发生改变．所制电极在电流密度为4．0A／cm^2、60．0℃、1．0mol／LH2SO4溶液中作阳极使用时其寿命可达30h．     

水热合成法制备锐钛矿型纳米TiO2粉体的研究

以工业硫酸氧钛为原料，尿素作沉淀剂，固定6MPa的初始压力和300r／min的搅拌速度，在110-150℃的反应温度、2-8h的反应时间、0．25-1．5mol／L的硫酸氧钛反应浓度的条件下，采用水热合成法制备了锐钛矿型纳米TiO2粉体．采用XRD、TEM、BET等测试手段对在不同条件下所制备粉体的物相组成、晶粒度、比表面积等进行了分析．结果表明，所制备的粉体均为锐钛矿型纳米TiO2．粉体的比表面积分布在124-240m^2／g、晶粒度分布在6．7-10．6nm．随着反应温度的升高和反应时间的延长，晶粒度增大，比表面积降低．随前驱体浓度的提高，晶粒度也增大，当前驱体浓度〈0．5mol／L时，比表面积随着前驱体浓度的增大而增大．当前驱体浓度〉0．5mol／L时，比表面积随着前驱体浓度的增大而减少．     

无团聚HfO2纳米粉体的湿化学法制备及性能表征

以化学沉淀法制备HfO2纳米粉体，借助XRD、SEM、TEM、BET、激光粒度测试仪等测试方法研究了不同制备工艺对HfO2纳米粉料团聚状态的影响．采用初始浓度0．5mol／L的溶液，稳定溶液pH为9、添加表面活性剂PEG、用无水乙醇处理水洗后的湿凝胶、在700℃下煅烧，能制备无团聚，平均粒径为25nm，呈正交晶型的HfO2纳米粉体．200MPa冷等静压成型的素坯在氢气中1800℃保温2h得到96％理论密度的主相为正交相，有少量单斜相存在的HfO2陶瓷烧结体。     

有机凝胶法制备Sr0.5Ba0.5Nb2O6铁电薄膜及其电性能研究

采用有机凝胶法制备了Sr0．5Ba0.5Nb2O6(SBN50)铁电薄膜．研究了pH值和EDTA的用量对Sr-Ba-Nb前驱体溶液稳定性的影响，并对不同pH值条件下获得的Sr-Ba-Nb干凝胶的热分解历程进行了对比．计算和实验结果表明，制备Sr-Ba-Nb前驱体溶液的最佳pH=8，EDTA：金属离子(摩尔比)=2：1．在700℃下退火30min所得SBN50薄膜为单一钨青铜结构多晶薄膜．室温下，测试频率1kHz时，薄膜的介电常数为221，介电损耗为0．02，剩余极化强度Pr=8．17μC／cm^2，矫顽场Ec=16．9kV／cm．     

水热法制备海绵钛负载TiO2膜

以H2O2为氧化剂、KOH为矿化剂,采用一步水热法在多孔海绵钛载体上制备了颗粒大小约为0.5μm的四方状锐钛矿TiO2膜,并研究了产物TiO2膜对目标降解物亚甲基蓝溶液的光催化性能,探讨了矿化剂浓度对产物TiO2膜晶型、形貌及光催化性能的影响.结果表明,KOH矿化剂有利于TiO2膜在海绵钛表面的生成与晶化,当KOH在0.12mol/L时,海绵钛负载TiO2膜有着最佳的光催化性能:光催化反应45min,亚甲基蓝溶液的降解率达95%.采用该法制备的TiO2光催化剂回收简单,反复利用后,其光催化性能无明显下降.     

KTa0.6Nb0.4O3粉体溶剂热和水热法合成的对比研究

以Nb2O5和Ta2O5为前驱反应物，KOH为矿化剂，采用水热法和溶剂热法两种合成工艺制备了KTa1-xNbxO3（KTN）陶瓷粉体．实验结果表明，反应溶剂（水／异丙醇）和矿化剂KOH的摩尔浓度是影响KTN粉体结构和形貌的关键因素．采用水热工艺制备的KTN粉体，当KOH浓度达到3mol／L、反应温度为523K、反应时间8h时，开始出现以焦绿石结构为主的KTN粉体；随着KOH的浓度和反应温度的增加，粉体中的钙钛矿结构成分随之增加，而焦绿石结构则逐渐减少，但始终难以完全消除．采用溶剂热法，在KOH浓度1-2mol／L、反应温度523K、反应时间8h的条件下，合成了立方相钙钛矿结构KTa0.6Nb0.4O3陶瓷粉体，KTN晶粒形状呈规则的立方体，尺寸约为30-50nm；最后对溶剂热法合成纳米粉体的机理进行了分析讨论．     

用改进的液相沉淀法制备ZnS纳米晶

以ZnSO4、（NH4）2S为原料，通过加入分散剂对传统的液相沉淀法进行改进，制备出ZnS的纳米粉末，并探讨了制备过程中沉淀、洗涤、干燥以及晶化等阶段的反应条件对产物的影响。结果表明：以丙三醇为分散剂、原料配比（n(ZnSO4)/n((NH4)2S)杰1：0.9、料液浓度比1：1，c(ZnSO4)、c((NH4)2S)均为0.2mol/L时为沉淀适宜工艺条件；干燥前对沉淀物用无水乙醇进行脱水处理，可有效地控制硬团聚体的产生；沉淀经400-600℃晶化1h，可得立方晶形β-ZnS纳米晶，产物为均匀球形，分散性较好；400℃晶化的产物晶粒尺寸约为40nm；600℃晶化的产物晶粒尺寸约为50nm。     

半化学法制备0.80Pb(Mg1/3Nb2/3)O3-0.20PbTiO3 陶瓷的研究

研究了制备纯钙钛矿相0．80Pb(Mg1／3Nb2／3)O3-0．20PbTiO3(缩写为PMNT)陶瓷的半化学法新工艺．详细讨论了除Nb2O5外，其它反应物以其非氧化物形态分别代替PbO、MgO和TiO2，以及PbTiO3或同成分的0．80PMN-0．20PT等钙钛矿相子晶对PMNT预烧粉体中钙钛矿相含量的影响；探讨了烧结温度对半化学法制备的PMNT陶瓷介电性能的影响，并对PMNT陶瓷的相组成、显微组织及介电性能进行了表征和测定．结果表明：提高镁组分的反应活性对提高预烧粉体中钙钛矿相含量的效果较好，同时以钛酸四丁酯取代TiO2的效果最好；半化学法工艺简单，能在850。C／2h预烧条件下制得几乎纯钙钛矿相的PMNT粉体，经过较低的烧结温度(950℃／2h)可制得致密的、介电性能优异的PMNT陶瓷．     

钛合金表面原位生长含α-Al2O3相高硬度陶瓷膜的研究

在NaAlO2溶液中，采用微等离子氧化法在Ti-6Al-4V合金表面制备出含α-Al2O3相高硬度陶瓷膜．利用显微硬度计分析了膜层的硬度及其分布，用落球冲击法、耐热循环冲击法研究了膜层与基体的界面结合情况，并探讨了在微等离子体氧化过程中电解液浓度和负相／正相电流比(Ic/Ia)对膜层相组成和力学性能的影响规律。结果表明：在浓度较高的铝酸钠溶液中(0．15～0．20mol／L)得到的膜层含有大量α-Al2O3相且随着Ic/Ia。比例减小α-Al2O3相的含量增加，此种膜层硬度为1100～1600Hk50k；而在低浓度溶液中(≤0．050mol／L)得到的膜层只含有Al2TiO5和金红石型TiO2，硬度仅为500～850Hk50g．横截面硬度分布：从界面处到膜的表层硬度逐渐增大并在达到最大值后缓慢下降,利用SEM观察了经落球冲击后膜层的表面的状态，发现膜层表面无裂纹及脱落的现象，膜层与基体结合良好，另外，在耐热循环冲击试验中厚度最低的膜层热冲击循环次数最高。     

交流阻抗法动态监测D2EHPA/煤油支撑液膜体系膜液流失

研究了NH4Cl在以多孔聚丙烯平板膜(Celgard 2400)为支撑体、磷酸二(2-乙基己基)酯(D2EHPA)为膜液载体和煤油为膜溶剂的支撑液膜体系中的分离过程,采用交流阻抗法动态监测支撑液膜的膜液流失过程,这种方法的优点是可以连续实时监测支撑液膜的膜液流失.通过IM6电化学工作站测出了不同时间下的膜电阻来监测支撑液膜膜液流失的各个阶段,同时考察了影响膜液流失的一些因素.结果表明,膜电阻能够实时反映出膜液流失情况,原料相初始浓度降低和载体浓度增加均使液膜流失加快.     

Recovery of phenol from aqueous solution by supported liquid membrane using vegetable oils as liquid membrane

The transport of phenol through a flat sheet supported liquid membrane (SLM) containing vegetable oil as liquid membrane (LM) has been investigated. The permeation of phenol was investigated by varying the experimental conditions like, selection of LM, support material, feed phase pH, stripping solution concentration, stirring speed and different initial concentration of phenol. It has been found that, each LM investigated in the present study shows the effective removal of phenol using polytetrafluoroethylene (PTFE) membrane and PP supported membrane as a solid support. Among the various oils tested, palm oil has chosen to be the best LM with permeability of 8.5x10(-6) m/s in acidic feed of pH 2.0 with 0.2 M sodium hydroxide as effective stripping agent. After 6 h all the phenol from the feed side gets transported to strip solution with an initial concentration of 100 mg/L. A concentration factor of five has been achieved in the present investigation easily with 0.2 M sodium hydroxide as stripping reagent. After 10 transport studies with one impregnation of LM, the LM showed no significant loss in the transport rate with average permeability of 7.9x10(-6) m/s with initial concentration 100 mg/L. Further study has also been attempted with cresols to explore the possibility of applying this to industrial wastewater under the optimized conditions for phenol. After 14 h of the transport studies in the phenol-formaldehyde industry wastewater, phenolic concentration in the feed solution was found to be below detectable level (1x10(-2) mg/L). For wood processing industry wastewater the transport takes place at the initial permeability of 7.1x10(-5) m/s. Thus it has been demonstrated the use of renewable, cheap, non toxic, naturally occurring vegetable oils as a novel, green liquid membrane for the recovery of phenol from aqueous solution in SLM, which has never been employed before in liquid membrane techniques.     

茶碱-铜(Ⅱ)离子配位分子印迹膜的制备及表征

以茶碱为模板分子,铜离子为配体、4-乙烯吡啶(4-VP)为功能单体、乙二醇二甲基丙烯酸酯(EDMA)为交联剂,在聚偏氟乙烯(PVDF)基膜上采用表面涂覆热聚合的方法制备了金属配位分子印迹膜,通过平衡结合实验研究了印迹膜对茶碱的结合性能和结合选择性。结果表明,铜离子的配位作用能提高印迹膜的结合性,在茶碱浓度为0.2 mmol/L时结合量从1.61μmol/g提高到了2.69μmol/g。在铜离子配位的作用下印迹膜对茶碱的结合能力高于同样化学组成的非印迹膜。相比于可可碱印迹膜对茶碱有较好的选择性,在浓度为0.05 mmol/L时选择性达到了2.39。     

New transparent conducting MgIn2O4---Zn2In2O5 thin films prepared by magnetron sputtering

New materials for a transparent conducting oxide film are demonstrated. Highly transparent Zn₂In₂O₅ films with a resistivity of 3.9 × 10⁻⁴ Ω cm were prepared on substrates at room temperature using a pseudobinary compound powder target composed of ZnO (50 mol.%) and In₂O₃ (50 mol.%) by r.f. magnetron sputtering. MgIn₂O₄---Zn₂In₂O₅ films were prepared using MgIn₂O₄ targets with a ZnO content of 0–100 wt.%. The resistivity of the deposited films gradually decreased from 2 × 10⁻³ to 3.9 × 10⁻⁴ Ω cm as the Zn/(Mg + Zn) atomic ratio introduced into the films was increased. The greatest transparency was obtained in a MgIn₂O₄ film. The optical absorption edge of the films decreased as the Zn/(Mg + Zn) atomic ratio was increased, corresponding to the bandgap energy of their materials. It was found that the resistance of the undoped Zn₂In₂O₅ films was more stable than either the undoped MgIn₂O₄, ZnO or In₂O₃ films in oxidizing environments at high temperatures.     

On-chip electro membrane extraction with online ultraviolet and mass spectrometric detection

Electro membrane extraction was demonstrated in a microfluidic device. The device was composed of a 25 μm thick porous polypropylene membrane bonded between two poly(methyl methacrylate) (PMMA) substrates, each having 50 μm deep channel structures facing the membrane. The supported liquid membrane (SLM) consisted of 2-nitrophenyl octyl ether (NPOE) immobilized in the pores of the membrane. The driving force for the extraction was a 15 V direct current (DC) electrical potential applied across the SLM. Samples containing the basic drugs pethidine, nortriptyline, methadone, haloperidol, loperamide, and amitriptyline were used to characterize the system. Extraction recoveries were typically in the range of 65-86% for the different analytes when the device was operated with a sample flow of 2.0 μL/min and an acceptor flow of 1.0 μL/min. With the sample flow at 9.0 μL/min and the acceptor flow at 0.0 μL/min, enrichment factors exceeding 75 were obtained during 12 min of operation from a total sample volume of only 108 μL. The on-chip electro membrane system was coupled online to electrospray ionization mass spectrometry and used to monitor online and real-time metabolism of amitriptyline by rat liver microsomes.     

纳米Fe3O4- 活性炭混合超级电容器电化学性能的研究

研究了以纳米Fe₃O₄和活性炭(AC)为电极材料的超级电容器. 以FeSO₄·7H₂O和氨水为原料, 采用微波法制备出平均粒径为36nm的Fe₃O₄纳米粒子. 组装了以6mol/L KOH溶液为电解液的Fe₃O₄/KOH/Fe₃O₄、AC/KOH/AC、Fe₃O₄/KOH/AC三种类型的模拟电容器. 用循环伏安、恒流充放电和交流阻抗法对电容器进行了电化学性能测试. 结果发现, 混合电容器的工作电压可达到1.2V. 电流密度为0.5mA/cm²时, 正/负极质量比为1.5的Fe₃O₄/KOH/AC电容器的能量密度达到9.25Wh/kg, 与AC/KOH/AC电容器相比, 能量密度提高了53.4%.     

纳米Fe3O4-还原氧化石墨烯复合修饰玻碳电极的制备及电化学检测多巴胺

通过电化学还原法制备纳米Fe₃O₄-还原氧化石墨烯复合修饰玻碳（Fe₃O₄-rGO/GCE）电极,用于多巴胺（DA）的检测。采用SEM、TEM和循环伏安对纳米Fe₃O₄-rGO复合材料进行表征。在pH为7.0的磷酸盐缓冲液（PBS）中,采用循环伏安法研究了DA在纳米Fe₃O₄-rGO/GC上的电化学行为。实验结果表明,较裸GC电极和rGO修饰（rGO/GC）电极,由于纳米Fe₃O₄与rGO的协同作用,纳米Fe₃O₄-rGO/GC显著增大了Fe₃O₄-rGO/GC复合材料电极电化学活性面积和氧化峰电流强度i_pa。DA的浓度在6.0×10^-8~2.0×10^-6 mol/L和2.0×10^-6~8.0×10^-5 mol/L范围内,与氧化峰电流强度i_pa呈良好的线性关系,检出限达4.0×10^-9 mol/L（信噪比S/N=3）。抗坏血酸和尿酸共存物几乎不干扰DA的测定,选择性高。Fe₃O₄-rGO/GC修饰电极用于盐酸DA注射液中的DA含量测定,获得结果较好,回收率为97.1%~103.9%。     

红壤土浸出液中SO42-对铜包钢耐蚀性能的影响研究

本文采用扫描电镜/能谱分析(SEM-EDS)、动电位极化、电化学阻抗谱技术研究了铜包钢接地材料受SO₄^2-浓度影响的腐蚀行为.研究结果表明在含有不同浓度的SO₄^2-的红壤土浸出液浸泡20 d,铜包钢都已出现点蚀现象.随着SO₄^2-浓度从0.05~0.2 mol/L逐渐增加,铜包钢腐蚀程度呈现先增后减弱的趋势,在0.05 mol/L的SO₄^2-浸出液中浸泡20天腐蚀最为严重,已腐蚀至内层钢.由于0.05 mol/L的SO₄^2-浸出液中腐蚀后的铜包钢表面已被较多的不导电的腐蚀产物覆盖,因此实验结果显示其阻抗值最大和腐蚀速率最慢.     

Determining crystallization kinetic parameters of Li2O–Al2O3–SiO2 glass from derivative differential thermal analysis curves

The kinetic parameters such as crystallization activation energy, E, and the frequency factor, ν, of Li₂O–Al₂O₃–SiO₂ glass were determined by a new non-isothermal method. The method is described by the equation

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, where β is the heating rate and T_f is the inflection-point temperature of differential thermal analysis (DTA). The value of T_f is determined as the maximum peak temperature on derivative differential thermal analysis (DDTA) curves. Values of E and ν of Li₂O–Al₂O₃–SiO₂ glass were also determined by two existing non-isothermal methods, namely the Kissinger plot and the Ozawa plot, and compared with those determined by isothermal method. Values of E and ν determined by the proposed equation were 332 kJ/mol and 1.4×10¹³ s⁻¹, respectively. They are excellent agreement with the isothermal analysis results, 336 kJ/mol and 1.8×10¹³ s⁻¹, respectively. In contrast, both the Kissinger equation and the Ozawa equation give much higher values of E and ν.     

Reaction between the tetragonal tungsten bronze niobate K2Sr4Nb10O30 and the perovskite Pb(Mg1/3Nb2/3)O3

The search for dielectric materials with a high dielectric constant and ′_r = ƒ(T) curves with a flat profile fitting the X7R specification is still ongoing. Promising results were obtained by mixing compounds with closely related structures, such as the tetragonal tungsten bronze (TTB) niobate K₂Sr₄Nb₁₀O₃₀ and the perovskite Pb(Mg_1/3Nb_2/3)O₃ (PMN). The present study, based on three methods of synthesis, explores the origin of the spreading out of the dielectric curves ′_r = ƒ(T). For the composition 10x K_0.2Sr_0.4NbO₃ (KSN) + (1 − x)Pb(Mg_1/3Nb_2/3)O₃ (PMN) with x = 0.3–0.6, the three synthesis methods provided similar characteristics and for the highest perovskite ratio (x = 0.3), the ′_r = ƒ(T) curve exhibits a flat profile. When lithium is used as a sintering agent, ′_r = ƒ(T) curves present a linear dependency with the temperature. These materials are also characterized by a structural and a microstructural inhomogeneity. Two phases TTB and perovskite type, different from KSN and PMN, are present after calcination and sintering, but not evenly distributed. The PbO loss during sintering also contributes to the evolution of the properties of the material.