Abstract
Three porous materials (Cu, a Cu-Ni alloy with 70 at.% Cu and Rh-modified Cu) have been tested as electrodes for the electroanalysis of nitrate and nitrite ions, in either neutral or basic media, using mainly a flow injection technique. Porous Cu and Cu-Ni were prepared by electrodeposition at high current density, exploiting the transient template action of hydrogen bubbles. Rh-modified Cu electrodes were obtained from porous Cu, through a galvanic displacement reaction. All materials had a linear response for both nitrates and nitrites, at concentrations up to 10−3 M, at least. Sensitivities, detection limits and stability were determined. Compared with Cu, used as a benchmark, (i) Rh-modified Cu had higher sensitivity for nitrates, comparable sensitivity for nitrites, lower or comparable detection limits and overall better stability; (ii) Cu-Ni had lower sensitivity, but exhibited lower detection limits and more stable performance for most analyte/medium combinations.
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Burakham R, Oshima M, Grudpan K, Motomizu S (2004) Simple flow-injection system for the simultaneous determination of nitrite and nitrate in water samples. Talanta 64:1259–1265
Gal C, Frenzel W, Möller J (2004) Re-examination of the cadmium reduction method and optimisation of conditions for the determination of nitrate by flow injection analysis. Microchim Acta 146:155–164
Kazemzadeh A, Ensafi AA (2001) Sequential flow injection spectrophotometric determination of nitrite and nitrate in various samples. Anal Chim Acta 442:319–326
Moorcroft MJ, Davis J, Compton RG (2001) Detection and determination of nitrate and nitrite: a review. Talanta 54:785–803
Milhano C, Pletcher D (2009) The electrochemistry and electrochemical technology of nitrate. In: White RE, Vayenas CG, Gamboa-Aldeco ME (ed) Modern aspects of electrochemistry. Vol. 45. Springer, Heidelberg. 1–61
Desai R, Villalba MM, Lawrence NS, Davis J (2009) Green approaches to field nitrate analysis: an electroanalytical perspective. Electroanalysis 21:789–796
Bodini ME, Sawyer DT (1977) Voltammetric determination of nitrate ion at parts-per-billion levels. Anal Chem 49:485–489
Fogg AG, Scullion SP, Edmonds TE, Birch BJ (1991) Direct reductive amperometric determination of nitrate at a copper electrode formed in situ in a capillary-fill sensor device. Analyst 116:573–579
Carpenter NG, Pletcher D (1995) Amperometric method for the determination of nitrate in water. Anal Chim Acta 317:287–293
Davis J, Moorcroft MJ, Compton RG, Wilkins SJ, Cardosi MF (2000) Electrochemical detection of nitrate and nitrite at a copper modified electrode. Analyst 125:737–742
Solak AO, Çekirdek P (2005) Square wave voltammetry determination of nitrate at freshly copper plated glassy carbon electrode. Anal Lett 38:271–280
Paixão TRLC, Cardoso JL, Bertotti M (2007) Determination of nitrate in mineral water and sausage samples by using a renewable in situ copper modified electrode. Talanta 71:186–191
Ning YF, Chen YP, Shen Y, Tang Y, Guo JS, Fang F, Liu SY (2013) Directly determining nitrate under wide pH range condition using a Cu-deposited Ti electrode. J Electrochem Soc 160:H715–H719
Moorcroft MJ, Nei L, Davis J, Compton RG (2000) Enhanced electrochemical detection of nitrite and nitrate at a Cu-30Ni alloy electrode. Anal Lett 33:3127–3137
Simpson BK, Johnson DC (2004) Electrocatalysis of nitrate reduction at copper-nickel alloy electrodes in acid media. Electroanalysis 16:532–538
Mattarozzi L, Cattarin S, Comisso N, Guerriero P, Musiani M, Vázquez-Gómez L, Verlato E (2013) Electrochemical reduction of nitrate and nitrite in alkaline media at Cu-Ni alloy electrodes. Electrochim Acta 89:488–496
Mattarozzi L, Cattarin S, Comisso N, Gerbasi R, Guerriero P, Musiani M, Vázquez-Gómez L, Verlato E (2013) Electrodeposition of Cu-Ni alloy electrodes with bimodal porosity and their use for nitrate reduction. ECS Lett 2:D58–D60
Mattarozzi L, Cattarin S, Comisso N, Gambirasi A, Guerriero P, Musiani M, Vázquez-Gómez L, Verlato E (2014) Hydrogen evolution assisted electrodeposition of porous Cu-Ni alloy electrodes and their use for nitrate reduction in alkali. Electrochim Acta 140:337–344
Shin HC, Dong J, Liu M (2003) Nanoporous structures prepared by an electrochemical deposition process. Adv Mater 15:1610–1614
Shin HC, Liu M (2004) Copper foam structures with highly porous nanostructured walls. Chem Mater 16:5460–5464
Kim JH, Kim RH, Kwon HS (2008) Preparation of copper foam with 3-dimensionally interconnected spherical pore network. Electrochem Commun 10:1148–1151
Nikolić ND, Popov KI (2010) Hydrogen co-deposition effects on the structure of electrodeposited copper. In: Djokić SS (ed) Modern aspects of electrochemistry. Vol 48. Springer, New York, pp. 1–70
Cherevko S, Chung CH (2011) Direct electrodeposition of nanoporous gold with controlled multimodal pore size distribution. Electrochem Commun 13:16–19
Nam DH, Kim RH, Han DW, Kim JH, Kwon HS (2011) Effects of (NH4)2SO4 and BTA on the nanostructure of copper foam prepared by electrodeposition. Electrochim Acta 56:9397–9405
Cherevko S, Xing X, Chung CH (2011) Hydrogen template assisted electrodeposition of sub-micrometer wires composing honeycomb-like porous Pb films. Appl Surf Sci 257:8054–8061
Plowman BJ, Lathe A, Jones LA, Bhargava SK (2015) Building with bubbles: the formation of high surface area honeycomb-like films via hydrogen bubble templated electrodeposition. Chem Commun 51:4331–4346
Shin HC, Liu M (2005) Three-dimensional porous copper–tin alloy electrodes for rechargeable lithium batteries. Adv Funct Mater 15:582–586
Cherevko S, Kulyk N, Chung CH (2012) Nanoporous Pt@AuxCu100–x by hydrogen evolution assisted electrodeposition of AuxCu100–x and galvanic replacement of Cu with Pt: electrocatalytic properties. Langmuir 28:3306–3315
Dima GE, de Vooys ACA, Koper MTM (2003) Electrocatalytic reduction of nitrate at low concentration on coinage and transition-metal electrodes in acid solutions. J Electroanal Chem 554-555:15–23
Comisso N, Cattarin S, Fiameni S, Gerbasi R, Mattarozzi L, Musiani M, Vázquez-Gómez L, Verlato E (2012) Electrodeposition of Cu-Rh alloys and their use as cathodes for nitrate reduction. Electrochem Commun 25:91–93
Janz GJ (1961) Silver-silver halide electrodes. In: Ives DJG, Janz J (eds) Reference electrodes. Academic Press, New York, pp. 179–230
Verlato E, Cattarin S, Comisso N, Mattarozzi L, Musiani M, Vázquez-Gómez L (2013) Reduction of nitrate ions at Rh-modified Ni foam electrodes. Electrocatalysis 4:203–211
Woods R (1976) Chemisorption at electrodes: hydrogen and oxygen on noble metals and their alloys. In: Bard AJ (ed) Electroanalytical Chemistry. Vol.9. Marcel Dekker, New York, pp. 1–162
Mattarozzi L, Cattarin S, Comisso N, Gerbasi R, Guerriero P, Musiani M, Vázquez-Gómez L, Verlato E (2015) Electrodeposition of compact and porous Cu-Zn alloy electrodes and their use in the cathodic reduction of nitrate. J Electrochem Soc 162:D236–D241
Vázquez-Gómez L, Cattarin S, Guerriero P, Musiani M (2008) Hydrogen evolution on porous Ni cathodes modified by spontaneous deposition of Ru or Ir. Electrochim Acta 53:8310–8318
Kear G, Barker BD, Walsh FC (2004) Electrochemical corrosion of unalloyed copper in chloride media—a critical review. Corros Sci 46:109–135
Rosca V, Duca M, de Groot MT, Koper MTM (2009) Nitrogen cycle electrocatalysis. Chem Rev 109:2209–2244
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Comisso, N., Cattarin, S., Guerriero, P. et al. Study of Cu, Cu-Ni and Rh-modified Cu porous layers as electrode materials for the electroanalysis of nitrate and nitrite ions. J Solid State Electrochem 20, 1139–1148 (2016). https://doi.org/10.1007/s10008-015-2915-7
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DOI: https://doi.org/10.1007/s10008-015-2915-7