Cd|KOH|NiOOH

Zn|NH4CI|MnO2

Li|LiClO4|MnO2

Pb|H2SO4|PbO2

H2|KOH|O2

Electrooxidation Kinetics of Formic Acid on Anodically Modified Silver-palladium Alloys

This is an open access article distributed under the terms of Creative Commons Attribution 4.0 International License (CC-BY 4.0).

DOI: https://doi.org/10.18500/1608-4039-2018-18-3-141-154

The electrocatalytic activity of electrode materials synthesized by anodic selective dissolution of Ag–Pd alloys based on silver (4 and 8 at. % Pd) was studied. The kinetic laws of the electrooxidation of formic acid on compact palladium and anodically modified Ag,Pd-alloys in an acidic sulphate solution have been established. The conditions for anodic oxidation of formic acid on Pd and Ag,Pd-alloys were determined depending on the composition of the electrode system and the mode of the preliminary electrochemical modification of the alloy with the use of non-stationary electrochemical measurements. The effect of the electrode surface development in the kinetics of formic acid anodic destruction is revealed.

Literature

1. Rice C., Ha S., Masel R. I., Waszczuk P., Wieckowski A., Barnard T. Direct formic acid fuel cells. J. Power Sources, 2002, vol. 111, pp. 83–89.

2. Carrette L., Friedrich K. A., Stimming U. Fuel cells – fundamentals and applications. Fuel cells, 2001, vol. 1, no. 1, pp. 5–39.

3. Yu X., Pickup P. G. Recent advances in direct formic acid fuel cells (DFAFC). J. Power Sources, 2008, vol. 182, pp. 124–132.

4. Lesiak B., Mazurkiewicz M., Malolepszy A., Stobinski L., Mierzwa B., Mikolajczuk-Zychora A., Juchniewicz K., Borodzinski A., Zemek J., Jiricek P. Effect of the Pd/MWCNTs anode catalysts preparation methods on their morphology and activity in a direct formic acid fuel cell. Applied Surface Science, 2016, vol. 387, pp. 929–937.

5. Bieloshapka I., Jiricek P., Vorokhta M., Tomsik E., Rednyk A., Perekrestov R., Jurek K., Ukraintsev E., Hruska K., Romanyuk O., Lesiak B. Pd-catalysts for DFAFC prepared by magnetron sputtering. Applied Surface Science, 2017, vol. 419, pp. 838–846.

6. Rice C. A., Wieckowski A. Electrocatalysis of Formic Acid Oxidation. In: Shao M. (ed.) Electrocatalysis in Fuel Cells. Lecture Notes in Energy, London, Springer, 2013, vol 9, pp. 43–67.

7. Jiang K., Zhang H.-X., Zou S., Cai W. B. Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications. Phys. Chem. Chem. Phys., 2014, vol. 16, pp. 20360–20376.

8. Marshakov I. K., Vvedensky A. V., Kondrashin V. Yu., Bokov G. A. Anodnoye rastvoreniye i selektivnaya korroziya splavov [Anodic dissolution and selective corrosion of alloys]. Voronezh, Izd-vo Voronezh. un-ta, 1988. 208 p. (in Russian).

9. Kaiser H. Untersuchungen rum umwandlungsverhalten von InSn-legierungen bei selektiver korrosion. Werkst. Korros., 1989, Bd. 40, S. 1–6.

10. Rambert S., Landolt D. Anodic dissolution single phase alloys. I. Surface composition changes on AgPd studied by Auger Electron spectroscopy. Electrochim. Acta, 1986, vol. 31, pp. 1421–1431.

11. Rambert S., Landolt D. Anodic dissoluton of binary single phase alloys. II. Behavior of CuPd, NiPd and AgAu in LiCl. Electrochim. Acta, 1986, vol. 31, pp. 1433–1441.

12. Gniewek J., Pezy J., Baker B. G., Bockris J. O’M. The effect of noble metal additions upon the corrosion of copper: an Auger-Spectroscopic study. J. Electrochem. Soc., 1978, vol. 125, pp. 17–23.

13. Pickering H. W., Wagner C. Electrolytic dissolution of binary alloys containing a noble metal. J. Electrochem. Soc., 1967, vol. 114, iss. 7, pp. 698–706.

14. Tamman G. Die chemischen und galvanischen Eigenschaften von mischkristallreihen und ihre Atom-Verteilung. Z. Anorg. Chem., 1919, Bd. 107, no. 1, S. 289–308.

15. Tamman G., Brauns E. Behaviour of gold and ist alloys with silver and copper toward nitric and sulphuric acid. Z. Anorg. Chem., 1931, Bd. 200, no. 1, S. 209–231.

16. Zartsyn I. D., Vvedensky A. V., Marshakov I. K. O neravnovesnosti poverkhnostnogo sloya pri anodnom rastvorenii gomogennykh splavov [On the nonequilibrium of the surface layer during the anodic dissolution of homogeneous alloys]. Elektrokhimiya [Russ. J. Electrochemistry], 1994, vol. 30, no. 4, pp. 544–565 (in Russian).

17. Pickering H. W., Byrne P. J. On preferential anodic dissolution of alloys in the low-current region and the nature of the critical potential. J. Electrochem. Soc., 1971, vol. 118, pp. 209–216.

18. Sieradzki K., Dimitrov N., Movrin D., McCall C., Vasiljevic N., Erlebacher J. The dealloying critical potential. J. Electrochem. Soc., 2002, vol. 149, pp. B370–B377.

19. Zartsyn I. D., Vvedensky A. V., Marshakov I. K. O prevrashcheniyakh blagorodnoy komponenty pri selektivnom rastvorenii gomogennogo splava v aktivnom sostoyanii [On the transformations of the noble component during the selective dissolution of a homogeneous alloy in the active state]. Zashchita metallov [Protection of metall], 1991, vol. 27, no. 1, pp. 3–12 (in Russian).

20. Zartsyn I. D., Vvedensky A. V., Marshakov I. K. Termodinamika neravnovesnykh fazovykh prevrashcheny pri selektivnom rastvorenii gomogennykh binarnykh splavov [Thermodynamics of non-equilibrium phase transformations during the selective dissolution of homogeneous binary alloys]. Zashchita metallov [Protection of metall], 1991, vol. 27, no. 6, pp. 883–891 (in Russian).

21. Landolt D. Contributions of surface analysis to corrosion science: Selective dissolution and oxidation phenomena in alloy corrosion. Surf. Interf. Anal., 1990, vol. 15, no. 7, pp. 395–404.

22. Hansen M., Anderko K. P. Constitution of Binary Alloys. New York, McGraw-Hill, 1958. 1305 p.

23. Kozaderov O. A. Massoperenos, fazoobrazovaniye i morfologicheskaya nestabilnost poverkhnostnogo sloya pri selektivnom rastvorenii gomogennykh metallicheskikh splavov. Dis. dr. him. nauk [Mass transfer, phase formation and morphological instability of the surface layer during the selective dissolution of homogeneous metal alloys]. Diss. Dr. Sci. (Chem.). Voronezh, 2016. 361 p. (in Russian).

24. Kozaderov O. A., Dorokhov A. V., Vvedenskii A. V. Kinetics of phase transformations in the surface layer of a binary alloy upon selective dissolution. IV. Ag–Pd|Ag+ system. Protection of Metals and Physical Chemistry of Surfaces, 2012, vol. 48, no. 4, pp. 411–418.

25. Chung S.-Y., Uhm S.-H., Lee J.-K., Kang S.-J., Tak Y.-S., Lee J.-Y. Electrocatalytic oxidation of HCOOH on Pt-based anodes. J. Ind. Eng. Chem., 2007, vol. 13, no. 3, pp. 339–344.

26. Wang Y., Wu B., Gao Y., Tang Y., Lu T., Xing W., Liu C. Kinetic study of formic acid oxidation on carbon supported Pd electrocatalyst. J. Power Source, 2009, vol. 192, pp. 372–375.

27. Chen Y.-X., Ye S., Heinen M., Jusys Z., Osawa M., Behm R. J. Application of in-situ attenuated total reflection-fourier transform infrared spectroscopy for the understanding of complex reaction mechanism and kinetics: formic acid oxidation on a Pt film electrode at elevated temperatures. J. Phys. Chem., 2006, vol. 110, pp. 9534–9544.

28. Bulushev D. A., Beloshapkin S., Ross J. R. Hydrogen from formic acid decomposition over Pd and Au catalysts. Catalysis today, 2010, vol. 154, pp. 7–12.

29. Galus Z. Fundamentals of Electrochemical Analysis. New York, Ellis Horwood, 1976. 313 p.

30. MacDonald D. D. Transient techniques in electrochemistry. New York, London, Рlenum Press, 1977, pp. 329.

31. Bobrinskaya E. V., Vvedenskii A. V., Kartashova T. V., Kirilova L. A. Ustanovlenie osobennostej adsorbcii PAOV po harakteru izmeneniya bestokovogo potenciala vodorodnogo ehlektroda [Determination of the features of the adsorption of PAOV on the nature of changes in the current-free potential of the hydrogen electrode]. Vestnik Voronezhskogo gosudarstvennogo universiteta, Seriya: Himiya, Biologiya, Farmaciya, 2007, no. 1, pp. 7–16 (in Russian).

32. Kirilova L. A. Kinetika anodnogo okisleniya formal’degida na zolote i splavah Ag-Au, Cu-Au v shchelochnyh rastvorah. Dis. kand. him. nauk [Kinetics of anodic oxidation of formaldehyde on gold and Ag-Au, Cu-Au alloys in alkaline solutions]. Diss. Cand. Sci. (Chem.). Voronezh, 2007. 172 p. (in Russian).

Heading: 
Full Text (PDF):
(downloads: 1817)