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

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posted on 06.06.2014 by Steffen Fischer, Dirk Hollmann, Stefanie Tschierlei, Michael Karnahl, Nils Rockstroh, Enrico Barsch, Patrick Schwarzbach, Shu-Ping Luo, Henrik Junge, Matthias Beller, Stefan Lochbrunner, Ralf Ludwig, Angelika Brückner
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(PP)­(NN)]+, 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 confirmed. UV/vis spectroscopy revealed the reorganization of the original heteroleptic photosensitizer during catalysis toward a homoleptic [Cu­(NN)2]+ species. Operando FTIR spectroscopy showed the formation of a catalytic diiron intermediate, which resembles well-known hydrogenase active site models.

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