Death and Rebirth: Photocatalytic Hydrogen Production by a Self- Organizing Copper-Iron System

摘要

This study provides detailed mechanistic insights into light-driven hydrogen production using an abundant copper-iron system. It focuses on the role of the heteroleptic copper photosensitizer [Cu(P~^P)(N~^N)] ~+ , which can be oxidized or reduced after photoexcitation. By means of IR, EPR, and UV/vis spectroscopy as well as computational studies and spectroelectrochemistry, the possibility of both mechanisms was con?rmed. UV/ vis spectroscopy revealed the reorganization of the original heteroleptic photosensitizer during catalysis toward a homoleptic [Cu(N~^N)2] ~+ species. Operando FTIR spectroscopy showed the formation of a catalytic diiron intermediate, which resembles well-known hydrogenase active site models.