A facile electropolymerization process was utilized to prepare electrodes modified with thin films of cobalt protoporphyrin IX. These thin films exhibited a high Faradaic efficiency (84±2 %) for the reduction of CO2 to CO in aqueous solutions near neutral pH with 450 mV of overpotential and a turnover frequency at zero overpotential (log(TOF0)) of −5.9. The production of CO was stable over several hours at these modest potentials. The use of a 13CO2 reactant led exclusively to 13CO as the product. Polymeric films of the unmetalated porphyrin did not demonstrate catalysis for CO2 reduction. UV/Vis spectroelectrochemical experiments indicate that the parent CoII complex is reduced to CoI at the electrode surface before interaction with CO2. It is proposed that the rate-determining step in the reduction of CO2 is the initial reduction of the CoII moiety to CoI, which binds CO2 and then undergoes a proton-coupled electron transfer and a loss of water to form CO. Additionally, a new metric for the evaluation of electrocatalysts, the catalytic efficiency, is proposed. The catalytic efficiency is the ratio of the power stored to power consumed for a given electrochemical reaction and can be used to describe both the kinetics and overpotential considerations of a given system.
|Original language||English (US)|
|Number of pages||10|
|State||Published - Nov 22 2016|
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry