10.1002/anie.201804359
Angewandte Chemie International Edition
COMMUNICATION
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derived carbons are attractive materials for CO2 capture at low
concentrations, e.g., for filtration of the molecule from flue gases.
At 298 K and a N2/CO2 ratio of 90/10, which are benchmark
conditions for this application, the selectivity of C-HAT-CN-550
and C-HAT-CN-700 is 63.8 and 53.6, respectively (Figure S17).
These values are not exceedingly high, and the likely reason for
this is that the pores are still large enough to host significant
amounts of N2. Due to its significant quadrupole moment it will
be attracted by the strong polarization inside the C-HAT-CN-X
materials in a comparable way as CO2 as we have pointed out in
a recent review article.[21] In other words, these materials are not
really attractive for CO2 selective capture – especially if the
similar high affinity to H2O is taken into consideration, which will
lead to less selective CO2 capture under real world conditions.
The strong CO2 binding is more attractive for the activation of
the molecule with regard to its catalytic conversion rather than
its selective capture in the presence of other gases. Preliminary
tests of the C-HAT-CN-700 in electrocatalytic CO2 reduction
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(Figure S18) show that there is
a
significant current
enhancement in CO2-saturated solution in comparison to N2-
saturated solution indicating the high catalytic activity.
[8]
In conclusion, we have reported a novel template-free synthesis
pathway towards microporous noble carbon materials with
nearly perfect C2N-type stoichiometry and high purity by
controlled condensation of preorganized HAT precursor
molecules. The significant amount of heteroatoms in these
materials leads to outstanding adsorption properties, as
indicated by high uptake of guest molecules such as H2O and
CO2 at low concentrations resulting from the combination of
strong polarization on specific adsorption sites and high
micropore volume. The C2N-type material is thus a promising
metal-free alternative for various catalytic conversions. The
precise atomic-level structural control over the carbon
microstructure provided by the controlled condensation of
precursor molecules like HAT-CN enables the controlled
synthesis of carbon materials with stabilities even exceeding
those of established porous carbons and with adsorption
properties which are so far only achieved with metal-organic
frameworks or zeolites.
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Details of synthetic procedures and characterization methods can be
found in the supporting information of this article.
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Acknowledgements
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M.O. and R.W. acknowledge financial support by a Liebig
Scholarship of the German Chemical Industry Fund (Stiftung
Stipendien Fonds der Chemischen Industrie, FCI).
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Keywords: carbon materials • hexaazatriphenylene • porosity •
nitrogen doping • physisorption
[20] M. Oschatz, M. Leistner, W. Nickel, S. Kaskel, Langmuir 2015, 31,
4040-4047.
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