Chemistry Reference
In-Depth Information
Fig. 4.1 a
Synthetic route to
microporous polycarbazole
CPOP-1;
b
nitrogen
adsorption-desorption
isotherms and the pore size
distribution calculated by
NLDFT (
inset
) of CPOP-1.
Reprinted with permission
from Ref. [
20
]. Copyright
2012, American Chemical
Society
2,992 m
2
g
−
1
, respectively. Excitingly, at 298 K and 100 bar, the H
2
adsorption
capacity of TND-1 and TND-2 is 27 and 13 mg g
−
1
. This prediction of POF
structures would direct the design of POF.
4.2.3 Lithium Modified POFs
The first study concerning Li-doped POFs was reported by Deng et al. [
26
]. CMP is
used as starting material, which is synthesized by PdII/CuI-catalyzed homocoupling
polymerization. Naphthalene anion radical salt was utilized for the doping experi-
ments. The resulting Li-CMP with 0.5 wt% Li exhibits a significantly high adsorption
of maximum 6.1 wt% at 1 bar, which is nearly four times that of the CMP (Fig.
4.4
).
This is close to POFs with high surface area and measured at high pressure.
In 2009, our group reported the design and synthesis of PAF-1, which showed
exceptionally high surface areas. At 77 K and 48 bar, its H
2
adsorption capac-
ity reached 7.0 wt% [
30
]. A series of PAFs that shared similar topology were
also obtained subsequently. At 60 bar and 77 K, H
2
uptake of PAF-3 and PAF-4
reached 5.5 wt% and 4.2 wt%, respectively. Matthew et al. presented a route for
lithiation of PAF-1 (Li@PAF-1) (Fig.
4.5
), resulting in an activated pore surface.
H
2
adsorption isotherms collected at 77 K and 1.2 bar exhibited a storage capacity
of 2.7 wt% for 5 %-Li@PAF-1 [
31
].
