Electrocatalytic Oxidation of Hydroxylamine on Glassy Carbon Electrodes Modified by Hybrid Copper-Cobalt Hexacyanoferrate Films

Abstract

Transition metal hexacyanoferrates (MHCFs) are one type of inorganic polymers and have been widely used in electrochemistry to electrocatalyze the oxidation of dopamine, 1 ascorbic acid, 2 hydroquinone, 2 NADH, 3 glutathione, 4,5 cysteine, 5 H2O2 6 and the reduction of Fe 3+ , 7 CO2, 8 H2O2. 9-11When combined with glucose oxidase, MHCF modified electrodes can also be applied as biosensors for glucose. [12][13][14] Hybrid metal hexacyanoferrates (M1M2HCFs) refer to those hexacyanoferrates in which the nitrogen atom in the cyano moiety coordinates to two different metal ions: M1 and M2. It can be regarded that a part of the lattice sites, which should be occupied by M1 in the absence of M2, are substituted by M2 when M2 also exists in the preparation solution. Although several papers on M1M2HCFs have been reported, 15-17 the number of papers about M1M2HCFs was far fewer than the number about single component MHCF. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] To our best knowledge, no paper on electrocatalytical properties of M1M2HCF-modified electrodes has been published.In our recent papers, [18][19][20] hybrid copper-cobalt hexacyanoferrate (CuCoHCF) films were electrodeposited on a substrate electrode and characterized by electrochemistry, XRD, ICP-AES and XPS. The results indicated that CuCoHCF was a substitution-type hybrid hexacyanoferrate in which the cyano moiety with its C atom coordinating to Fe(II), and N atom coordinating to Cu(II) or Co(II), formed the edge of a cubic lattice. Fe(II) occupied a part of the lattice sites and the remaining lattice sites were taken by Cu(II) and Co(II). Electrochemistry showed that CuCoHCF had excellent electrochemical reversibility and stability over a wide pH range of 4 -10. Comparative voltammetric studies showed different electrochemical properties from that of single component CoHCF and CuHCF. CuCoHCF film-modified electrode exhibited obvious electrocatalysis for both reduction and oxidation of hydrogen peroxide and the oxidation of NO2 -.Hydroxylamine, a derivative of ammonium, is known as a kind of reducing agent widely used in industry and pharmacy. It is one of the intermediate products of nitrogen-cycle and plays an important role in life science. For example, hydroxylamine is a well-known mutagen, which induces highly specific mutations with the nucleic acid cytosine, and is a moderately toxic substance that has been known to cause both reversible and irreversible physiological changes associated with methemoglobinemia. 21,22 Moreover, some hydroxylamine derivatives also constitute a great part of anticancer drugs. 23 Many methods have been developed for the determination of hydroxylamine because of its toxicity, biological functions and broad industrial utilizations. Kolasa has reviewed traditional methods. 24 More recently, electrochemical detection (ECD), 25,26 spectrophotometric, 27 chromatographic 28,29 methods and some combinations of them such as HPLC-ECD, 30 CE (capillary electrophoresis)-ECD 31 have been successfully applied to the determination of...

Recent Updates of Chemically Modified Electrodes in Analytical Chemistry

“…Structures of Dendrimers and b-Cyclodextrin of similar complexes is prepared by electrochemical methods for analytical applications [113]. For example, metal hexacayno-ferrate (MHCF, M Fe, Co, Ni and In) complexes for SO 3 2À and S 2 O 3 2À oxidation in the presence of various supporting electrolytes [114], CoHCF for hydrazine, NiHCF-NO complexes for AA [115 ± 117], NiHCF for thiopurine (as well as bovine albumin serum (BSA) interactions studies) [118], InHCF for NO oxidative detection [119], Nafion-coated InHCF for alkali metal ion and NH 4 [120], hybrid CoCuHCF for hydroxylamine [121] and oxalate oxidase (OxlOx)-coupled RuFeNiHCF for urinary oxalate [122] detections. In a similar way, CuPtX 6 (X Cl and Br) mixed valence compounds are also prepared simply by potential cycling of CuCl 2 and K 2 PtX 6 in KCl solution for oxidation studies of NO 2 À , AA, S 2 O 3 2À , NO and reduction reaction of H 2 O 2 [123,124].…”

Differential pulse voltammetric determination of hydroxylamine at an indenedione derivative electrodeposited on a multi-wall carbon nanotube modified glassy carbon electrode

“…Numerous methods have been developed for the determination of hydroxylamine. [10][11][12][13][14][15][16][17][18][19][20][21][22][23] For example, chromatographic, 10 spectrophotometric, [11][12][13] and electrochemical, [14][15][16][17][18][19][20][21][22][23] methods have been successfully applied to the determination of hydroxylamine. In this regard, we reported the preparation of a coumestan derivative modified carbon paste electrode, 19 and a rutin multi-wall carbon nanotubes modified glassy carbon electrode, 20 and their application in the electrocatalytic oxidation of hydroxylamine.…”

Electrocatalytic and voltammetric determination of sulfhydryl compounds through iron nitroprusside modified graphite paste electrode

“…[10][11][12][13][14][15] Metal nitroprusside films are not of easy preparation and 617 Electrocatalytic and Voltammetric Determination of Sulfhydryl Compounds Vol. 14, No.…”