@conference {434, title = {A DFT-based determination of the mechanism of electrochemical reduction of CO$_{2}$ to CO by a cobalt-Schiff base catalyst}, year = {2017}, month = {8{\textendash}10 Nov 2017}, pages = {P024}, publisher = {9th Electronic Structure and Processes at Molecular-Based Interfaces Workshop}, address = {National University of Singapore, Singapore}, abstract = {

We perform density functional theory (DFT) based calculations to investigate the reduction of carbon dioxide CO2 to carbon monixide CO using a cobalt-Schiff base catalyst, Co(salen). DFT calculated formation energies and reduction potentials showed that CO2 is reduced to CO via a [Co(salen)-COOH] intermediate. The first step of the mechanism involves the reduction of electrically neutral [Co(salen)]\ to [Co(salen)]-\ anion, followed by an electrophilic addition of CO2. Furthermore, the sigma bond formed between cobalt metal center and\ CO2\ involves a back-donation and partial charge transfer from cobalt to carbon. [Co(salen)-COOH] is further reduced to [Co(salen)-CO] and CO is released from the catalyst along with water H2O.

}, author = {Meliton R. Chiong III and Francis N. C. Paraan} }