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Cobaloxime Complex Salts: Synthesis, Patterning on Carbon Nanomembranes and Heterogeneous Hydrogen Evolution Studies
Author(s) -
Oswald Eva,
Gaus AnnaLaurine,
Kund Julian,
Küllmer Maria,
Romer Jan,
Weizenegger Simon,
Ullrich Tobias,
Mengele Alexander K.,
Petermann Lydia,
Leiter Robert,
Unwin Patrick R.,
Kaiser Ute,
Rau Sven,
Kahnt Axel,
Turchanin Andrey,
Delius Max,
Kranz Christine
Publication year - 2021
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.202102778
Subject(s) - catalysis , cobalt , electrochemistry , photocatalysis , chemistry , hydrogen , carbon fibers , materials science , combinatorial chemistry , nanotechnology , chemical engineering , inorganic chemistry , electrode , organic chemistry , composite number , engineering , composite material
Cobaloximes are promising, earth‐abundant catalysts for the light‐driven hydrogen evolution reaction (HER). Typically, these cobalt(III) complexes are prepared in situ or employed in their neutral form, for example, [Co(dmgH) 2 (py)Cl], even though related complex salts have been reported previously and could, in principle, offer improved catalytic activity as well as more efficient immobilization on solid support. Herein, we report an interdisciplinary investigation into complex salts [Co(dmgH) 2 (py) 2 ] + [Co(dmgBPh 2 ) 2 Cl 2 ] − ,TBA +[ Co ( dmgBPh 2 ) 2 Cl 2 ] -and [Co(dmgH) 2 (py) 2 ] + BArF − . We describe their strategic syntheses from the commercially available complex [Co(dmgH) 2 (py)Cl] and demonstrate that these double and single complex salts are potent catalysts for the light‐driven HER. We also show that scanning electrochemical cell microscopy can be used to deposit arrays of catalysts [Co(dmgH) 2 (py) 2 ] + [Co(dmgBPh 2 ) 2 Cl 2 ] − ,TBA +[ Co ( dmgBPh 2 ) 2 Cl 2 ] -and [Co(dmgH) 2 (py)Cl] on supported and free‐standing amino‐terminated ∼1‐nm‐thick carbon nanomembranes (CNMs). Photocatalytic H 2 evolution at such arrays was quantified with Pd microsensors by scanning electrochemical microscopy, thus providing a new approach for catalytic evaluation and opening up novel routes for the creation and analysis of “designer catalyst arrays”, nanoprinted in a desired pattern on a solid support.