Defence of doctoral thesis: Canyan Che – Electrochemical reaction of quinines at conducting polymer electrodes for electrical energy devices
Linköpings universitet, Campus Norrköping
Opponent: Prof. Mieczyslaw Lapkowski, Silesian University of Technology
Supervisor: Prof. Xavier Crispin, Linköping University
Co-supervisors: Magnus Jonsson, Mikhail Vagin, Viktor Gueskine, Linköping University
Update 191128: Due to technical problems, the live-streaming is cancelled. The presentation will be made available at www.treesearch.se/forskning/treeseach-defences after the defence.
Proton-coupled multielectron transfer reactions are of great abundance in Nature. In particular, two-proton-two-electron transfers in quinone/hydroquinone redox couples are behind oxidative phosphorylation (ADP-to-ATP) and photosystem II. The redox processes of neurotransmitters, as a platform for brain activity read-out, are two-proton two-electron transfers of quinones. Moreover, humic acids, which constitute a major organic fraction of soil, turf, coal, and lignin, which forms as a large-scale surplus product from forest and paper industry, contain a large quantity of polyphenols, which can undergo the exchange of two electrons per aromatic ring accompanied with transfers of two protons. This makes polyphenol-based biopolymers, such as lignin, promising green-chemistry renewable materials for electrical energy storage or generation. The application of intact or depolymerized polyphenols in electrical energy devices such as fuel cells and redox flow batteries requires appropriate electrode materials to ensure efficient proton-coupled electron transfer reactions occurring at the solid-liquid interface. Moreover, investigation of the biological quinones reaction calls for porous, soft, biocompatible materials as implantable devices to reduce the rejection reaction and pain.
At common electrode materials such as platinum and carbons, quinone/hydroquinone redox processes are rather irreversible; in addition, platinum is very costly. Conducting polymers (CPs), poly(3,4-ethylenedioxythiophene) (PEDOT) in particular, offer an attractive option as metal-free electrode material for these reactions due to their molecular porosity, high electrical and ionic conductivity, solution processability, resistance to acid media, as well as high atomic abundance of their constituents.
This thesis explores the possibility of utilizing CPs as electrode materials for driving various quinone redox reactions. Firstly, we studied the electrocatalytic activity and mechanism of PEDOTs for the generic hydroquinone reaction and their application in a fuel cell. Secondly, the mechanism of integrating lignosulfonate (LS) into CP matrices and optimization strategies were explored in order to boost energy storage capacity. Thirdly, we attained mechanistic understanding of the influence of ionic transport and proton management on the thermodynamics and kinetics of the electrocatalysis on CPs, thereby providing steps towards the design of quinone-based electrical energy storage devices, such as organic redox flow batteries (ORFB).