Lithium-coupled electron transfer reactions of nano-confined WO x within Zr-based metal-organic framework.

Autor: Ghuffar HA; Department of Chemistry and Biochemistry, The University of Oklahoma, Norman, OK, United States., Noh H; Department of Chemistry and Biochemistry, The University of Oklahoma, Norman, OK, United States.
Jazyk: angličtina
Zdroj: Frontiers in chemistry [Front Chem] 2024 Jun 14; Vol. 12, pp. 1427536. Date of Electronic Publication: 2024 Jun 14 (Print Publication: 2024).
DOI: 10.3389/fchem.2024.1427536
Abstrakt: Interfacial charge transfer reactions involving cations and electrons are fundamental to (photo/electro) catalysis, energy storage, and beyond. Lithium-coupled electron transfer (LCET) at the electrode-electrolyte interfaces of lithium-ion batteries (LIBs) is a preeminent example to highlight the importance of charge transfer in modern-day society. The thermodynamics of LCET reactions define the minimal energy for charge/discharge of LIBs, and yet, these parameters are rarely available in the literature. Here, we demonstrate the successful incorporation of tungsten oxides (WO x ) within a chemically stable Zr-based metal-organic framework (MOF), MOF-808. Cyclic voltammograms (CVs) of the composite, WO x @MOF-808, in Li + -containing acetonitrile (MeCN)-based electrolytes showed an irreversible, cathodic Faradaic feature that shifted in a Nernstian fashion with respect to the Li + concentration, i.e., ∼59 mV/log [(Li + )]. The Nernstian dependence established 1:1 stoichiometry of Li + and e - . Using the standard redox potential of Li +/0 , the apparent free energy of lithiation of WO x @MOF-808 (ΔG app,Li ) was calculated to be -36 ± 1 kcal mol -1 . ΔG app,Li is an intrinsic parameter of WO x @MOF-808, and thus by deriving the similar reaction free energies of other metal oxides, their direct comparisons can be achieved. Implications of the reported measurements will be further contrasted to proton-coupled electron transfer (PCET) reactions on metal oxides.
Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
(Copyright © 2024 Ghuffar and Noh.)
Databáze: MEDLINE
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje