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ChemComm
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DOI: 10.1039/C6CC05430G
COMMUNICATION
Journal Name
13CO2 provides 13CO, further confirming that CO was issued from
CO2 reduction.
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A TOF of 178 h-1 in CO was obtained from a 3h electrolysis
(corresponding to 532 catalytic cycles per immobilized
electroactive catalyst). It corresponds to the net production of
8.5 ꢀmol of CO, while the selectivity just slightly decreased
(80%). A maximum TON of 750 was obtained. Interestingly,
when the tetraphenyl iron porphyrin (TPP) substituted by a
12.
13.
14.
carboxylic acid group on one phenyl ring (TPPCO2H
covalently attached to the carbon nanotubes similarly to CATCO2H
= 2 10-9 mol cm-2, see Supporting Information for preparation
) was
15.
16.
17.
18.
19.
(Γ
of the catalyst and of the modified electrode surface), CO was
also obtained. It was however produced with lower selectivity
(77% after 1h electrolysis and 51% after 3h electrolysis) and in
smaller quantities (4.5 ꢀmol after 3h electrolysis, see Figure S2).
TPPCO2H is thus a less selective catalyst than CATCO2H, but it is
however remarkable that it leads to CO formation with correct
yields.
In summary we have successfully modified carbon nanotubes by
attaching Fe porphyrin through a covalent bond. The supported
complex is highly selective and active for the reduction of
carbon dioxide in neutral water at low overpotential. This hybrid
material is promising and the grafting strategy may be extended
to other carbon forms, including graphene and related graphene
oxide. Metallic as well as semi-conductive materials may also be
modified along these lines, and it may open new opportunities
for the development of photo-electrochemical cells for selective
CO2 conversion. Finally, such molecularly modified surfaces are
good platforms for investigating the mechanisms for catalysis,
an area that should be vigorously investigated by combining in-
situ spectroscopic techniques and electrochemical approaches.
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Notes and references
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PhD fellowship to A. M. from Labex MiChem is gratefully
acknowledged. P. Decorse and H. Lecoq (Univ. Paris Diderot) are
gratefully thanked for XPS (P. D) and SEM (H. L) analysis.
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