Issue 22, 2024

Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(ii) derivative anchored with a ‘scorpionate’ precursor as a potential electrocatalyst for heterogeneous H2 evolution

Abstract

A new doubly carboxylato-bridged Co(II) dinuclear complex, [Co(bdtbpza)(NCS)]2 (1), was obtained in a satisfactory yield by employing a ‘scorpionate’-type precursor, bdtbpza {bis-(3,5-di-tert-butylpyrazol-1-yl)acetate}, and was then structurally characterized. Single-crystal X-ray diffraction analysis revealed that, in 1, each Co(II) is penta-coordinated, leading to a distorted trigonal–bipyramidal geometry within the coordination environment of N3O2. Weak antiferromagnetic coupling within the Co(II) ions in 1 was found based on the isotropic spin Hamiltonian H = −J(S1·S2) for the Si = 3/2 system. For evaluating the spin density distribution and the mechanism for the magnetic exchange coupling, DFT analysis was performed, with the calculated result agreeing the experimental magnetic data. A study into electrochemical H2 evolution, involving cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatographic (GC) analyses of the graphite electrode modified with the cobalt complex in a neutral aqueous solution revealed the high catalytic activity of the complex with a low overpotential toward H2O reduction. The faradaic efficiency of the catalyst was found to be 83.7% and the di-cobalt catalyst-modified electrode displayed quite an interesting H2-evolution activity compared with that of bare electrodes. These results are encouraging for the future potential application of 1 in water splitting.

Graphical abstract: Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(ii) derivative anchored with a ‘scorpionate’ precursor as a potential electrocatalyst for heterogeneous H2 evolution

Supplementary files

Article information

Article type
Paper
Submitted
18 Mar 2024
Accepted
05 May 2024
First published
07 May 2024

Dalton Trans., 2024,53, 9358-9368

Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(II) derivative anchored with a ‘scorpionate’ precursor as a potential electrocatalyst for heterogeneous H2 evolution

K. Das, B. B. Beyene, C. Massera, E. Garribba, M. S. El Fallah, A. Frontera, C. Hung and A. Datta, Dalton Trans., 2024, 53, 9358 DOI: 10.1039/D4DT00807C

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