铁氰化钆修饰电极的固态电化学及电催化性能

制备了一种新的稀土铁氰化物——铁氰化钆(GdHCF), 并对其进行了表征. 元素分析、EDX和TGA结果表明, GdHCF的计量式为NaGdFe(CN)6•12H2O(在NaCl溶液中制备), 红外光谱结果显示GdHCF晶体中有两种形式的水分子存在, 一种是靠氢键结合的填隙水分子(5个), 一种是与Gd配位的配位水分子(7个)；XPS结果表明GdHCF中铁为+2价, 钆为+3价. 将GdHCF固定到石墨(SG)电极上(GdHCF/SG), 研究了它的固态电化学性能, 其循环伏安曲线上表现出一对良好且稳定的氧化还原峰, 式量电位E0′几乎不随扫速而变化(在10~300 mV•s−1范围内, E0′平均值为(197±3) mV)；并且E0′与支持电解质中阳离子(Na+)活度的对数(lgaNa+)之间呈线性关系, 斜率为54.1 mV, 这一特性关系可用于测定NaCl溶液中Na+的活度. 进一步研究的结果表明, GdHCF对神经递质多巴胺(DA)和抗坏血酸(AA)的电化学氧化均具有催化作用, 催化电流随DA(或AA)浓度的增加而增加.

Solid-state Electrochemistry of Gadolinium Hexacyanoferrate Modified Electrode and Its Electrocatalytic Property

A new electroactive polynuclear inorganic compound of rare earth metal, gadolinium hexacyanoferrate (GdHCF), was prepared and characterized using the techniques of FTIR spectroscopy, thermogravimetric analysis (TGA), UV-Vis spectrometry, X-ray photoelectron spectroscopy (XPS), ICP atomic emission spectoscopy, and EDX. The results of ICP atomic emission spectroscopy, EDX, and TGA indicated that the prepared GdHCF sample had a stoichiometry of NaGdFe(CN)6•12H2O (when GdHCF was prepared in NaCl solution). The FTIR spectrum of GdHCF showed that there were two types of water molecules in the structure of GdHCF: one was the interstitial water (5 H2O), which resulted from the association of water due to H-bonding, and the other was water coordinated with Gd (7 H2O). The results obtained using XPS showed that the oxidation state of Fe and Gd in the GdHCF sample was +2 and +3, respectively. GdHCF was immobilized on the surface of spectroscopically pure graphite (SG) electrode forming the GdHCF/SG electrode, and the solid-state electrochemistry of the resultant electrode was studied using cyclic voltammetry. The cyclic voltammetric results indicated that the GdHCF/SG electrode exhibited a pair of welldefined and stable redox peaks with the formal potential of E0′=(197±3) mV. The effects of the concentration of the supporting electrolyte on the electrochemical characteristics of GdHCF were studied, and the results showed that the value of E0′ increased linearly with the activity of the cationic ion of the supporting electrolyte (lgaNa+), with a slope of 54.1 mV, which may become a novel method for determining the activity of Na+ in solution. Further experimental results indicated that GdHCF had electrocatalytic activities toward the oxidation of dopamine (DA), and ascorbic acid (AA), and the electro- catalytic current increased linearly with the concentration of DA (or AA) in the range of 1.0~10.0 mmol•L−1 (for DA) or 0.5~20.0 mmol•L−1 (for AA).