Determination of electrochemical electron-transfer reaction standard rate constants at nanoelectrodes: Standard rate constants for ferrocenylmethyltrimethylammonium(III)/(II) and hexacyanoferrate(III)/(II)

Zhang Y; Zhou JZ; Lin LL; Lin ZH

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Determination of electrochemical electron-transfer reaction standard rate constants at nanoelectrodes: Standard rate constants for ferrocenylmethyltrimethylammonium(III)/(II) and hexacyanoferrate(III)/(II)

机译：纳米电极上电化学电子转移反应的标准速率常数的测定：二茂铁基甲基三甲基铵（III）/（II）和六氰合铁酸盐（III）/（II）的标准速率常数

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The most common approximation of electroneutrality is inappropriate for analyzing the voltammetric response of nanoelectrodes. Therefore, the microelectrode theory for extracting the standard rate constant k(0) for electron transfer from steady-state voltammograms is invalid for nanoelectrodes. Unlike previous approaches, we considered the influence of the interfacial potential distribution caused by the absence of electroneutrality. We estimated the magnitude of the error at low overpotential incurred as a result of ignoring the absence of electroneutrality and found that it was small. In this region, electrochemical reaction appears to be limited by the rate of electron transfer. Under these conditions, k(0) can be obtained from steady-state voltammogram data in a low overpotential region according to an approximate form of the Butler-Volmer equation. This procedure can greatly simplify analysis and calculation of the rate constant k(0) at nanoelectrodes. Steady-state voltammogram of equal-concentration hexacyanoferrate(III)/(II) (Fe(CN)(6)(3-)/Fe(CN)(6)(4-)) and ferrocenylmethyltrimethylammonium(III)/(II) (FcTMA(2+)/FcTMA(+)) redox couples were investicated at Pt-Ir nanoelectrodes in the presence of a support electrolyte. k(0) for Fe(CN)(6)(3-)/Fe(CN)(6)(4-) and FcTMA(2+)/FcTMA(+) at Pt-Ir nanoelectrodes were evaluated.

机译：电子中性的最常见近似不适用于分析纳米电极的伏安响应。因此，用于从稳态伏安图中提取电子转移的标准速率常数k（0）的微电极理论对于纳米电极是无效的。与以前的方法不同，我们考虑了由于不存在电子中性而引起的界面电位分布的影响。我们估计了由于忽略了电子中性而导致的低电位下误差的大小，发现误差很小。在该区域，电化学反应似乎受到电子转移速率的限制。在这些条件下，可以根据Butler-Volmer方程的近似形式，从低超电势区域的稳态伏安数据获得k（0）。该程序可以大大简化纳米电极上速率常数k（0）的分析和计算。等浓度六氰合铁氰化物（III）/（II）（Fe（CN）（6）（3-）/ Fe（CN）（6）（4-））和二茂铁基甲基三甲基铵（III）/（II）的稳态伏安图（FcTMA（2 +）/ FcTMA（+））氧化还原对在支持电解质存在的情况下在Pt-Ir纳米电极上进行了研究。 Fe（CN）（6）（3-）/ Fe（CN）（6）（4-）和FcTMA（2 +）/ FcTMA（+）在Pt-Ir纳米电极上的k（0）进行了评估。

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《Electroanalysis》 |2008年第13期|共5页
作者
Zhang Y; Zhou JZ; Lin LL; Lin ZH;
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正文语种 eng
中图分类电化学、电解、磁化学;
关键词
nanoelectrodes; Fe(CN)(6)(3-)/Fe(CN)(6)(4-); FcTMA(2+)/FcTMA(+); heterogeneous electron transfer reactions; standard rate constant; NANOMETER-SIZED ELECTRODES; STEADY-STATE VOLTAMMOGRAMS; VOLTAMMETRIC RESPONSE; PLATINUM-ELECTRODES; DOUBLE-LAYER; FABRICATION; DIMENSIONS; ELECTRONEUTRALITY; MICROELECTRODES;

机译：纳米电极;Fe（CN）（6）（3-）/ Fe（CN）（6）（4-）;FcTMA（2 +）/ FcTMA（+）;异质电子转移反应;标准速率常数;纳米级电极稳态伏安图;伏安响应;铂电极;双层;制备;尺寸;电子极性;微电极;

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1. Determination of electrochemical electron-transfer reaction standard rate constants at nanoelectrodes: Standard rate constants for ferrocenylmethyltrimethylammonium(III)/(II) and hexacyanoferrate(III)/(II) [J] . Zhang Y, Zhou JZ, Lin LL, Electroanalysis . 2008,第13期

机译：纳米电极上电化学电子转移反应的标准速率常数的测定：二茂铁基甲基三甲基铵（III）/（II）和六氰合铁酸盐（III）/（II）的标准速率常数
2. Electron-transfer reactions: reductions of various double-chain surfactant cobalt(III) complexes by hexacyanoferrate(II) in microheterogeneous media [J] . Nagaraj Karuppiah, Murugan Krishnan Senthil, Thangamuniyandi Pilavadi Monatshefte fur Chemie . 2015,第6期

机译：电子转移反应：在微非均相介质中六氰合铁酸盐（II）还原各种双链表面活性剂钴（III）配合物
3. Electron-transfer reactions: reductions of various double-chain surfactant cobalt(III) complexes by hexacyanoferrate(II) in microheterogeneous media [J] . Karuppiah Nagaraj, Krishnan Senthil Murugan, Pilavadi Thangamuniyandi Monatshefte für Chemie - Chemical Monthly . 2015,第6期

机译：电子转移反应：在微非均相介质中六氰合铁酸盐（II）还原各种双链表面活性剂钴（III）配合物
4. Cobalt(Ii) hexacyanoferrate and chromium (III) hexacyanoferrate based chemical sensors fo the determination of hydrogen peroxide [C] . Bor Iuan Jan, Meng Shan Lin International meeting on chemical sensors . 1998

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5. Part I Effect of Resonance on Sigma Constants, Acidity Constants of Thiophenols. Part II The Reaction of Thiourea with Epoxides. Part III The Reaction of Thiacyclopropanes and Thiacyclobutane with Organolithium Compounds [D] . Andersen, Harry M. 1952

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6. Analytical Applications of Reactions of Iron(III) and Hexacyanoferrate(III) with 210-Disubstituted Phenothiazines [O] . Helena Puzanowska-Tarasiewicz, Joanna Karpińska, Ludmiła Kuźmicka 2009

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7. Electron-transfer Kinetics of Transition-metal Complexes in Lower Oxidation States. Part III. Electrochemical Rate Constants for the Fe(II)/Fe(I) Redox Systems [O] . Tetsuo Saji, Tamaki Yamada, Shigeru Aoyagui 1975

机译：较低氧化态中过渡金属配合物的电子转移动力学。第三部分。 Fe（II）/ Fe（I）氧化还原系统的电化学率常数
8. Reliability of Standard Rate Constants for Rapid Electrochemical Reactions [R] . Gennett, T., Weaver, M. J. 1984

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Determination of electrochemical electron-transfer reaction standard rate constants at nanoelectrodes: Standard rate constants for ferrocenylmethyltrimethylammonium(III)/(II) and hexacyanoferrate(III)/(II)

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