Department of Chemistry, Faculty of Science, Cairo University, Egypt.
Anal Chim Acta. 2012 Jun 12;730:60-5. doi: 10.1016/j.aca.2011.10.070. Epub 2011 Nov 15.
Peracetic acid (PAA) has been selectively electroanalyzed in the presence of a large excess of hydrogen peroxide (H(2)O(2)), about 500 fold that of PAA, using Au (111)-like gold electrode in acetate buffer solutions of pH 5.4. Au(111)-like gold electrode was prepared by a controlled reductive desorption of a previously assembled thiol, typically cysteine, monolayer onto the polycrystalline gold (poly-Au) electrode. Cysteine molecules were selectively removed from the Au(111) facets of the poly-Au electrode, keeping the other two facets (i.e., Au(110) and Au(100)) under the protection of the adsorbed cysteine. It has been found that Au(111)-like gold electrode positively shifts the reduction peak of PAA, while, fortunately, shifts the reduction peak of H(2)O(2) negatively, achieving a large potential separation (around 750 mV) between the two reduction peaks as compared with that (around 450 mV) obtained at the poly-Au electrode. This large potential separation between the two reduction peaks enabled the analysis of PAA in the presence of a large excess of H(2)O(2). In addition, the positive shift of the reduction peak of PAA gives the present method a high immunity against the interference of the dissolved oxygen.
过氧乙酸(PAA)在大量过氧化氢(H₂O₂)存在下被选择性地进行电分析,H₂O₂的量约为 PAA 的 500 倍,使用的是在 pH 5.4 的乙酸缓冲溶液中的类金(111)金电极。类金(111)金电极是通过将先前组装的硫醇(典型的半胱氨酸)单层在多晶金(多-Au)电极上进行受控还原脱附来制备的。半胱氨酸分子从多-Au 电极的 Au(111)晶面中被选择性地去除,而其他两个晶面(即 Au(110)和 Au(100))则受到吸附的半胱氨酸的保护。研究发现,类金(111)金电极使 PAA 的还原峰正向移动,而 H₂O₂的还原峰则负向移动,与在多-Au 电极上获得的还原峰(约 450 mV)相比,实现了两个还原峰之间的大电势分离(约 750 mV)。这种两个还原峰之间的大电势分离使得在大量 H₂O₂存在下分析 PAA 成为可能。此外,PAA 还原峰的正向移动使本方法对溶解氧的干扰具有高抗干扰性。