Integrated Study of the Thiocyanate Anion Electrooxidation by Electroanalytical and Computational Methods

Integrated Study of the Thiocyanate Anion Electrooxidation by Electroanalytical and Computational Methods Научная публикация

Журнал

Journal of The Electrochemical Society
ISSN: 0013-4651 , E-ISSN: 1945-7111

Вых. Данные

Год: 2021, Том: 168, Номер: 12, Номер статьи : 125501, Страниц : DOI: 10.1149/1945-7111/ac39d4

Авторы

Mendkovich Andrey ¹ , Kozyrev Yuriy ¹ , Kokorekin Vladimir ^1,2 , Luzhkov Victor ^3,4 , Rusakov Alexander ⁵

Организации

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia
2	Sechenov First Moscow State Medical University (Sechenov University), 119991 Moscow, Russia
3	Department of Fundamental Physico-Chemical Engineering, Lomonosov Moscow State University, Moscow 119991, Russia
4	Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, Russia
5	P. G. Demidov Yaroslavl State University, 150000 Yaroslavl, Russia

The mechanism of the electrochemical oxidation of thiocyanate anion in acetonitrile was studied by cyclic voltammetry, chronoamperometry, electrolysis, digital simulations and quantum chemical calculations. The experimental data indicated complex character of the reaction mechanism, which includes reactions of thiocyanate anion with the products of its oxidation, thiocyanate radical and thiocyanogen. It was proposed that the last reaction takes place in the reduction of thiocyanogen as well. The DFT PCM-SMD M06–2X/aug-CC-pVQZ calculations show that the reaction of thiocyanate anion with thiocyanate radical and disproportionation of thiocyanogen anion radical are thermodynamically favorable. The effects of the mentioned reactions on the shape of the curves of cyclic voltammetry and chronoamperometry as well as that of the mass transfer regime are discussed.

Mendkovich A. , Kozyrev Y. , Kokorekin V. , Luzhkov V. , Rusakov A.
Integrated Study of the Thiocyanate Anion Electrooxidation by Electroanalytical and Computational Methods
Journal of The Electrochemical Society. 2021. V.168. N12. 125501 . DOI: 10.1149/1945-7111/ac39d4 WOS Scopus OpenAlex

Web of science:	WOS:000725857300001
Scopus:	2-s2.0-85121770539
OpenAlex:	W3211681903

БД	Цитирований
OpenAlex	7
Scopus	7
Web of science	7