Issue 12, 2024

Electrochemical control over stoichiometry via cation intercalation into Chevrel-phase sulphides (CuxMo6S8, x = 1–3)

Abstract

This work presents a systematic investigation of the electrochemical intercalation of aqueous copper cations into the Chevrel phase (CP) Mo6S8 and its effect on the host's electronic and structural characteristics as a function of stoichiometry. The electrochemical potentials at which copper intercalates into the CP Mo6S8 host in 1 M CuSO4 were identified for CuxMo6S8 (x = 1–3) as 0.23 V, 0.11 V, and 0.055 V (vs. Cu/Cu2+) for Cu1Mo6S8, Cu2Mo6S8, and Cu3Mo6S8, respectively, and correlated via ex situ PXRD to stoichiometric content. Potentials were also identified that yield non-stoichiometric phases with traceable Cu content-dependent structural changes. Ab initio DFT calculations were performed to probe thermodynamic stability of CuxMo6S8 CP compositions and the metal-to-semiconductor transitions as a function of copper content. Lastly, we demonstrate that the SK-pre-edge intensity is a successful probe for intercalant content: as copper equivalents increase, so does charge transfer to the partially occupied S 3p orbitals, resulting in a decrease in the pre-edge intensity corresponding to the excitation of a S 1s-to-3p/Mo 4d hybridized orbital.

Graphical abstract: Electrochemical control over stoichiometry via cation intercalation into Chevrel-phase sulphides (CuxMo6S8, x = 1–3)

Supplementary files

Article information

Article type
Paper
Submitted
28 Nov 2023
Accepted
07 Feb 2024
First published
09 Feb 2024

J. Mater. Chem. A, 2024,12, 7199-7206

Electrochemical control over stoichiometry via cation intercalation into Chevrel-phase sulphides (CuxMo6S8, x = 1–3)

K. A. Ritter, K. G. Mason, S. Yew, J. T. Perryman, J. C. Ortiz-Rodríguez, N. R. Singstock, B. A. Wuille Bille, C. B. Musgrave and J. M. Velázquez, J. Mater. Chem. A, 2024, 12, 7199 DOI: 10.1039/D3TA07333E

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