1,3-Dimethyl-2-phenyl-1Н-benzo[d]imidazolium Iodide—A Representative of a New Class in the Family of Metal-Free Organic Catalysts: Electrochemical Properties and Electrocatalytic Activity in the Reaction of Formation of Molecular Hydrogen

A. V. Dolganov; Долганов А. В.; L. A. Klimaeva; Климаева Л. А.; S. G. Kostryukov; Кострюков С. Г.; D. V. Chugunov; Чугунов Д. Б.; A. D. Yudina; Юдина А. Д.; A. Sh. Kozlov; Козлов А. Ш.; A. S. Zagorodnova; Загороднова А. С.; A. V. Tankova; Танкова А. В.; V. O. Zhirnova; Жирнова В. О.; O. V. Tarasova; Тарасова О. В.; A. V. Knyazev; Князев А. В.

doi:10.31857/S0044453723090042

1,3-Dimethyl-2-phenyl-1Н-benzo[d]imidazolium Iodide—A Representative of a New Class in the Family of Metal-Free Organic Catalysts: Electrochemical Properties and Electrocatalytic Activity in the Reaction of Formation of Molecular Hydrogen

Authors: Dolganov A.V.¹, Klimaeva L.A.¹, Kostryukov S.G.¹, Chugunov D.V.¹, Yudina A.D.¹, Kozlov A.S.¹, Zagorodnova A.S.¹, Tankova A.V.¹, Zhirnova V.O.¹, Tarasova O.V.¹, Knyazev A.V.¹
Affiliations:
1. Ogarev National Research Mordovia State University
Issue: Vol 97, No 9 (2023)
Pages: 1362-1368
Section: ELECTROCHEMISTRY. GENERATION AND STORAGE OF ENERGY FROM RENEWABLE SOURCES
Submitted: 26.02.2025
Published: 01.09.2023
URL: https://rjeid.com/0044-4537/article/view/668668
DOI: https://doi.org/10.31857/S0044453723090042
EDN: https://elibrary.ru/XJKECC
ID: 668668

Cite item

Full Text

Open Access
Restricted Access

Access granted
Restricted Access

Subscription or Fee Access

Abstract
About the authors
References
Supplementary files
Statistics

Abstract

The electrochemical properties and electrocatalytic activity of 1,3-dimethyl-2-phenyl-1H-benzo[d]imidazolium-3 iodide (I), a representative of a new class of organic metal-free electrocatalysts, in the reaction of formation of molecular hydrogen, in the presence of acids of various strengths (methanesulfonic acid (CH3SO3H), perchloric acid (HClO4), and trifluoroacetic acid (CF3COOH)) have been studied. It is shown that the efficiency of the electrocatalytic process strongly depends on pKa of the acids used. Using gas chromatography and preparative electrolysis at half-wave potentials, it was shown that molecular hydrogen formed with high Faraday yields in all cases. The behavior of the catalytic wave on the cyclic voltammogram (CV), at various ratios of acid and catalyst concentrations in the presence of all acids is typical for the process proceeding according to a homogeneous mechanism. The mechanism of the process was studied by the density functional method (DFT), and its main intermediates were identified. The protonation of electrochemically generated radicals at the C-2 carbon atom of compound I, with the formation of a C-protonated radical cation, was shown to be the key stage of the electrocatalytic hydrogen evolution reaction (HER).

Keywords

molecular hydrogen, metal-free catalysts, benzimidazole

References

Turner J.A. // Science. 2004. V. 305. P. 972.https://doi.org/10.1126/science.1103197
Chisholm G., Zhao T., Cronin L. // Elsevier. 2022. P. 559.https://doi.org/10.1016/B978-0-12-824510-1.00015-5
Armaroli N., Balzani V. // ChemSusChem. 2011. V. 4. P. 21.
Hosseini S.R., Ghasemi S., Ghasemi S.A. // ChemistrySelect. 2019. V. 4. № 23. P. 6854–6861. https://doi.org/10.1002/slct.201901419
Belhadj H., Messaoudi Y., Khelladi M.R. et al. // Intern. J. of Hydrogen Energy. 2022. V. 47. № 46. P. 20129.https://doi.org/10.1016/j.ijhydene.2022.04.151
Gao X., Deng H., Dai Q. et al. // Catalysts. 2021. V. 12. № 1. P. 2. https://doi.org/10.3390/catal12010002
Das M., Khan Z.B., Biswas A. et al. // Inorg. Chem. 2022. V. 61. № 45. P. 18253. https://doi.org/10.1021/acs.inorgchem.2c03074
Zhao Y., Zhang J., Zhang W. et al // Intern. J. of Hydrogen Energy. 2021. V. 46. № 72. P. 35550. https://doi.org/10.1016/j.ijhydene.2021.03.085
Sun H., Xu X., Song Y. et al. // Adv. Funct. Mater. 2021. V. 31. № 16. P. 2009779. https://doi.org/10.1002/adfm.202009779
Mairanovskii S.G. // Russian Chemical Reviews 1991. V. 60. P. 1085. https://doi.org/10.1070/RC1991v060n10ABEH001131
Dolganov A.V., Tarasova O.V., Ivleva A.Y. et al. // Intern. J. of Hydrogen Energy. 2017. V. 42. № 44. P. 27084. https://doi.org/10.1016/j.ijhydene.2017.09.080
Dolganov A.V., Tarasova O.V., Moiseeva D.N. et al // Intern. J. of Hydrogen Energy. 2016. V. 41. № 22. P. 9312. https://doi.org/10.1016/j.ijhydene.2016.03.131
Dolganov A.V., Balandina A.V., Chugunov D.B. et al. // Russ. J. Gen. Chem. 2020. V. 90. № 7. P. 1229.https://doi.org/10.1134/S1070363220070099
Dolganov A.V., Tanaseichuk B.S., Pryanichnikova M.K. et al. // J. Phys. Org. Chem. 2019. V. 32. № 5. e3930.https://doi.org/10.1002/poc.3930
Dolganov A.V., Muryumin E.E., Chernyaeva O.Y. et al. // Materials Chemistry and Physics. 2019. V. 224. P. 148.https://doi.org/10.1016/j.matchemphys.2018.12.006
Dolganov A.V., Tanaseichuk, B.S., Tsebulaeva Y.V. et al. // Int. J. Electrochem. Sci. 2016. P. 9559.https://doi.org/10.20964/2016.11.24
Dolganov A.V., Tarasova O.V., Balandina A.V. et al. // Russ. J. Org. Chem. 2019. V. 55. № 7. P. 938.https://doi.org/10.1134/S1070428019070030
Dolganov A.V., Tanaseichuk B.S., Yurova V.Yu et al. // Intern. J. of Hydrogen Energy 2019. V. 44. № 39. P. 21495.https://doi.org/10.1016/j.ijhydene.2019.06.067
Dolganov A.V., Tanaseichuk B.S., Moiseeva D.N. et al. // Electrochem. Commun. 2016. V. 68. P. 59.https://doi.org/10.1016/j.elecom.2016.04.015
Dolganov A.V., Chernyaeva O.Y., Kostryukov S.G. et al. // Intern. J. of Hydrogen Energy. 2020. V. 45. № 1. P. 501.https://doi.org/10.1016/j.ijhydene.2019.10.175
Dolganov A.V., Tanaseichuk B.S., Tarasova O.V. et al. // Russ. J. Electrochem.2019. V. 55. № 8. P. 807.https://doi.org/10.1134/S1023193519080056
Ganz O.Yu., Klimaeva L.A., Chugunov D.B. et al. // Russ. J. Phys. Chem. 2022. V. 96. № 5. P. 954.https://doi.org/10.1134/S0036024422050120
Zhu X.-Q., Zhang M.-T., Yu A. et al. // J. Am. Chem. Soc. 2008. V. 13. № 8. P. 2501.https://doi.org/10.1021/ja075523m
Stephens P.J., Devlin F.J., Chabalowski C.F. et al. // J. Phys. Chem. 1994. V. 98. № 45. P. 11623. https://doi.org/10.1021/j100096a001
Ditchfield R., Hehre W.J., Pople J.A. // The J. of Chem. Physics 1971. V. 54. № 2. P. 724. https://doi.org/10.1063/1.1674902
Schmidt M.W., Baldridge K.K., Boatz J.A. et al. // J. Comput. Chem. 1993. V. 14. № 11. P. 1347. https://doi.org/10.1002/jcc.540141112
Felton G.A.N., Glass R.S., Lichtenberger D.L. et al. // Inorg. Chem. 2006. V. 45. № 23. P. 9181. https://doi.org/10.1021/ic060984e
Savéant J.-M. // ACS Catal. 2018. V. 8. № 8. P. 7608.https://doi.org/10.1021/acscatal.8b02007
Savéant J.-M. // Chem. Rev. 2008. V. 108. № 7. P. 2348.https://doi.org/10.1021/cr068079z
Saveant J.-M. // ChemElectroChem. 2016. V. 3. № 12. P. 1967.https://doi.org/10.1002/celc.201600430