Macromolecular Engineering of the Outer Coordination
Sphere of [2Fe-2S] Metallopolymers to Enhance Catalytic Activity for
H2 Production
Posted on 2018-11-08 - 20:15
Small-molecule
catalysts inspired by the active sites of [FeFe]-hydrogenase
enzymes have long struggled to achieve fast rates of hydrogen evolution,
long-term stability, water solubility, and oxygen compatibility. We
profoundly improved on these deficiencies by grafting polymers from
a metalloinitiator containing a [2Fe-2S] moiety to form water-soluble
poly(2-dimethylamino)ethyl methacrylate metallopolymers (PDMAEMA-g-[2Fe-2S]) using atom transfer radical polymerization
(ATRP). This study illustrates the critical role of the polymer composition
in enhancing hydrogen evolution and aerobic stability by comparing
the catalytic activity of PDMAEMA-g-[2Fe-2S] with a nonionic water-soluble metallopolymer based on poly(oligo(ethylene
glycol) methacrylate) prepared via ATRP (POEGMA-g-[2Fe-2S]) with the same [2Fe-2S] metalloinitiator. Additionally,
the tunability of catalyst activity is demonstrated by the synthesis
of metallocopolymers incorporating the 2-(dimethylamino)ethyl methacrylate
(DMAEMA) and oligo(ethylene glycol) methacrylate (OEGMA) monomers.
Electrochemical investigations into these metallo(co)polymers show
that PDMAEMA-g-[2Fe-2S] retains complete
aerobic stability with catalytic current densities in excess of 20
mA·cm–2, while POEGMA-g-[2Fe-2S] fails to reach 1 mA·cm–2 current
density even with the application of high overpotentials (η
> 0.8 V) and loses all activity in the presence of oxygen. Random
copolymers of the two monomers polymerized with the same [2Fe-2S]
initiator showed intermediate activity in terms of current density,
overpotential, and aerobic stability.
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Brezinski, William
P.; Karayilan, Metin; Clary, Kayla E.; McCleary-Petersen, Keelee C.; Fu, Liye; Matyjaszewski, Krzysztof; et al. (2018). Macromolecular Engineering of the Outer Coordination
Sphere of [2Fe-2S] Metallopolymers to Enhance Catalytic Activity for
H2 Production. ACS Publications. Collection. https://doi.org/10.1021/acsmacrolett.8b00765
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AUTHORS (10)
WB
William
P. Brezinski
MK
Metin Karayilan
KC
Kayla E. Clary
KM
Keelee C. McCleary-Petersen
LF
Liye Fu
KM
Krzysztof Matyjaszewski
DE
Dennis H. Evans
DL
Dennis L. Lichtenberger
RG
Richard S. Glass
JP
Jeffrey Pyun