Оksana HERTSYK1, Myroslava KOVBUZ1, Tetiana HULA1, Nataliia PANDIAK2
1Ivan Franko National University of Lviv Kyryla and Mefodia Str. 6, 79005 Lviv, Ukraine e-mail: o_hertsyk@yahoo.com
2 Ukrainian National Forestry University, Gen. Chuprynka Str. 103, 79057 Lviv, Ukraine
DOI: https://doi.org/10.37827/ntsh.chem.2020.60.118
ELECTROCATALYSIS INVOLVING AMORPHOUS METAL ELECTRODES
The effect of chemical composition of amorphous metal electrodes with different elemental composition (i.e. Al87.0Y5.0Ni8.0, Fe80.0Si6.0B14.0, Fe78,5Ni1.0Mo0.5Si6.0B14.0, Fe81,0Ni1.0Nb0.5Mo0.5Si3.0B14.0, Fe73,1Cu1.0Nb3.0Si15.5B7.4) on their electrocatalytic activity in the reactions of the decomposition of peroxide –O–O– bonds in hydrogen peroxide H2O2 and organic oligoperoxide compounds based on vinyl acetate, 2-tert-butyl peroxy-2-methyl-5-hexen-3-yne and maleic anhydride was studied. The electrochemical reduction of H2O2 and organic oligoperoxsde on AMA-electrodes by cyclic voltammetry is investigated. The dependencies of the rate of electrocatalytic processes on the concentration of supporting electrolyte, the rate of scanning of potential, the concentration of depolarizer and the duration of the initial spontaneous (in the absence of external potential) interaction of the peroxides compounds with the electrode surface were investigated. The rate constants of the decomposition of –O–O– bonds in peroxides of different structure were determined. In the case of the electrocatalytic AMA electrode Al87.0Y5.0Ni8.0, the process of dissociation of –O–O– bonding by the reductive mechanism is the most probable: H2O2 + e → OH– + OH∙ In the case of AMA electrodes based on Fe (especially Fe73,1Cu1.0Nb3.0Si15.5B7.4) the decomposition of –O–O– bonds follows preferential oxidation mechanism: H2O2 – e → OH– + OH∙ Due to their high absorption ability, oligoperoxide molecules can undergo conformational changes on the surface of the electrode. This affects the stability of the peroxide bond significantly. The functional groups of oligoperxides show affinity to localized electrons on the electrode surface. This leads to the elongation of the –O–O– bond and facilitates the fragmentation of the oligomers. The amorphous alloys Fe73,1Cu1.0Nb3.0Si15.5B7.4 and Fe81,0Ni1.0Nb0.5Mo0.5Si3.0B14.0 have a higher catalytical activity in decomposition of H2O2.
Keywords: amorphous metallic alloy, hydrogen peroxide, oligoperoxide, electrocatalytic activity.
References:
-
1. Boichyshyn L. M., Hertsyk O. M., Kovbuz M. O. Thermal modification of amorphous metal alloys: nanostructuring
and properties. – Mississauga, Ontario: Library and Archives Canada Cataloguing in Publication, Nova Printing
Inc., 2019. 138 р.
2. Seruga M., Hasenay D. Electochemical and surface properties of of aluminium in citric acid solutions. J. Appl.
Electroch. 2001. Vol. 31. P. 961–967. (https://doi.org/10.1023/A:1017556323508).
3. Sheng W., Zhouand Z., Ciao M. et al. Correlating hydrogen oxidation and evolution activity on platinum at
different pH with measured hydrogen binding energy. Nat. Commun. 2015. Vol. 6. P. 1–6.
(https://doi.org/10.1038/ncomms6848).
4. Durst J., Siebel H., Simon C. et al. New insights into the electrochemical hydrogen oxidation and evolution
reaction mechanism. Energy Environ. Sci. 2014. Vol. 7. P. 2255–2260. (https://doi.org/10.1039/c4ee00440j).
5. Schalenbach M., Zeradjanin A.R., Kassian O. et al. A perspective on Low-Temperature Water Electrolysis –
Challenges in Alkaline and Acidic Technology. Int. J. Electrochem. Sci. 2018. Vol. 13. P. 1173–1226.
(https://doi.org/10.20964/2018.02.26).
6. Kovbuz M.A., Hertsyk O.M., Boichyshyn L.M. Catalytically active electrodes in the redox processes of oligomeric
peroxides. Russ. J. Electrochem. 2011. Vol. 47(10). P. 1194–1198. (https://doi.org/10.1134/S1023193511100089).
7. Boichyshyn L., Danyliak M.-O., Kotur B. Surface structure and catalytic activity of amorphous metallic alloys
Fe–Nb–B–RE (RE =Y, Gd, Tb, Dy) in alkaline solution. Adsorpt. Sci. and Techn. 2017. Vol. 35(7–8). P. 623–629.
(https://doi.org/10.1177/0263617417703757).
8. Lu X., Xue H., Gong H. et al. 2D Layered Double Hydroxide Nanosheets and Their Derivatives Toward Efficient
Oxygen Evolution Reaction. Nano-Micro Lett. 2020. Vol. 12. P. 86–92. (https://doi.org/10.1007/s40820-020-00421-5).
9. Danyliak M.-O., Boichyshyn L. M., Pandiak N. L. Hydrogen evolution reaction on the oxidized surfaces of the
Fe-based amorphous alloys. Acta Phys. Pol. A. 2018. Vol. 133(4). P. 1103–1107.
(https://doi.org/10.12693/APhysPolA.133.1103).
10. Hertsyk O. M., Pereverzeva T. H., Boichyshyn L. M. et al. Influence of heat treatment and oligomeric coatings
on the corrosion resistance of amorphous alloys based on aluminium. Mat. Sci. 2019. Vol. 54(4). P. 526–534.
(https://doi.org/10.1007/s11003-019-00213-2).
11. Mariano N., Souza C., May J., Kuri S. Influence of Nb content on the corrosion resistance and saturation
magnetic density of FeCuNbSiB alloys. Mat. Sci. and Eng. 2003. Vol. 354(1–2). P. 1–5.
(https://doi.org/10.1016/S0921-5093(02)00032-1).
How to Cite
Hertsyk O., Kovbuz M., Hula T., Pandiak N. ELECTROCATALYSIS INVOLVING AMORPHOUS METAL ELECTRODES Proc. Shevchenko Sci. Soc. Chem. Sci. 2020 Vol. LX. P. 118-126.