Studying carbon dioxide-reduction by Fe-Ni Sulfides with modern electronic structure methods: A case of multistate reactivity?

Recently, pentlandite (Fe4.5Ni4.5S8) electrodes have been introduced as viable materials for the evolution of dihydrogen and the reduction of CO2 with remarkable properties in terms of overpotentials, efficiencies and durability. However, at this point a systematic improvement of the pentlandite material is impeded by a lack of mechanistic insight. The work proposed in here aims at elucidating the mechanistic details of the CO2 reduction on an atomic scale by means of modern electronic structure methods. A central aspect of the proposed research concerns the exploration of the contribution of electronically excited states to the observed reactivity. On account of the structural and electronic properties of pentlandite such contributions are expected to be prominent.