Efficient oxygen electrocatalysis on special active sites: A theoretical study

Oxygen electrocatalysis will be pivotal in future independent of fossil fuels. Renewable energy production will rely heavily on oxygen electrocatalysis as a method for storing energy from intermittent energy sources such as the wind and sun in the form of chemical bonds and to release the energy stored in these bonds in an eco-friendly fashion in fuel cells.

This thesis explores catalysts for oxygen electrocatalysis and how carefully designed local structures on catalysts surfaces termed special active sites can influence the activity. Density functional theory has been used as a method throughout this thesis to understand these local structure effects and their influence on surface reactions.

The concept of these special active sites is used to explain how oxygen evolution reaction (OER) catalysts can have activities beyond the limits of what was previously thought possible. The concept is used to explain the increase in activity observed for the OER catalyst ruthenium dioxide when it is mixed with nickel or cobalt.

Manganese and cobalt oxides when in the vicinity of gold also display an increase in OER activity which can be explained by locally created special active sites. Density functional theory calculation provides an insight into the how the activity is increased at these special active sites and proposes a modified reaction mechanism for the oxygen evolution reaction on these sites.

Another type of special active site can explain the production of hydrogen peroxide on nickel and cobalt incorporated in ruthenium dioxide at high overpotentials during the oxygen reduction reaction (ORR). Density functional theory calculations were used to explain this phenomenon. The special active sites concepts are used to propose a general unified approach to increase the efficiency for oxygen electrocatalysis (ORR and OER) using organic functional groups on another class of catalysts.

These consist of graphene sheets modified to have a local porphyrine site with different transition metals ions as model systems.