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Communication
Imidazole-linked Crystalline Two-Dimensional
Polymer with Ultrahigh Proton-Conductivity
Kayaramkodath Chandran Ranjeesh, Rajith Illathvalappil, Sairam Dnyaneshwar
Veer, Joseph Peter, Vivek Chandrakant Wakchaure, - Goudappagouda,
K. Vipin Raj, Sreekumar Kurungot, and Sukumaran Santhosh Babu
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b06080 • Publication Date (Web): 11 Sep 2019
Downloaded from pubs.acs.org on September 15, 2019

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Page 1 of 6 Journal of the American Chemical Society

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Imidazole-linked Crystalline Two-Dimensional Polymer with Ultrahigh
8 Proton-Conductivity
9
10 Kayaramkodath Chandran Ranjeesh,†,§ Rajith Illathvalappil,§,‡ Sairam Dnyaneshwar Veer,†,§
11 Joseph Peter,Ψ Vivek Chandrakant Wakchaure,†,§ Goudappagouda,†,§ K. Vipin Raj,§,‡ Sreekumar
12
Kurungot,§,‡ Sukumaran Santhosh Babu*,†,§
13
14 †Organic Chemistry Division, National Chemical Laboratory (CSIR-NCL), Dr. Homi Bhabha Road, Pune-4110 08,
15 India
16 ΨSacred Heart College, Kochi-682 013, Kerala, India
17
§Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201 002, India
18
19 ‡Physical and Materials Chemistry Division, National Chemical Laboratory (CSIR-NCL), Pune-4110 08, India
20
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22 Abstract: Proton-exchange membrane fuel cells are promising energy devices for sustainable future due to green features,
23 high power density, and mild operating conditions. A facile proton-conducting membrane plays a pivotal role to boost
24 the efficiency of fuel cells and hence focused research in this area is highly desirable. Major issues associated with the
25 successful example of Nafion resulted in the search for alternate proton conducting materials. Even though proton carrier
26 loaded crystalline porous organic frameworks have been used for proton-conduction, the weak host-guest interactions
27 limited its practical use. Herein, we developed a crystalline 2D-polymer comprised of benzimidazole units as the integral
28 part, prepared by the condensation of aryl acid and diamine in polyphosphoric acid medium. The imidazole linked-2D-
29 polymer exhibits ultrahigh proton conductivity (3.2 × 10-2 Scm-1) (at 95% relative humidity and 95 °C) in the pristine state,
which is highest among the undoped porous organic frameworks so far reported. The present strategy of crystalline
30
proton-conducting 2D-polymer will lead to the development of new high performing crystalline solid proton conductor.
31
32
33
34 The rise in global energy demand and depleting pristine state have rarely been used for proton
35 nonrenewable resources impart serious energy crisis.1 In conduction, instead, mostly served as an insulating 1D-
36 this context, significant efforts in identifying alternate channel for proton carriers such as phosphoric acid,
37 energy sources such as proton-exchange membrane fuel imidazole, p-toluene sulfonic acid etc.8 Here the weak
38 cells (PEMFCs) have been devoted.2 As an emerging green host-guest interaction leads to unavoidable leaching of
39 and sustainable energy source, PEMFCs have attracted proton carriers from the channels. The post
40 much attention in the current decade.2 A facile proton functionalization is also restricted due to the nonuniform
41 conduction is vital in the performance of FCs and hence doping of proton carriers and the lack of deeper
42 significant amount of research has been directed towards understanding of the mechanism. In short, the current
43 it.3 Subsequently, a polyelectrolyte membrane, Nafion4 strategies for developing COF-based proton conductors
44 has been emerged as an efficient membrane separator in rely either on doping with external proton carriers8,9 or on
45 FCs due to its robust structure, high proton conductivity randomly integrated pendant groups in the framework.10
46 and reusability without significant loss of activity. The Even though doping is simple and effective, the overall
47 need for more effective PEMs directed the research control on uniform loading of dopant and achieving a
48 towards structurally modified new materials with reliable result is not consistent. In this context, a proton
49 enhanced proton conduction.5 carrier linked 2D-polymer can be a better candidate for
Recently, crystalline porous materials such as covalent proton-conduction. Surprisingly, the proton-conducting
50
and metal-organic frameworks (COFs and MOFs), and feature of an imidazole linked 2D-polymer is hitherto
51
hydrogen-bonded frameworks (HOFs) have gathered reported.
52
53 attention due to its framework tunability, chemical We aimed to synthesize a benzimidazole-linked 2D-
54 stability, ease of synthesis and feasibility of hybridization polymer by using a monomer 3, which can undergo facile
55 with other materials.6 Moreover, COFs, MOFs, and HOFs reaction with 1,2,4,5-tetraaminobenzene 4 in the presence
56 have been attempted for proton-conducting applications.7 of polyphosphoric acid (PPA) (Fig. 1a). To confirm the
57 As one of the successful strategies, many proton carrier feasibility of 2D-polymerization, we successfully
doped COFs and MOFs exhibited excellent proton- synthesized two model derivatives M1 and M2 in good
58
conducting behavior. However, till this date, COFs in the yield (Fig. 1a, Scheme S1, S2). Even though PPA mediated
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imidazole synthesis is well explored for many small from carbon atoms of benzimidazole ring and signals at
1 molecules and linear polymers by the co-condensation 132, 127, 114 ppm from remaining aromatic rings.
2 reactions of aryl acid and o-diamine,11 not yet exploited Conclusive evidence is obtained from the peak at 153 ppm
3 for a crystalline 2D-polymer synthesis. Moreover, the corresponding to carbon atom 12, assigned on the
4 formation of two model derivatives motivated to go benzimidazole ring (Fig. 2b, inset). Comparison of the
5 further with the same synthetic route. UV-Vis absorption spectrum of BIP oligomers with model
6 a) derivatives that are absorbing in the 280-480 nm range
7 indicated the presence of benzimidazole moiety (Fig. S4).
8 A broad peak extending to the near-infrared region in the
9 solid-state diffuse reflectance spectrum also endorses the
10 1.6 nm 2D-polymerization (Fig. 2c). X-ray photoelectron
11 spectroscopy (XPS) analysis of BIP, after extensive
12 washing with organic solvents and water, clearly showed
13 peaks for C1S, N1S, and O1S and confirmed the absence of
14 BIP trapped polyphosphoric acid used for synthesis (Fig. 2d).
15 150 oC,
Thermogravimetric analysis (TGA) revealed the high
180 oC, After

16
24 hr 24 hr Washing thermal stability of BIP, comparable to stable COFs
17 reported (Fig. 2e).13
3
18 b)
19
20
21
22
c) d) e)
23
24
25 C N
26
27 Figure 1. a) Synthetic for BIP (hydrogen atoms have been
28 removed for clarity), photographs showing the progress of
29 polymerization of BIP, and chemical structure of monomers
30 M1 and M2. b) TEM image of BIP showing the presence of
31 layered sheets. c) TEM-high-angle annular dark-field image
32 and corresponding element mapping of BIP for d) C, e) N.
33 As we envisioned, PPA based synthetic route provided a
34 thermodynamically controlled condensation reaction of Figure 2. a) FT-IR spectra of 3, 4, M1, M2, and BIP. b) 13C
35 the monomers12 to form stable benzimidazole-linked 2D- CP-MAS NMR spectrum of BIP, asterisks denote spinning
36 polymer (Fig. 1a, S1). Note that the multilayer stacks of the sidebands. c) Solid-state diffuse reflectance UV-Vis-NIR
37 2D-polymer structure as revealed by transmission spectra of M1, M2, and BIP. d) XPS and e) TGA of BIP.
38 electron microscope (TEM) images of BIP suspension in
39 The permanent porosity of BIP evaluated by measuring
methanol points to the extended 2D-polymerization and
40 N2 adsorption isotherm at 77 K showed reversible type I
the multilayer stacks could be formed as a result of π-π
41 adsorption isotherm for the microporous structure of BIP
stacking of the individual 2D-polymer layers (Fig. 1b, S1).
42 (Fig. 3a).14 The Brunauer-Emmett-Teller (BET) surface
The composition of BIP is confirmed by TEM elemental
area of the activated BIP sample was found to be 510 m2/g
43 mapping (Fig. 1c-e). Scanning electron microscope (SEM)
with a narrow pore size distribution profile centered at 1.6
44 image showed the bulk structure of BIP composed of
nm (Fig. 3b), which is matching with the calculated
45 layered-sheets (Fig. S3). A comparison of the Fourier-
distance as shown in Fig. 1a. The powder X-ray diffraction
46 transform infrared (FT-IR) spectrum of BIP (Fig. 2a) with
(PXRD) pattern of BIP exhibited an intense peak at 4.2°,
47 all the starting materials and model derivatives reveals N-
corresponding to the reflection from the (100) plane (Fig.
48 H stretching as a broad peak ranging from 3412 cm-1 (free
3c). The peak at 2θ = 25° is due to the reflection from the
49 N-H) to 3200 cm-1 (hydrogen-bonded N-H), while intense
(001) plane.13 The corresponding π-π stacking distances
50 new bands appeared at 1634 cm-1 (C=N), which can be
between 2D-polymer layers were calculated to be 3.8 Å
51 assigned to vibrations of the benzimidazole ring skeleton.
from the d-spacing between 001 planes (Fig. 3c).
52 The intensity of the C=O band at 1691 cm-1 in 3 is
Structural simulations with an eclipsed AA-stacking
53 substantially disappeared in BIP, which suggested the full
structure generated an XRD curve that is consistent with
54 consumption of monomers during 2D-polymerization. 13C
the experimental profile (Fig. 3c-3e, S5, 6). It is clear from
cross-polarization magic angle spinning nuclear magnetic
55 the PXRD analysis that PPA assisted synthetic route helps
resonance (13C CP-MAS NMR) spectrum of BIP (Fig. 2b)
56 to undergo thermodynamically controlled condensation
contains signals located at 153, 142 and 99 ppm arising
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reaction of the monomers,12 which resulted in a crystalline with all well-known proton-conducting porous materials,
1 framework. reported to date (Table S4). We have investigated the
2 a) b) 1.6 nm time-dependent proton conductivity of BIP and as shown
3
Adsorption
600 Desorption
6 in Fig. 4e, a negligible difference observed over 10 hours
4

dv(r)(cc/nmg)
of measurement implies that efficient proton conductivity
N2 uptake (ccg )
-1

5 400
4 can be retained for longer hours. In addition, the proton
6 conductivity of BIP is supported by the low electrical
7 200 2 conductivity (~5.2 x 10-8 S/cm), which has a negligible
8 effect on proton conductivity of BIP (Fig. S10).16
0
9 0.0 0.5 1.0 0 10 20 The role of water molecules in high proton conductivity
Relative Pressure (P/P0) Pore Width (nm)
10 c) d) e) was confirmed by comparison of the conductance of BIP
BIP
11 by exposing it to H2O and D2O vapor at 25 oC and 98%
12 RH (Fig. 4f). The conductivity values were varied as 2.9 ×
Intensity (a. u.)

13 10-3 (H2O) and 2.0 × 10-3 (D2O) Scm-1. The observed drop in
14 conductivity for D2O compared to that of the H2O
15 Simulated exposed sample under identical condition can be
16 attributed to the heavier isotopic effect of D2O. Deuteron
17 conductivity experiment points to Grotthus-type
18 mechanism, supported by a decrease in charge carrier
19 10 20 30 40 velocity upon replacing proton with deuteron. The lack of
2 (degree) 0.38 nm
20 anhydrous conductivity and available deuteron
21 conductivity at a slower rate, in turn, ascertain the vital
Figure 3. a) BET N2 sorption isotherm curves of BIP
22 measured at 77 K. b) Pore-size distribution profile of BIP. c)
role of water molecules in the conduction process. The
23 PXRD profiles of BIP; simulated pattern for an AA stacking porous nature of the framework allows diffusion of water
24 mode of BIP is provided for comparison. d) Top and e) side molecules through the nanochannels, making a network
views of the layered 2D-polymer resulted from eclipsed AA of hydrogen bonds available for the facile proton
25
stacking. conduction. Density functional theory calculations on a
26
fragment consists of two layers also support this kind of a
27 A proton conduction study was carried out by the AC mechanism assisted by hydrogen-bonded water molecules
28 impedance method using compacted pellets of BIP in the nanochannels (Fig. S11-13).
29 having a thickness of 1.44 mm after saturating for 12 h a)100 100 b)
30 (Fig. 4). The proton conductivity was measured at
Relative Humidity

31 different temperatures (from 30 to 95 ᵒC) under varying

90 90 2k

Temperature
-Z'' ()
32 relative humidity (RH) (from 50 to 95%). Even though 80 80

33 BIP exhibited lower proton conductivity below 60 oC (Fig. 70 70

1k
60% RH

34 S7), the measurements below 60% RH resulted in only

70% RH
80% RH
60 60 95% RH
35 noisy signals (Fig. S8). Hence, BIP is not an active proton 0
0.00 0.01 0.02 0.03 0 1000 2000
36 transporter under anhydrous condition. The conductivity Conductivity (S/cm) Z' ()

37 value increased with an increase in temperature and RH, c) 40 o

60 C
o
d) -3

38 and concluded that BIP exhibited highest proton- 70 C

o
80 C
-4
conductivity of 3.2  10-2 Scm-1 at 95 °C under 95% RH
In (scm )

o
Ea = 0.31 eV
39
95 C
-1
-Z'' ()

20
40 (Fig. 4, Table S1,2). The Nyquist plots were obtained at
-5
41 different RHs (from 60 to 95%) by keeping a constant
42 temperature of 95 oC, and at different temperatures (from
0 -6
43 60 to 95 ᵒC) under constant RH, 95% (Fig. 4b,c). Nyquist 0 20
Z' ()
40 2.7 2.8 2.9
-1
3.0
1000/T (K )
44 plots displayed a noticeable decrease of resistance with e) 40 After 1h f) 200
-3
After 2h H2O 2.9 x 10 S/cm

45 increasing RH, indicates that the conductivity of BIP After 4h

-3
D2O 2.0 x 10 S/cm
After 8h

46 increases with a rise in humidity and the high water After 10h
-Z'' ()
-Z''()

20
affinity is confirmed by the contact angle and water vapor 100
47
sorption measurements (Movie S1 and Fig. S9). It
48
indicates that water plays a significant role in the proton-
49 0 0
conduction pathway. The activation energy determined 0 20 40 0 100 200
50 Z' () Z' 
using temperature-dependent conductivity profiles of BIP
51 was found to be 0.31 eV (Fig. 4d), which suggests the
52 Figure 4. a) Variation of temperature and humidity
possibility of a Grotthuss-type mechanism.15 BIP pellet dependent proton conductivity of BIP. Nyquist plots of BIP
53 retains excellent proton conductivity and Table S3 measured b) under 95 ᵒC at different RH and c) 95 % RH at
54 summarises the reliable performance of BIP from three different temperatures. d) Arrhenius plots for BIP at
55 different batches under the best performing condition. different temperatures. e) Time-dependent Nyquist plots of
56 Interestingly, for the first time, a pristine 2D-framework BIP measured at 95 oC and under 95% RH. f) Comparison of
57 shown high proton conductivity, which is comparable
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