Effects of alkali metal cations on oxygen reduction on N-containing carbons viewed as the interplay between capacitive and electrocatalytic properties:Experiment and theory

Igor A. Pašti, Ana S. Dobrota, Nemanja M Gavrilov, Gordana Ćirić-Marjanović, Slavko Mentus


The development of new electrocatalysts for oxygen reduction reaction (ORR) is crucial for sustainable energy economy. Both fundamental understanding of surface processes under operating conditions and suitable ORR activity measurements are necessary to select the best electrocatalyst candidate. To contribute to this matter, in the present study, we show that both the nature of alkali metal cations (Li+, Na+ and K+), composing supporting aqueous hydroxide solution, as well as the potential sweep rate in rotating disk electrode voltammetry measurements, influence the results of measurements of ORR activities of N-containing nanocarbons. Based on Density Functional Theory calculations, we conclude that specific interactions of hydrated cations with oxygen functional groups are responsible for such behavior, leading to a close interplay between the electrode double layer charging and the parallel Faradaic process on carbon surface. From a practical point of view, the presented results indicate that it is necessary to standardize carefully the ORR measurements on different carbon materials.


carbon electrocatalyst; ORR activity measurements; catalyst selectivity; double layer capacitance

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M. Winter, R. J. Brodd, Chem. Rev. 104 (2004) 4245 (https://doi.org/10.1021/cr020730k)

N. M. Markovic, P. N. Ross, Surf. Sci. Rep. 45 (2002) 117 (https://doi.org/10.1016/S0167-5729(01)00022-X)

K. Gong, F. Du, Z. Xia, M. Durstock, L. Dai, Science 323 (2009) 760 (https://doi.org/10.1126/science.1168049)

I. A. Pašti, A. J. Ležaić, N. M. Gavrilov, G. Ćirić-Marjanović, S. V. Mentus, Synth. Met. 246 (2018) 267 (https://doi.org/10.1016/j.synthmet.2018.11.003)

I. A Pašti, N. M. Gavrilov, A. S. Dobrota, M. Momčilović, M. Stojmenović, A. Topalov, D. M. Stanković, B. Babić, G. Ćirić-Marjanović, S. V. Mentus, Electrocatal. 6 (2015) 498 (https://doi.org/10.1007/s12678-015-0271-0)

G. Chen, M. Li, K. A. Kuttiyiel, K. Sasaki, F. Kong, C. Du, Y. Gao, G. Yin, R. R. Adzic, Electrocatal. 7 (2016) 305 (https://doi.org/10.1007/s12678-016-0309-y)

V. R. Stamenkovic, B. Fowler, B. S. Mun, G. Wang, P. N. Ross, C. A. Lucas, N. M. Marković, Science 315 (2007) 493 (http://doi.org/10.1126/science.1135941)

I. A. Pasti, N. M. Gavrilov, S. V. Mentus, Int. J. Electrochem. Sci. 7 (2012) 11076 (http://www.electrochemsci.org/papers/vol7/71111076.pdf)

N. Hodnik, C. Baldizzone, S. Cherevko, A. Zeradjanin, K. J. J. Mayrhofer, Electrocatal. 6 (2015) 237 (https://doi.org/10.1007/s12678-015-0255-0)

S Mentus, I Pasti, IPSI BgD Trans. Adv. Res. 16 (2013) (http://ipsitransactions.org/journals/papers/tar/2013jan/p4.pdf)

S. S. Kocha, K. Shinozaki, J. W. Zack, D. J. Myers, N. N. Kariuki, T. Nowicki, V. Stamenkovic, Y. Kang, D. Li, D. Papageorgopoulos, Electrocatal. 8 (2017) 366 (https://doi.org/10.1007/s12678-017-0378-6)

A. N. Frumkin, Z. Physik. Chem. A164 (1933) 121

D. Strmcnik, K. Kodama, D. van der Vliet, J. Greeley, V. R. Stamenkovic, N. M. Marković, Nature Chem. 1 (2009) 466 (https://doi.org/10.1038/nchem.330)

B. Garlyyev, S. Xue, M. D. Pohl, D. Reinisch, A. S. Bandarenka, ACS Omega 3 (2018) 15325 (https://doi.org/10.1021/acsomega.8b00298)

S. Xue, B. Garlyyev, S. Watzele, Y. Liang, J. Fichtner, M. D. Pohl, A. S. Bandarenka, ChemElectroChem 5 (2018) 2326 (https://doi.org/10.1002/celc.201800690)

D. Karačić, S. Korać, A. S. Dobrota, I. A. Pašti, N. V. Skorodumova, S. J. Gutić, Electrochim. Acta 297 (2019) 112 (https://doi.org/10.1016/j.electacta.2018.11.173)

N. Gavrilov, I. A. Pašti, M. Mitrić, J. Travas-Sejdić, G. Ćirić-Marjanović, S. V. Mentus, J. Power Sources 220 (2012) 306 (https://doi.org/10.1016/j.jpowsour.2012.07.119)

N. Gavrilov, I. A. Pašti, M. Vujković, J. Travas-Sejdic, G. Ćirić-Marjanović, S. V. Mentus, Carbon 50 (2012) 3915 (https://doi.org/10.1016/j.carbon.2012.04.045)

J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865 (https://doi.org/10.1103/PhysRevLett.77.3865)

P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G.L. Chiarotti, M. Cococcioni, I. Dabo, A.D. Corso, S. Fabris, G. Fratesi, S. de Gironcoli, R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri, L. Martin-Samos, N. Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto, C. Sbraccia, S. Scandolo, G. Sclauzero, A.P. Seitsonen, A. Smogunov, P. Umari, R.M. Wentzcovitch, J. Phys.: Condens. Matter 21 (39) (2009) 395502 (http://dx.doi.org/10.1088/0953-8984/21/39/395502)

A.S. Dobrota, I.A. Pašti, S. V. Mentus, N. V. Skorodumova, Phys. Chem. Chem. Phys. 19 (2017) 8530 (https://doi.org/10.1039/c7cp00344g)

N. P. Diklić, A. S. Dobrota, I. A. Pašti, S. V. Mentus, B. Johansson, N. V. Skorodumova, Electrochim. Acta 297 (2019) 523 (https://doi.org/10.1016/j.electacta.2018.11.108)

H.J. Monkhorst, J.D. Pack, Phys. Rew. B 13 (1976) 5188 (https://doi.org/10.1103/PhysRevB.13.5188)

S. Grimme, J Comput. Chem. 27 (2006) 1787 (https://doi.org/10.1002/jcc.20495)

A.S. Dobrota, S. Gutić, A. Kalijadis, M. Baljozović, S. V. Mentus, N. V. Skorodumova, I.A. Pašti, RSC Adv. 6 (2016) 57910 (http://dx.doi.org/10.1039/C6RA13509A)

A.J. Bard, L.R. Faulkner, Electrochemical Methods Fundamentals and Applications, 2nd ed., John Wiley & Sons, Inc, 2001.

D. W. H. Rankin, CRC handbook of chemistry and physics, 89th edition, Ed. David R. Lide, Taylor & Francis, 2008.

R. E. Davis, G. L. Horvath, C. W. Tobias, Electrochim. Acta. 12 (1967) 287 (https://doi.org/10.1016/0013-4686(67)80007-0)

G. Ćirić-Marjanović, I. Pašti, S. Mentus, Progress Mater. Sci. 69 (2015) 61 (https://doi.org/10.1016/j.pmatsci.2014.08.002)

D. Hulicova, M. Kodama, H. Hatori, Chem. Mater. 18 (2006) 2318 (https://doi.org/10.1021/cm060146i)

DOI: https://doi.org/10.2298/JSC190426072P

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