室温下甲苯中C6-60和C6-70的电化学检测

采用铂微电极观察到了室温下(25±1)℃甲苯单一溶剂中C60和C70的六步单电子电化学还原过程.在甲苯中采用一般的有机相支持电解质溶解度差,电势窗口也不宽.实验结果表明,离子液体[Tetrahexylammonium bis(trifluoromethylsulfonyl)imide,THA-Tf2N]在甲苯中具有良好的溶解度,因而可以作为这种非极性溶剂的理想支持电解质,并且该体系可以提供宽达-3.7 V(相对于二茂铁电对,Fe /Fe)的电化学还原窗口,这是在室温下实现C6-60和C6-70的电化学检测的主要原因.     

富勒烯碳-60,碳-70的电化学研究进展

短短的几年,随着各种物理与化学研究方法的相继介入,以C_(60)和C_(70)为代表的富勒烯研究取得了令人瞩目的成就。跟踪最新进展,引文41篇,本文就其电化学方面的研究工作做了系统的综述。     

基于石墨烯和室温离子液体复合物溶胶修饰的玻碳电极制备尿酸电化学传感器

将石墨烯(GN)与室温离子液体(IL)1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6),以适当比例研磨成胶状IL-GN,修饰在玻碳电极(GC)上制备了IL-GN/GC。利用原子力显微镜AFM表征IL-GN的形成。由于石墨烯和室温离子液体的协同作用,该电极显示了对H2O2良好的催化性能,基于尿酸氧化酶将之制备成生物传感器,用于尿酸(UA)直接电化学检测,并进行了传感器的抗干扰性能及实际血样中尿酸的检测实验。结果表明,此传感器检测尿酸的线性范围为0.002~4.5 mmol/L,相关系数为0.995,检出限为0.85μmol/L,响应时间为10 s。此传感器制备简便,稳定性好,抗干扰能力强,可用于实际血清中尿酸的检测,为尿酸的测定提供了新方法。     

室温离子液体电化学稳定性的研究

随着绿色化学的发展,人们对室温离子液体(RTIL)的研究已日益备受重视,较早发现的如由二烷基咪唑正离子(EMI^ )和氯化铝负配离子(A1Cl4^-)组成的离子液体(氯化铝类离子液体),具有许多优良的物理化学性质,如电导率高,在高温下仍有很低的蒸汽压,电化学稳定性好(即有宽阔的电化学窗口),     

在离子液体中电化学还原合成2-氨基苯甲醚

利用循环伏安法研究了2-硝基苯甲醚在离子液体中的电化学还原行为。以Cu为工作电极,石墨电极为对电极,饱和甘汞电极(SCE)为参比电极,在室温离子液体中电化学还原2-硝基苯甲醚合成2-氨基苯甲醚。优化了电解实验条件,在最佳实验条件(E= -1.0 V, T=50 ℃, c=74.4 mmol·L-1, Q=6 F·mol-1, Y=10:1)下2-氨基苯甲醚的产率最高可达51.3%。在离子液体中电化学合成2-氨基苯甲醚,反应条件温和,避免了有毒易挥发的溶剂、催化剂及其他支持电解质等的使用;并实现了离子液体的重复利用,为2-氨基苯甲醚提供了一条新的绿色化合成路线。     

不同离子液体中硝基苯的电化学还原

研究了硝基苯在N-甲基咪唑对甲基苯磺酸([Mim][PhSO3])和1-丁基-3-甲基咪唑六氟磷酸([Bmim][PF6])两种离子液体中的电化学还原反应.循环伏安法测试显示,硝基苯在[Mim][PhSO3]中只出现一个还原峰,是一个受扩散控制的不可逆电化学反应,而在[Bmim][PF6]中出现两对氧化还原峰,表明其还原产物随离子液体性质的不同而异.     

气相C60与甲苯,氯化苄和对二甲苯反应研究

在质谱离子源内,气相C_(60)分别与甲苯、氯化苄、对二甲苯产生的主要碎片离子及自由基反应,生成了C_(60)的多种气相衍生物离子,表明气相下C_(60)具有很活泼的化学性质。     

应用扫描电化学显微镜研究电子在室温离子液体与1,2-二氯乙烷混合溶液/水相界面上的转移反应

应用扫描电化学显微镜研究了室温离子液体(Omim·Tf2N)与1,2-二氯乙烷(DCE)混合溶液/水界面上的电子转移反应. 在保持共同离子(Tf2N-)的浓度比恒定及异相电子转移反应由界面电势差所决定的条件下, 研究了离子液体和DCE混合溶液中二茂铁(Fc)与水相中亚铁氰化钾[K4Fe(CN)6]之间异相电子转移反应. 探讨了混合溶液中离子液体的体积分数(xRTIL)的变化对混合溶液/水界面上电子转移反应的影响. 结果表明, 随着xRTIL的减小(从1减小到0.1), Fc在混合溶液中的扩散系数单调递增(从2.730×10-7 cm2·s-1增加到9.131×10-6 cm2·s-1); 而异相电子转移反应速率常数(k)则先逐渐减小(从8.0 mol-1·cm·s-1减小到0.32 mol-1·cm·s-1), 之后又略有增大(从0.32 mol-1·cm·s-1增大到0.48 mol-1·cm·s-1). 对这种现象可能的原因进行了较详细探讨.     

Electrochemical Determination of NDPhA via its Electrocatalysis at Porous Au Electrode in Room Temperature Ionic Liquid

N‐Nnitrosodiphenylamine (NDPhA) is a typical kind of nonvolatile nitrosamine. Its electrochemical oxidation occurs usually at relative positive potentials (>1.1 V) even at catalytic noble metal electrodes in aqueous solutions. The formation of oxide and evolution of oxygen at such high potentials makes the analysis of NDPhA on noble metal electrodes difficult. Accordingly, its electrochemical analysis is usually performed in anhydrous organic electrolytes. In this work, room temperature ionic liquid [BMIM⁺] [BF ] acting as electrolyte was introduced in this electrochemical analysis systems. It acts as supporting electrolyte itself, has good solubility of organic compounds, and allows a wide performance potential window of noble electrode, and in turn, highly electrocatalytic noble electrode of platinum or gold can be used as working electrodes. After the investigation of the electrocatalytic behavior of NDPhA at a gold electrode in this room temperature ionic liquid electrolyte, high sensitive determination of NDPhA was designed. It is demonstrated that the electrochemical response of NDPhA is determined by a surface‐controlled process. Therefore, a sensor with high sensitivity was constructed by applying porous Au electrodes with highly electrocatalytic activity and large active surface area. The present approach on one hand broadens the application field of room temperature ionic liquids, and on the other hand provides a sensitive analytical method for environmental detection.     

基于室温离子液体的活化石墨烯粉末超级电容储能性能

室温离子液体(RTILs)具有电压窗口高等优点,被认为是实现超级电容高性能储能的绿色电解液。但是,离子液体的电导率低、粘度高,使得其储能性能不佳。本文探究了溶剂效应对离子液体超级电容储能性能的影响。以石墨烯粉末为活性材料,选取1-丁基-3-甲基咪唑四氟硼酸盐为离子液体,通过添加乙腈溶剂配置了具有不同摩尔分数ρIL的电解液(从0.25到1.0)。结果表明,溶剂效应对超级电容性能的影响与电压扫描速率或电流密度密切相关。低扫描速率下,溶剂对储能基本没有影响,而高扫描速率下,添加溶剂可显著提升比电容(在ρIL=0.25时,增加~2倍)。这是由于溶剂削弱了离子-离子间交互作用,从而降低了电解液粘度(~29倍),内阻(~5.5倍)和介电弛豫时间(~6.3倍)。在ρIL=0.25时,超级电容最大能量和功率密度分别为65.2 Wh·kg~(-1)和18066.6 W·kg~(-1),显著优于近期文献报道结果。特别地,当工作温度提升到50°C时,其能量密度将达到85.5 Wh·kg~(-1),显著高于传统水系、有机电解液超级电容和铅酸电池,与镍金属氢化物和锂离子电池性能相当。     

金刚石和类金刚石的常温常压电化学合成

采用线性扫描伏安(LSV)\, X射线粉末衍射和拉曼光谱等方法对电化学还原法从CCl4\|NaCl\|\[BMIM\]BF4体系合成金刚石的可能性进行了研究. LSV研究结果表明, CCl4可在白金研究电极表面直接还原而不需要NaCl作为电子媒介. 采用恒电势电解的方法可在白金研究电极上获得黑色还原产物. 采用X射线粉末衍射和拉曼光谱对研究电极表面形成的黑色产物进行了表征, 在XRD图谱中可观察到金刚石的特征峰, 在拉曼光谱中1 332 cm-1附近可观察到金刚石结构的特征吸收峰, 表明产物中存在金刚石相. 这些结果表明, 采用电化学方法在常温常压下将CCl4转化为金刚石的方法是可行的.     

Electrochemical Determination of Ascorbic Acid in Room Temperature Ionic Liquid BPPF6 Modified Carbon Paste Electrode

A room temperature ionic liquid N‐butylpyridinium hexafluorophosphate (BPPF₆) was used as a binder to make an ionic liquid modified carbon paste electrode (IL‐CPE), which showed good characteristics such as simple preparation procedure, fast electrochemical response and good conductivity. The electrochemical oxidation of ascorbic acid (AA) on the new IL‐CPE was carefully studied. The oxidation peak potential of AA on the IL‐CPE appeared at 109 mV (vs. SCE), which was about 338 mV decrease of the overpotential compared to that obtained on the traditional carbon paste electrode (CPE) and the oxidation peak current was increased for about four times. The electrochemical parameters of AA on the IL‐CPE were calculated with the charge transfer coefficient (α) and the electrode reaction rate constant (k_s) as 0.87 and 0.800 s^?1, respectively. Based on the relationship of the oxidation peak current and the concentration of AA a sensitive analytical method was established with cyclic voltammetry. The linear range for AA determination was in the range from 1.0×10^?5 to 3.0×10^?3 mol/L with the linear regression equation as I_p (μA)=?2.52–0.064C (μmol/L) (n=13, γ=0.9942) and the detection limit was calculated as 8.0×10^?6 mol/L (3σ). The proposed method was free of the interferences of coexisting substances such as dopamine (DA) and amino acids etc., and successfully applied to the vitamin C tablets determination.     

Electrochemical formation and properties of two-component films of transition metal complexes and C60 or C70

The electrochemically active polymers have been formed during electro-reduction carried out in solution containing fullerenes, C₆₀ or C₇₀, and transition metal complexes of Pd(II), Pt(II), Rh(III), and Ir(I). In these films, fullerene moieties are covalently bounded to transition metal atoms (Pd and Pt) or their complexes (Rh and Ir) to form a polymeric network. All films exhibit electrochemical activity at negative potentials due to the fullerene cages reduction process. For all studied metal complexes, yields of formation of films containing C₇₀ are higher than yields of electrodeposition of their C₆₀ analogs. C₇₀ /M films also exhibit higher porosity in comparison to C₆₀/M layers. The differences in film morphology and efficiency of polymer formation are responsible for differences in electrochemical responses of these films in acetonitrile containing supporting electrolyte only. C₇₀/M films shows more reversible voltammeric behavior in negative potential range. They also show higher potential range of electrochemical stability. Processes of film formation and electrochemical properties of polymers depend on the transition metal ions or atoms bonding fullerene cages into polymeric network. The highest efficiency of polymerization was observed for fullerene/Pd and fullerene/Rh films. In the case of fullerene/Pd films, the charge transfer processes related to the fullerene moieties reduction in negative potential range exhibit the best reversibility among all of the studied systems. Capacitance performances of C₆₀/Pd and C₇₀/Pd films deposited on the porous Au/quartz electrode were also compared. Capacitance properties of both films are significantly affected by the conditions of electropolymerization. Only a fraction of the film having a direct contact with solution contributes to pseudocapacitance. Capacitance properties of these films also depend on the size of cations of supporting electrolyte. The C₇₀/Pd film exhibits much better capacitance performance comparison to C₆₀/Pd polymer.     

离子液体在CO_2电还原反应过程中的催化作用与机理研究

在1-丁基3-甲基咪唑三氟甲基磺酸盐([Bnlim][CF_3SO_3])/碳酸丙烯酯(PC)溶液中,采用循环伏安曲线、交流阻抗谱及阻抗模拟方法,研究了CO_2在Au上发生电还原反应的速率控制步骤与离子液体的催化作用.结果表明,在CO_2电还原反应过程中,吸附态CO_2经单电子还原生成CO_2~-自由基是速率控制步骤.由于离子液体的催化作用,CO_2在[Bmim][CF_3SO_3]/PC溶液中电还原的过电位比在四丁基三氟甲基磺酸铵([Bu_4N][CF_3SO_3])/PC溶液中降低了239 mV.交流阻抗测试结果表明,离子液体中的阳离子[Bmim]~+吸附在Au电极表面,形成离子液体吸附层,吸附态的CO_2分子经单电子还原后生成CO_2~·-)自由基,与周围离子液体发生相互作用,形成中间体[Bmim-CO_2]_(ad),降低了CO_2~(·-)的能量状态,使得CO_2电还原反应的过电位大幅度降低.     

6-磺酰氯香豆素的室温燐光特性

通过多种重原子微扰剂和实验条件的选择,成功地实现了C6SCl在数种基质上的RTP发射。发现Pb(Ⅱ)盐是这种RTP发射的最有效的外部重原子微扰剂。在滤纸基质上,以1mol/L Pb(Ac)_2作重原子微扰剂获得了强度高且信/背比亦高的RTP信号,λ_(ex)/λ_(em)=320/496nm。0.2μl点样体积中,C6SCl含量在4～200pmol范围内与RTP信号强度呈良好的线性关系。