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Charged Macromolecular Rhenium Bipyridine Catalysts with Tunable CO 2 Reduction Potentials
Author(s) -
Sahu Swagat,
Cheung Po Ling,
Machan Charles W.,
Chabolla Steven A.,
Kubiak Clifford P.,
Gianneschi Nathan C.
Publication year - 2017
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.201701901
Subject(s) - electrocatalyst , catalysis , polymer , rhenium , chemistry , electrochemistry , ammonium , nanoparticle , bipyridine , inorganic chemistry , polymer chemistry , materials science , organic chemistry , nanotechnology , electrode , crystal structure
A series of polymeric frameworks with functional assemblies were designed to alter the catalytic activity of covalently bound Re I electrocatalysts. Norbornenyl polymers containing positively charged quaternary ammonium salts, neutral phenyl, or negatively charged trifluoroborate groups were end‐labelled with a Re I fac ‐tricarbonyl bipyridine electrocatalyst via cross metathesis. Electrochemical studies in acetonitrile under an inert atmosphere and with saturated CO 2 indicate that the quaternary ammonium polymers exhibit a significantly lower potential for CO 2 reduction to CO (ca. 300 mV), while neutral polymers behave consistently with what has been reported for the free, molecular catalyst. In contrast, the trifluoroborate polymers displayed a negative shift in potential and catalytic activity was not observed. It is demonstrated that a single catalytically active complex can be installed onto a charged polymeric framework, thereby achieving environmentally tuned reduction potentials for CO 2 reduction. These materials may be useful as polymer‐based precursors for preparing catalytic and highly ordered structures such as thin films, porous catalytic membranes, or catalytic nanoparticles.