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首页> 外文会议>International Symposium on Hydrogen at Surface and Interfaces, May, 2000, Toronto >THE PHASE-SHIFT METHOD FOR THE OVER-POTENTIALLY DEPOSITED HYDROGEN (OPD H) AT THE POLY-Ir/H_2SO_4 AQUEOUS ELECTROLYTE INTERFACE
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THE PHASE-SHIFT METHOD FOR THE OVER-POTENTIALLY DEPOSITED HYDROGEN (OPD H) AT THE POLY-Ir/H_2SO_4 AQUEOUS ELECTROLYTE INTERFACE

机译：在Poly-Ir / H_2SO_4电解质界面上过势沉积氢（OPD H）的相移方法

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摘要

The phase-shift method for the Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the polycrystalline Ir (poly-Ir)/0.1 M H_2SO_4 aqueous electrolyte interface has been studied using cyclic voltammetric and ac impedance techniques. At the intermediate frequencies, the simplified equivalent circuit for the cathodic H_2 evolution reaction and the corresponding phase-shift equation are well fitted to the interface. The phase-shift profile (-φ vs. E) for the intermediate frequencies, i.e., the phase-shift method, can be used as an experimental method to determine the Langmuir adsorption isotherm (θ vs. E) at the interface regardless of the cathodic H_2 evolution reaction. At the poly-Ir/0.1 M H_2SO_4 electrolyte interface, the UPD H has not been observed due to a high H~+ concentration. The equilibrium constant (K) and the standard free energy (ΔG_(ads) of the OPD H are 2.0 X 10~(-4) and 21.1 kJ/mol, respectively. The criterion of the UPD H and the OPD H is the H adsorption sites and processes rather than the H_2 evolution reaction. The UPD H and the OPD H on the poly-Ir surface act as two distinguishable electroadsorbed H species.
机译：在多晶Ir（poly-Ir）/0.1 M H_2SO_4水性电解质界面上，欠电位沉积的氢（UPD H）和过电位沉积的氢（OPD H）的Langmuir吸附等温线的相移方法一直是使用循环伏安法和交流阻抗技术进行了研究。在中频处，用于阴极H_2放出反应的简化等效电路和相应的相移方程很好地拟合到界面上。中频的相移曲线（-φvs. E），即相移法，可以用作确定界面处Langmuir吸附等温线（θvs. E）的实验方法，而无论阴极H_2析出反应。在聚-Ir / 0.1 M H_2SO_4电解质界面上，由于高H +浓度，未观察到UPDH。 OPD H的平衡常数（K）和标准自由能（ΔG_（ads）分别为2.0 X 10〜（-4）和21.1 kJ / mol，UPD H和OPD H的判据为H吸附位点和过程而不是H_2的放出反应聚Ir表面的UPD H和OPD H是两个可区分的电吸附H物种。

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