S-1 Supporting Information Proton Conductive Nanosheets Formed by ...
Supporting Information
Proton Conductive Nanosheets Formed by Alignment of Metallo-Supramolecular Polymers Rakesh K. Pandey,a Utpal Rana,a Chanchal Chakraborty,b Satoshi Moriyamab and Masayoshi Higuchi*a a
Electronic Functional Materials Group, National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan. bInternational Center for Materials Nanoarchitectonics (MANA), NIMS, Tsukuba 305-0044, Japan.
Corresponding Author Dr. Masayoshi Higuchi Email: [email protected] Tel & Fax: +81-29-860-4721
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Contents: Figure S1. FTIR spectra of polyFe-PSA, PSA and polyFe. Figure S2. HRMS spectrum of polyFe-PSA. Figure S3. HRTEM images of polyFe, polyFe-PSA and STEM images of polyFe-PSA. Figure S4. Photograph of the sample bottles in natural light and UV light showing the emission. Figure S5. Nyquist plots for polyFe-PSA at several humidity levels. Figure S6. Nyquist plot for polyFe. Figure S7. Nyquist plots for PSA pellet at 90 %RH and Bode plots for polyFe-PSA and PSA at 40 %RH. Figure S8. Arrhenius plots for activation energy determination in polyFe-PSA. Figure S9. Nyquist plot for polyFe (with CF3SO3-) counter anions at 100 %RH and room temperature.
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Fig. S1. FTIR spectra of polyFe-PSA, PSA and polyFe.
Fig. S2. HRMS spectrum of polyFe-PSA.
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Fig. S3. (a), (b): TEM images of polyFe having acetate counter anions, (c) HRTEM image of polyFe-PSA showing the layered stacking of nanosheets, (d) (e) STEM images of a single rod of polyFe-PSA showing the presence of regions consisting of C, N, Fe and S in the polymer.
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Fig. S4. (a) Sample bottles of PSA, polyFe-PSA and polyFe in DMSO in natural light, (b) showing their respective emission under UV light. Quenched emission of PSA is clearly seen in polyFe-PSA, (c) Emission titration by stepwise addition of 10 m Fe(OAc)2 into 50 m PSA solution (excitation at 520 nm) and (d) Emission titration by stepwise addition of 10 m polyFe into 50 m PSA solution (excitation at 520 nm). Note: If PSA chromophores are intercalated in polyFe inter-lamellar region and subsequently assemble in nanosheets, they are subjected to a different geometrical and chemical environment than the pristine PSA. Usually, the blue shifted and quenched emission suggests H-type aggregation. One can argue that the quenching could be due to the Fe ions present in the polymer therefore, in order to study the effect of Fe ions to the emission of PSA, we carried out emission titration by step-wise adding Fe(OAc)2 into the solution of PSA as shown in Figure 4a. . The emission, as can be seen from the figure remains largely unaffected, however, a little increase in the emission can be seen with each addition of Fe ions, which suggests that dilution gradually brings down the aggregation rate in PSA. We also carried out another emission titration by stepwise addition of polyFe into the PSA solution as shown in Figure 4b. In this case, the systematic decrease in the emission of PSA associated with blue shift suggests the intercalation and aggregate formation of PSA molecules between the polymer chains.
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Fig. S5. Nyquist plots for polyFe-PSA at several humidity levels inset shows the high frequencies region.
Fig. S6. Nyquist plots for polyFe at 90 %RH, inset shows the activation energy determination.
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Fig. S7. (a) Nyquist plot for PSA pellet at 90 % RH, and (b) Bode total impedance and (c) Phase angle plots for polyFe-PSA and PSA pellet at 40 %RH. PolyFe-PSA has lower impedance than PSA.
Fig. S8. Arrhenius plots for activation energy determination at low, intermediate and high %RH.
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Fig. S9. Nyquist plot for polyFe (with CF3SO3-) counter anions at 100 %RH and room temperature. A much lower conductivity than polyFe-PSA was obtained.
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Proton Conductive Nanosheets Formed by Alignment of Metallo-Supramolecular Polymers Rakesh K. Pandey,a Utpal Rana,a Chanchal Chakraborty,b Satoshi Moriyamab and Masayoshi Higuchi*a a
Electronic Functional Materials Group, National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan. bInternational Center for Materials Nanoarchitectonics (MANA), NIMS, Tsukuba 305-0044, Japan.
Corresponding Author Dr. Masayoshi Higuchi Email: [email protected] Tel & Fax: +81-29-860-4721
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Contents: Figure S1. FTIR spectra of polyFe-PSA, PSA and polyFe. Figure S2. HRMS spectrum of polyFe-PSA. Figure S3. HRTEM images of polyFe, polyFe-PSA and STEM images of polyFe-PSA. Figure S4. Photograph of the sample bottles in natural light and UV light showing the emission. Figure S5. Nyquist plots for polyFe-PSA at several humidity levels. Figure S6. Nyquist plot for polyFe. Figure S7. Nyquist plots for PSA pellet at 90 %RH and Bode plots for polyFe-PSA and PSA at 40 %RH. Figure S8. Arrhenius plots for activation energy determination in polyFe-PSA. Figure S9. Nyquist plot for polyFe (with CF3SO3-) counter anions at 100 %RH and room temperature.
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Fig. S1. FTIR spectra of polyFe-PSA, PSA and polyFe.
Fig. S2. HRMS spectrum of polyFe-PSA.
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Fig. S3. (a), (b): TEM images of polyFe having acetate counter anions, (c) HRTEM image of polyFe-PSA showing the layered stacking of nanosheets, (d) (e) STEM images of a single rod of polyFe-PSA showing the presence of regions consisting of C, N, Fe and S in the polymer.
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Fig. S4. (a) Sample bottles of PSA, polyFe-PSA and polyFe in DMSO in natural light, (b) showing their respective emission under UV light. Quenched emission of PSA is clearly seen in polyFe-PSA, (c) Emission titration by stepwise addition of 10 m Fe(OAc)2 into 50 m PSA solution (excitation at 520 nm) and (d) Emission titration by stepwise addition of 10 m polyFe into 50 m PSA solution (excitation at 520 nm). Note: If PSA chromophores are intercalated in polyFe inter-lamellar region and subsequently assemble in nanosheets, they are subjected to a different geometrical and chemical environment than the pristine PSA. Usually, the blue shifted and quenched emission suggests H-type aggregation. One can argue that the quenching could be due to the Fe ions present in the polymer therefore, in order to study the effect of Fe ions to the emission of PSA, we carried out emission titration by step-wise adding Fe(OAc)2 into the solution of PSA as shown in Figure 4a. . The emission, as can be seen from the figure remains largely unaffected, however, a little increase in the emission can be seen with each addition of Fe ions, which suggests that dilution gradually brings down the aggregation rate in PSA. We also carried out another emission titration by stepwise addition of polyFe into the PSA solution as shown in Figure 4b. In this case, the systematic decrease in the emission of PSA associated with blue shift suggests the intercalation and aggregate formation of PSA molecules between the polymer chains.
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-40
100 % RH 90 % RH 80 % RH 70 % RH 60 % RH 50 % RH 40 % RH -1.5
-20
Z img x 106
Z img x 106
-30
-1.0
-10
-0.5
0.0 0
0 0
50
100 Zreal x 106
5
Zreal x 106
150
200
Fig. S5. Nyquist plots for polyFe-PSA at several humidity levels inset shows the high frequencies region.
Fig. S6. Nyquist plots for polyFe at 90 %RH, inset shows the activation energy determination.
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Fig. S7. (a) Nyquist plot for PSA pellet at 90 % RH, and (b) Bode total impedance and (c) Phase angle plots for polyFe-PSA and PSA pellet at 40 %RH. PolyFe-PSA has lower impedance than PSA.
Fig. S8. Arrhenius plots for activation energy determination at low, intermediate and high %RH.
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Fig. S9. Nyquist plot for polyFe (with CF3SO3-) counter anions at 100 %RH and room temperature. A much lower conductivity than polyFe-PSA was obtained.
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