Communication
ChemComm
Japan Association for Chemical Innovation. The XAFS
spectra were recorded at the BL01B1 and BL14B2 stations
in SPring-8, Harima, Japan (Proposal no. 2020A1254 and
2020A1604, respectively). The authors acknowledge Prof.
T. Kyotani for his advice, Prof. H. Kato for his kind support
in Raman spectroscopy, Prof. Y. Nishina for his advice on
catalysis, and Mr S. Yoshida for his kind support in 13C NMR
measurements.
Fig. 4 (a) Methanol adsorption isotherms (298 K) of Ni-P_8e_873(0)
before (black), under (red) and after (blue) the application of a mechanical
force (213 MPa). (b) Fluctuation of methanol vapour pressure inside the
chamber during applying/releasing a mechanical force to Ni-P_8e_873(0).
Conflicts of interest
There are no conflicts to declare.
Notes and references
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As demonstrated in Fig. 4a, the methanol adsorption amount is
decreased by applying a mechanical force (213 MPa). When the
force is released, the adsorption amount is completely recov-
ered. These results indicate reversible nanopore contraction/
recovery by mechanical force. Such force-responsive behaviour
has not been reported in conventional activated carbons.14 The
elasticity of Ni-P_8e_873(0) is further demonstrated by the
force-driven methanol liquid–gas phase transition (Fig. 4b).15
Ni-P_8e_873(0) is placed in a closed chamber containing
methanol vapour and the adsorption equilibrium is established
at P/P0 = 0.916. When a force (213 MPa) is applied to
Ni-P_8e_873(0), the methanol vapour pressure is increased to
P/P0 = 0.922, indicating force-driven desorption of methanol,
which was adsorbed on Ni-P_8e_873(0). When the force is
removed, the vapour pressure decreases to P/P0 = 0.916 because
of the re-adsorption of methanol in recovered Ni-P_8e_873(0).
Moreover, a good repeatability is demonstrated against press-
ing with 213 MPa three times. This phenomenon is also
confirmed using ethanol as an adsorbate (Fig. S21, ESI†). Note
that the change of P/P0 caused by the dead-volume change is
negligible compared to the result of Fig. 4b (Fig. S22, ESI†).
Fig.
4 clearly indicates that the OCF functions as an
elastic nanosponge. The mechanically soft OCFs are expected
to be used for new applications such as force-responsive
electrocatalysis.
In summary, a new type of OCF with mechanical flexibility
has been synthesized by a simple carbonization of Ni porphyrin
monomer with eight ethynyl groups. A large number of ethynyl
groups in a monomer molecule is effective to develop micro-
porosity, and the largest recorded SBET (673 m2 gÀ1) is achieved
in OCF materials reported thus far. The OCFs have uniform-
sized micropores and the ordered framework containing single
Ni atom sites with the Ni–N4 coordination structure. Further-
more, the OCFs have a unique mechanical flexibility, and force-
driven reversible phase transition has been demonstrated. 20 F. McCoy, D. C. Apperley, B. Variano, H. Sussman, D. Loeven,
P. Boyd and R. K. Malcolm, Int. J. Pharm., 2018, 548, 689–697.
21 M. J. Matthews, M. A. Pimenta, G. Dresselhaus, M. S. Dresselhaus
These findings offer the opportunity to design new systems
using flexible carbonaceous frameworks containing single
and M. Endo, Phys. Rev. B: Condens. Matter Mater. Phys., 1999, 59,
metal atoms, paving the way for multiple applications of OCFs
involving catalysts, adsorbents, and gas separation/storage.
This work was supported by JST CREST Grant no.
JPMJCRI18R3; the ‘‘Five-star Alliance’’ in ‘‘NJRC Mater. & Dev.’’;
R6585–R6588.
22 Y. H. Lv, Z. Xin, X. Meng, M. Tao and Z. C. Bian, Microporous
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6010 | Chem. Commun., 2021, 57, 6007–6010
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