Tetrazole-Substituted isomeric ruthenium polypyridyl complexes for low overpotential electrocatalytic CO2 reduction

Giri, Bishnubasu and Mahata, Arup and Kella, Tatinaidu and Shee, Debaprasad and De Angelis, Filippo and Maji, Somnath (2022) Tetrazole-Substituted isomeric ruthenium polypyridyl complexes for low overpotential electrocatalytic CO2 reduction. Journal of Catalysis, 405. pp. 15-23. ISSN 0021-9517

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Abstract

Introducing tetrazole moiety to the ligand framework of two isomeric ruthenium catalysts, cis/trans-[Ru(tpy)(mtzp)(CH3CN)]2+ (tpy = 2,2′:6′,2′'-terpyridine, mtzp = 2-(1-methyl-1H-tetrazol-5-yl)pyridine), for the electrochemical reduction of CO2 to CO has altered the catalytic pathway with significantly low overpotential (0.37 V) compared to its analogous catalysts. Without manipulating steric effects, only the electronic nature of tetrazole moiety enables CO2 binding to ruthenium center to form metallocarboxylate intermediate just after one-electron reduction. This is the first synthesized isomeric pair of ruthenium complex follow ECE (E = electron transfer, C = chemical reaction) mechanism for electrocatalytic reduction of CO2. By successful characterization of the Ru–CO intermediate with the help of 13C NMR, spectro-electrochemical studies and analysis of byproducts formed during the electrocatalysis, a mechanism of CO2 reduction has been established in presence of water and anhydrous conditions which is further supported by density functional theory (DFT). © 2021 Elsevier Inc.

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IITH Creators:

IITH Creators	ORCiD
Mahata, Arup	UNSPECIFIED
Shee, Debaprasad	https://orcid.org/0000-0002-3503-8098
Maji, Somnath	http://orcid.org/0000-0001-6047-1339

Item Type:

Article

Additional Information:

Financial support received from SERB project no. ECR/2016/000382, Council of Scientific and Industrial Research (CSIR) (fellowship to B.G.) and IIT Hyderabad is gratefully acknowledged. Special thanks to Dr. Debjyoti Ray, Dr. Piu Chawdhury and Dr. Deepak Raikwar for their help. F. D. A. thanks the Ministero Istruzione dell’Universita‘ e della Ricerca (MIUR) and the University of Perugia through the program ‘‘Dipartimenti di Eccellenza 2018–2022’’ (grant AMIS).

Uncontrolled Keywords:

Carbon dioxide reduction; Electrocatalysis; Overpotential; Reaction mechanisms; Ruthenium

Subjects:

Chemistry
Chemical Engineering

Divisions:

Department of Chemical Engineering
Department of Chemistry

Depositing User:

. LibTrainee 2021

Date Deposited:

28 Jul 2022 10:29

Last Modified:

28 Jul 2022 10:29