Au/PATP/PANI膜电极和Au/PATP/PANI/TiO2膜电极的光电化学

聚苯胺（PANI）是一种结构、 性质不同于聚乙炔和聚吡咯的新型导电高聚物,有着十分广泛的应用[1,2].近年来利用光电化学研究聚苯胺的电子结构、 掺杂情况引起人们的重视[3～5].在酸性溶液中电聚合制备聚苯胺的循环伏安曲线上出现两对氧化还原峰,其峰值电位分别为E11/2=0.13 V和E21/2=0.7 V(对饱和甘汞电极).通过改变电极电位,可获得部分氧化态、还原态、氧化态等3种状态的聚苯胺.部分氧化态具有金属导电性,还原态和氧化态均为绝缘体.本文测量3种状态聚苯胺膜电极的光电响应,首次得到其光电流谱,发现聚苯胺一些新的光电化学实验结果.提出了覆盖绝缘体的金属内发射的光电化学模型.同时,在聚苯胺膜上电沉积纳米TiO2微粒膜,得到广谱区的复合光电材料.     

PANI的内光电发射

利用电化学方法在自组装一层对氨基硫醇（PATP）的金电极上制备三种氧化还原态的聚苯胺（PANI）膜，PANI底层比较致密，表面呈山包状，该膜在K3Fe(CN)6/K4Fe(CN)6溶液的循环伏安图表明了部分氧化氮PANI膜具有良好的电子传输性能，从光电流谱得到氧化态PANI的禁带能为1．45eV，首次发现部分氧化态PANI膜的光电流谱遵循Fowler定律（IPCE^1/2-hv呈线性），具有内光电发射的性质，通过Fowler图得出部分氧化态PANI的绝缘母体的禁带宽度为3．33eV，并且证实该绝缘母体为还原态PANI，从Mott-Schottky图昨到部分氧化态和还原态PANI的平带电位都为0．63V(vs,SCE)，提出了和PANI的颗粒金属岛导电模型一致的内光电发射机理来解释部分氧化态PANI的光电化学过程。     

锆表面氧化膜的光电化学研究

用光电化学方法研究了金属锆的表面初始氧化膜和线性电势扫描形成阳极氧化膜．光电流作用谱上的阳极和阴极光电流取决于电极电势,而与成膜和测量溶液基本无关．光电流作用谱和瞬态光电流响应说明锆表面氧化膜为双层结构,内层为ＺｒＯ＿２外层为ＺｒＯ＿２·（Ｈ＿２Ｏ）＿ｎ．光电流可以来自内、外层的光生载流子和基底金属的内光注入电子迁移至电极／溶液界面与溶液中的氧化还原对反应,光电流作用谱的分析给出了三个过程的光学间能值,分别为４．５ｅＶ、３．０ｅＶ和２．０ｅＶ．     

纳米尺度TiO2聚苯胺多孔膜电极光电化学研究

用光电流作用谱，光电流－电势图等光电化学方法研究了ＴｉＯ２／聚本胺复合多孔膜电极在不含氧化还原和含有没氧化还原对体系中的光电转换过程。结果说明，ＴｉＯ２／聚苯胺复合多孔膜电极为双层ｍ－型半导体结构，ＴｉＯ２多孔膜的禁带宽度为３．２ｅＶ，外层聚苯胺膜的禁带宽度为２．８８ｅＶ。     

金属氢化物电极表面处理方法及其表面氧化膜研究：Ⅰ.富镍表面处理及氧化？

发展了两种贮氢合金表面处理新方法。光电子能谱和循环伏安实验表明，经过处理后得到了富镍表面层，可提高电极的反应性能、采用光电化学方法对不同处理的电极表面由动电位氧化形成的氧化膜进行了表征，分别观察到与表面膜吸附氢氧化和氧化还原反应有关的阳极光电流和阴极光电流，同时依照电极在循环过程中的光电流变化区分了两种处理方法的得到的表面层抗氧化性能之差异     

TiO_2聚苯胺复合膜的光电化学

利用电化学方法制备了TiO2 聚苯胺 (PANI)复合膜 .该膜具有比TiO2 或PANI膜更宽的吸收谱区 ,并且不同于利用聚苯胺光敏化的TiO2 膜 ,表现为两者复合材料膜的性质 .扫描电镜图表明 ,TiO2 微粒不完全覆盖着PANI膜 .根据TiO2 微粒光电流谱带的阈值能可得复盖在部分氧化态聚苯胺膜上的TiO2 微粒的禁带宽度为 3.0eV .部分氧化态聚苯胺膜的光电流谱遵循Fowler定律 ( 1/2 ～hυ成线性 ) .通过Fowler图得出部分氧化态聚苯胺的绝缘母体禁带宽度为 3.33eV ,并证实该绝缘母体为还原态聚苯胺 .从Mott Schottky图得到在 0 .0 5mol/LK3Fe(CN) 6 /K4 Fe(CN) 6 溶液中 (pH =8.52 )部分氧化态聚苯胺的平带电位为 0 .13V ,掺杂浓度为 5.3× 10 18cm- 3;TiO2 PANI复合膜的平带电位为 - 0 .6 5V ,掺杂浓度为 9.1× 10 19cm- 3.解释了TiO2 PANI复合膜的光电化学过程并描绘出其能带图 .利用TiO2 PANI复合膜能够有效地光降解苯酚溶液 .     

导电高聚物修饰纳米尺度TiO~2多孔膜电极的光电化学研究

用光电化学方法研究了用导电高聚物修饰的纳米晶TiO~2多孔膜电极在不含氧化还原对和含不同氧化还原对体系电解质溶液中的光电转换过程。TiO~2/导电高聚物多孔膜电极为双层n型半导体结构,内层TiO~2多孔膜的禁带宽度为3.26eV,外层聚吡咯(PPy)膜的禁带宽度为2.23eV,而聚苯胺(PAn)膜的禁带宽度为2.88eV。用导电高聚物修饰半导体电极能使其在可见光区的光吸收增加,光电流增强,且起始波长红移至>600nm,使宽禁带半导体电极的光电转换效率得到明显改善。     

纳米尺度TiO2微粒多孔膜电极光电化学

用光电流作用谱、光电流-电势图和瞬态光电流谱等光电化学方法研究了TiO2多孔膜电极在含不同氧化还原体系的电解质溶液中的光电转换过程.结果说明TiO2多孔股为n-型半导体，其禁带宽度为3.26eV.当在电解质溶液中加入醌二苯酸（BQ／HQ），TiO2多孔膜电极的光电流作用谱形基本与没加氧化还原对时类似。在可见光区的光电流拖尾是由于醌被光激发，然后给出电子到TiO2多孔膜导带而产生阳极光电流.而在电解质溶液中加入Fe（CN）3-6-／4-时，TiO2多孔膜电极的光电流作用谱有明显的改变.除了在小于380nm短波区有光电流峰外，还在400-600nm的可见光区观察到宽的光电流峰，大大增加了光电流转换效率.同时在小于-0.2V下为阳极光电流，在-0.2V～0.3V电势区间为明显阴极光电流，在大于0.3V下可观察到较弱的阳极光电流.当电极电势大于-0.2V时，光电流瞬态谱在开始光照时有一阴极瞬态光电流尖峰，然后转变为阳极稳态光电流.这是因为当电极电势较负时，Fe（CN）4-6与TiO2的电子传递络合物可以吸收光子，光生电子迅速注入TiO2导带，然后还原溶液中的而产生阴极光电流.     

聚苯胺修饰超微盘电极上镉(Ⅱ)的表面络合吸附波

用直径7 μm的碳纤维组合成超微圆盘电极,以聚苯胺修饰电级.以阶梯扫描法、循环伏安法、双阶跃计时电量法和交流阻抗法等,研究了Cd2＋在该电极上的表面络合吸附特性和电极过程.在循环伏安图上出现两个还原峰,实验和理论都证明,由于电极表面的聚苯胺对Cd2＋的特性吸附,形成电活性的表面吸附态络合物.因此,这种表面络合物首先被还原,形成峰电位－0.90 V处的表面络合吸附波,还原峰电位比Cd2＋直接还原电位（－0.98 V）正移,循环反扫时,氧化波无峰形.根据实验数据推测了电极过程的反应机理,证实该还原波具有扩散和表面反应同时控制的表面络合吸附波的特性.理论计算与实验基本一致,并求得了表面吸附态配合物的形成常数、吸附量和表面络合反应的动力学参数.实验还证实,在峰电位－1.06 V 处的还原波,是Cd2＋的表面吸附还原态诱导而产生的催化氢波.     

强度调制光电流谱研究纳晶CdSe薄膜电极的界面电荷转移过程

用强度调制光电流谱（ＩＭＰＳ）研究纳晶ＣｄＳｅ薄膜电极在多硫化钠溶液中的界 面电荷转移性能．从不同外加电压和不同溶液浓度下的光电流谱响应所得到的参数归 一化稳态光电流和表面态寿命,分析了界面电荷的直接转移和间接转移过程以及电荷 复合过程,并与多晶ＣｄＳｅ薄膜电极的结果进行了比较．     

Protonation of leucoemeraldine in the solid state and in solution

The protonation of leucoemeraldine in power form and in N-methylpyrrolidinone (NMP) solution by HCIO₄ and HBF₄ has been studied by x-ray photoelectron spectroscopy (XPS), infrared (IR), and ultraviolet (UV)-visible absorption spectroscopy. In powder form, less than 25% of the amine nitrogens can be protonated in the absence of oxygen. The effects of oxygen on the degree of protonation and the distribution of amine and imine units upon deprotonation of the salt are investigated. The degree of protonation in leuccemeraldine can be increased to about 50% with 3 M HCIO₄, similar to that achievable with emeraldine base in powder form. In NMP solution, leucoemeraldine is easily oxidized by dissolved oxygen. Protonation of both leucoemeraldine and emeraldine base in NMP solutions results in metastable species which gradually undergo deprotonation. The resulting products are affected by the O₂ content of the solutions. © 1993 John Wiley & Sons, Inc.     

聚苯胺修饰电极膜厚度的理论公式及其验证

本文提出了用于计算聚苯胺修饰电极膜厚度的理论公式,它实用于恒电流法和循环扫描伏安法制得的膜,经验证理论和实验相符合.文中还讨论了PANI密度及摩尔体积的计算和化学测定方法.     

Synthesis and characterization of aluminum–polyaniline thin films and membranes

Polyaniline (PAni) films of different intrinsic oxidation states, including emeraldine salt, emeraldine base and leucoemeraldine base, were synthesized. Free‐standing membranes and thin film bilayers of aluminum–polyaniline were fabricated by magnetron sputter deposition of aluminum onto polyaniline films. Aluminum–polyaniline samples were analyzed by transmission electron microscopy (TEM) to investigate the microstructures of specimens, including cross‐sectional TEM micrographs of the metal‐polyaniline interfacial structure not previously reported in the literature. Auger electron spectroscopy (AES) and X‐ray photoelectron spectroscopy (XPS) were employed to study the chemical bonding and interaction between deposited aluminum and polyaniline at the interface. Results indicated that the intrinsic oxidation state of the polyaniline influenced the chemistry of the aluminum–polyaniline interface. Distinct interaction between aluminum and polyaniline in the emeraldine salt‐form was observed. However, there was no evidence of direct interactions of the aluminum with emeraldine base and leucoemeraldine base polyaniline. Copyright © 2005 John Wiley & Sons, Ltd.     

Measurement of the peroxidation of Brji-35 in aqueous solution by hemin and horseradish peroxidase catalyzed fluorogenic reaction

The non-ionic surfactant Brij-35 can easily be oxidized in solution by dissolved oxygen upon light radiation during its storage. Various factors, such as light radiation, temperature, pH, ionic strength as well as dissolved oxygen influencing the stability of Brij-35 were studied. The results showed that light radiation is the most important factor inducing the oxidation by the dissolved oxygen. The oxidized product was confirmed, indirectly, to be the peroxide of Brij-35 based on a number of evidences. The extent of the oxidation can be traced by a peroxidase or hemin catalyzed fluorogenic reaction with p-hydroxyphenylacetic acid as a substrate. The concentration of the peroxide in a Brij-35 solution (0.8%, w/v) stored at room temperature for a month is in the range of 9 × 10^–5 mol/L.     

Improved Potentiometric and Optic Sensitivity of Polyaniline Film to Dissolved Oxygen by Incorporating Iron‐Porphyrin

Polyaniline (PAn) films can be used in an electrochemical and optical combination system to amplify the optical signal for dissolved oxygen (DO) detection. To further improve the sensitivity of PAn film to DO, an oxygen‐sensitive molecule, Fe(III) meso‐tetera (4‐sulfonatophenyl) porphyrin (FeTSPP) is incorporated into PAn during the film generation. Results show that, after incorporating FeTSPP into the PAn matrix, both optical and potentiometric responses to DO are improved. The optimal optical signal is obtained under the application of ?2.5 μA to the modified electrode. Under this applied current, both optical and potentiometric signals show linear relations with the DO concentration within the range of 0.00–4.63 mg L^?1, and the sensitivities for optical and potentiometric signals are 4.18 grayscale units mg^?1 L and 13.39 mV mg^?1 L, respectively.     

Measurement of the peroxidation of Brji-35 in aqueous solution by hemin and horseradish peroxidase catalyzed fluorogenic reaction

The non-ionic surfactant Brij-35 can easily be oxidized in solution by dissolved oxygen upon light radiation during its storage. Various factors, such as light radiation, temperature, pH, ionic strength as well as dissolved oxygen influencing the stability of Brij-35 were studied. The results showed that light radiation is the most important factor inducing the oxidation by the dissolved oxygen. The oxidized product was confirmed, indirectly, to be the peroxide of Brij-35 based on a number of evidences. The extent of the oxidation can be traced by a peroxidase or hemin catalyzed fluorogenic reaction with p-hydroxyphenylacetic acid as a substrate. The concentration of the peroxide in a Brij-35 solution (0.8%, w/v) stored at room temperature for a month is in the range of 9 × 10^–5 mol/L. Received: 8 February 1999 / Revised: 13 April 1999 / Accepted: 17 April 1999     

Concentration determination of oxygen nanobubbles in electrolyzed water

Water electrolysis is well known to produce solutions supersaturated with oxygen. The oxygen in electrolyzed solutions was analyzed with a dissolved oxygen meter and the Winkler method of chemical analysis. The concentration of oxygen measured with the dissolved oxygen meter agreed with that obtained using the Winkler method. However, measurements using a 10-fold dilution method showed a larger concentration of dissolved oxygen compared to the above methods. We developed a modified Winkler method to measure total oxygen concentration more accurately, which agreed with the results obtained from the 10-fold dilution experiment. The difference in measurements is due to the existence of oxygen nanobubbles, as confirmed by the observation of dynamic light scattering using a laser. Further analysis of the oxygen nanobubbles demonstrated that the stability of the nanobubbles was sufficient for chemical reaction and solvation to bulk solution.     

The effects of UV radiation on anodic wave of human serum

Polarographic anodic oxidation wave that can be correlated to total antioxidant capacity (TAC) in Human serum corresponds to 2H+ and 2e process. The limiting current of the wave, which is proportional to TAC, is strongly influenced by UV light intensity and irradiation time. A mechanism has been proposed to explain the effects of UV on anodic wave related to antioxidant behavior. Results show that decomposition processes follow to the excitation a transitory product at three different light intensities at 340 nm. The number of decomposition products increase with increasing light intensity. The rate of oxygen radical capture ability of the serum antioxidants might be estimated by comparing the changes of anodic wave in the absence and presence of naturally dissolved oxygen.     

铂电极在碱性含氧溶液中的预还原处理对鲁米诺电 致化学发光的影响

研究了铂电极的不同预极化处理过程对碱性鲁米诺阳极电致化学发光(ECL)和阳极极化曲线的影响,发现在碱性含氧溶液中预还原处理的铂电极可增强0.22V(vs.SCE)处发光峰强度,且催化产生1.07V(vs.SCE)附近氧气析出过程并伴随产生明显的ECL发光峰;在酸性溶液中预处理电极可抑制这些活性。给出了催化氧气析出的可能作用机理：在碱性溶液中溶解氧还原生成了吸附在铂电极表面的(OH^-)~a~d~s,从而回忆了氧气的析出过程。同时给出了在碱性含氧溶液中预还原的铂电极上两个可能的ECL反应通道：(1)在0.22V鲁米诺阴离子氧化为鲁米诺自由基,然后与溶解氧反应而发光;(2)1.07V处析出的新鲜氧与鲁米诺阴离子反应而发光。     

改进的假高稀技术合成聚苯胺三聚体和四聚体及其紫外光谱的研究

提出了一条合成还原态的苯基封端聚苯胺齐聚物的新方法:即苯胺二聚体的Schiff碱或苯胺三聚体的Schiff碱在酸性溶液中缓慢水解,形成聚苯胺二聚体和三聚体的盐酸盐,这些盐酸盐与二苯胺或N-苯基-对苯二胺反应,经苯肼还原,生成还原态的苯基封端的聚苯胺三聚体和四聚体.用红外、核磁、元素分析和基底辅助激光解吸质谱对其进行了表征,并用紫外光谱对还原态的三聚体和四聚体的化学氧化过程进行了跟踪研究.