Theoretical Study of oxygen reduction reaction (ORR) on poly-terthiophene

We report on an investigation of the overall mechanism of the reaction of reduction of molecular oxygen (ORR reaction) on poly-terthiophene by means of Density Functional Theory (DFT) computation. The calculations predict a large electron affinity of terthiophene (THP) of ~2.4 eV in aqueous phase that supports the idea that activation of the polymer catalyst occurs via an initial one-electron reduction step. The activation step is followed by O2 addition and a one-proton-one-electron coupled reduction to form a key stable peroxide radical anion intermediate THP-OOH-. The anion undergoes a unimolecular dissociation leading to hydro-peroxide OOH- anion formation (the 2-electron reduction pathway of molecular oxygen) over an activation barrier of ~ 0.16 eV selectively over hydroxide OH- anion (the 4-electron reduction pathway of O2) over an activation barrier of ~ 0.29 eV. Henry Eyring’s transition state theory predicts the rate of OOH- evolution to be ~ two orders of magnitude faster than OH- evolution.

Grantor dc:publisher

State University of New York at Buffalo

Year dc:date.issued

2018

Author dc:creator

• Wang, Xiaoyu; 0000-0001-7549-6010

Contributors dc:contributor

• Dupuis, Michel
• Chemical and Biological Engineering

• chemical engineering

Statement dc:rights

• Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.
• Copyright retained by author.

Language dc:language

eng

Handle dc:identifier

http://hdl.handle.net/10477/78008

OAI record oai:identifier

https://ubir.buffalo.edu/oai/request?verb=GetRecord&metadataPrefix=qdc&identifier=oai%3Aubir.buffalo.edu%3A10477%2F78008