Electrochemical Mechanisms of Copper Bipyridine Complexes in Dichloromethane and Water

Christian D. Haas; Andrew Lazicki; Emerson Tran Lam; Ryan Van Daele; Emily Carroll; Johna Leddy

doi:10.1149/2754-2734/acd466

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Electrochemical Mechanisms of Copper Bipyridine Complexes in Dichloromethane and Water

Journal article

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Electrochemical Mechanisms of Copper Bipyridine Complexes in Dichloromethane and Water

Christian D. Haas, Andrew Lazicki, Emerson Tran Lam, Ryan Van Daele, Emily Carroll and Johna Leddy

ECS Advances, Vol.2(2), 020502

05/11/2023

DOI: 10.1149/2754-2734/acd466

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Abstract

Abstract Voltammetric mechanisms for copper bipyridine complexes are evaluated for Cu(bpy)\textsubscript{3}(PF\textsubscript{6})\textsubscript{2} in dichloromethane (DCM), Cu(bpy)\textsubscript{3}(ClO\textsubscript{4})\textsubscript{2} in water, and copper bipyridine complexes formed {\it in situ} from a stoichiometric 1:3 mix of Cu(II) and bpy in water. The mechanism for Cu(bpy)\textsubscript{3}(PF\textsubscript{6})\textsubscript{2} in aprotic DCM is a simple irreversible (slow) heterogeneous electron transfer, $\mathbb{E}_{irrev}$, with a standard heterogeneous electron transfer rate of 6 $\times$ 10\textsuperscript{-4} cm s\textsuperscript{-1}. For Cu(bpy)\textsubscript{3}(ClO\textsubscript{4})\textsubscript{2} in water near pH 6, the mechanism is a six species square scheme, with multiple chemical and electrochemical steps. Voltammetric morphologies for Cu(bpy)\textsubscript{3}(PF\textsubscript{6})\textsubscript{2} in DCM and Cu(bpy)\textsubscript{3}(ClO\textsubscript{4})\textsubscript{2} in water were evaluated by established diagnostics and modeled with digital simulations. Established diagnostics underrepresent the complexity of copper bipyridines in water. For the complexes formed {\it in situ}, the stoichiometric ratio is insufficient to form only Cu(bpy)\textsubscript{3}\textsuperscript{2+}, so an equilibrium model that characterizes speciation at given pH and electrode potentials is used. Solvent, pH, and speciation impact the observed voltammetry of copper bipyridine complexes.

Details

Title: Subtitle: Electrochemical Mechanisms of Copper Bipyridine Complexes in Dichloromethane and Water
Creators: Christian D. Haas
Andrew Lazicki
Emerson Tran Lam
Ryan Van Daele
Emily Carroll
Johna Leddy
Resource Type: Journal article
Publication Details: ECS Advances, Vol.2(2), 020502
DOI: 10.1149/2754-2734/acd466
ISSN: 2754-2734
eISSN: 2754-2734
Grant note: DOI: 10.13039/100009228, name: Iowa Energy Center, award: 21-IEC-011; DOI: 10.13039/100000183, name: Army Research Office, award: W911NF-19-1-0208
Language: English
Date published: 05/11/2023
Academic Unit: Chemistry
Record Identifier: 9984410801302771

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