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Photocatalytic Hydrogen Generation from Water with Iron Carbonyl Phosphine Complexes: Improved Water Reduction Catalysts and Mechanistic Insights
Author(s) -
Gärtner Felix,
Boddien Albert,
Barsch Enrico,
Fumino Koichi,
Losse Sebastian,
Junge Henrik,
Hollmann Dirk,
Brückner Angelika,
Ludwig Ralf,
Beller Matthias
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201003564
Subject(s) - chemistry , catalysis , phosphine , photochemistry , photocatalysis , ligand (biochemistry) , catalytic cycle , hydrogen , triethylamine , inorganic chemistry , organic chemistry , biochemistry , receptor
Abstract An extended study of a novel visible‐light‐driven water reduction system containing an iridium photosensitizer, an in situ iron(0) phosphine water reduction catalyst (WRC), and triethylamine as sacrificial reductant is described. The influences of solvent composition, ligand, ligand‐to‐metal ratio, and pH were studied. The use of monodentate phosphine ligands led to improved activity of the WRC. By applying a WRC generated in situ from Fe 3 (CO) 12 and tris[3,5‐bis(trifluoromethyl)phenyl]phosphine (P[C 6 H 3 (CF 3 ) 2 ] 3 , Fe 3 (CO) 12 /PR 3 =1:1.5), a catalyst turnover number of more than 1500 was obtained, which constitutes the highest activity reported for any Fe WRC. The maximum incident photon to hydrogen efficiency obtained was 13.4 % (440 nm). It is demonstrated that the evolved H 2 flow (0.23 mmol H 2 h −1 mg −1 Fe 3 (CO) 12 ) is sufficient to be used in polymer electrolyte membrane fuel cells, which generate electricity directly from water with visible light. Mechanistic studies by NMR spectroscopy, in situ IR spectroscopy, and DFT calculations allow for an improved understanding of the mechanism. With respect to the Fe WRC, the complex [HNEt 3 ] + [HFe 3 (CO) 11 ] − was identified as the key intermediate during the catalytic cycle, which led to light‐driven hydrogen generation from water.