1-Hydro-1,10-phenanthrolinium perchlorate and 1,10-Dihydro-1,10-phenanthrolinium Perchlorate in the Reaction of Electrocatalytic Production of Molecular Hydrogen

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Abstract

Using the cyclic voltammetry method, the electrochemical and electrocatalytic properties for hydrogen evolution reaction of the 1-hydro-1,10-phenanthrolinium perchlorate (I) and 1,10-dihydro-1,10-phenanthrolinium perchlorate (II) in the presence of CF3COOH were studied. The presence of hydrogen atoms at nitrogen in heterocyclic compounds has a significant effect on the electrochemical properties and the efficiency of the electrocatalytic process. The transition from 1-hydro-1,10-phenanthrolinium perchlorate (I) to 1,10-dihydro-1,10-phenanthrolinium perchlorate (II) leads to an increase in the efficiency of the process (higher TOF and TON values), despite identical mechanisms. The DFT method was used to study the mechanisms of the processes taking place and identify key intermediates.

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About the authors

A. D. Yudina

National Research Ogarev Mordovia State University

Author for correspondence.
Email: dolganov_sasha@mail.ru
ORCID iD: 0000-0002-1269-1609
Russian Federation, Bolshevistskaya st. 68, Saransk 430005

T. V. Boykova

National Research Ogarev Mordovia State University

Email: dolganov_sasha@mail.ru
Bolshevistskaya st. 68, Saransk 430005

O. Yu. Ganz

National Research Ogarev Mordovia State University

Email: dolganov_sasha@mail.ru
Russian Federation, Bolshevistskaya st. 68, Saransk 430005

L. A. Klimaeva

National Research Ogarev Mordovia State University

Email: dolganov_sasha@mail.ru
ORCID iD: 0000-0003-3050-4720
Russian Federation, Bolshevistskaya st. 68, Saransk 430005

Yu. V. Ulyakina

National Research Ogarev Mordovia State University

Email: dolganov_sasha@mail.ru
Russian Federation, Bolshevistskaya st. 68, Saransk 430005

A. A. Burmistrova

National Research Ogarev Mordovia State University

Email: dolganov_sasha@mail.ru
Russian Federation, Bolshevistskaya st. 68, Saransk 430005

T. O. Karpunina

National Research Ogarev Mordovia State University

Email: dolganov_sasha@mail.ru
Russian Federation, Bolshevistskaya st. 68, Saransk 430005

E. V. Okina

National Research Ogarev Mordovia State University

Email: dolganov_sasha@mail.ru
Russian Federation, Bolshevistskaya st. 68, Saransk 430005

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Supplementary files

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2. Fig. 1. Structural formulas of compounds 1a, 1b, 1c

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3. Fig. 2. Cyclic voltammogram of compounds 1b (a) and 1c (b); C = 1 mM, glassy carbon electrode (GC), 100 mV/s, CH3CN, 0.1 M Bu4NBF4, Ag/AgCl/KClaq

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4. Fig. 3. Cyclic voltammogram of 1 mM compounds 1b (a) and 1c (b), deaerated with argon, at 1–10 mM equivalents of CF3COOH, scan rate 100 mV/s; 0.1 M solution of (n-С4H9)4NBF4 in CH3CN was used as a background electrolyte, the working electrode was glassy carbon (S = 0.0314 cm2), the reference electrode was a standard silver chloride electrode (E0 = 0.33 V (CH3CN) in contrast to Fc/Fc+)

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5. Fig. 4. Energy diagram of the reaction of formation of molecular hydrogen in the presence of compound 1b and H+

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6. Scheme 1. Manifestation of the synergistic effect of the reaction of obtaining molecular hydrogen in the presence of 1,10-phenanthroline

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7. Scheme 2. Cation–radical redox transition in compounds 1b and 1c

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8. Scheme 3. Mechanism of formation of molecular hydrogen in the presence of compounds 1b, 1c and CF3COOH at potentials E = –0.80 V

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9. Figure from Contents

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