Supporting Information
An Open Framework Chalcogenide of (H
3O)KCu
6Ge
2S
8nH
2O Exhibiting High Mixed Proton-Electron Conduction
Guo-Qin Zhang,a Zhi-Yuan Yao,a Jin Zhang,a Hong-Bin Luo,a Ya-Ru Kong,a Yang Zou,*a Zheng-Fang Tian,*b Xiao-Ming Ren*a,c,d
a State Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, P.
R. China
b Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Ministry of Education, Hubei University, Wuhan 430062, P. R. China
c College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211816, P. R. China
d State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023, P. R. China
Email:
[email protected] (ZFT) [email protected] (YZ) [email protected](XMR)
Figure S2: SEM images of the samples (ad) prepared using the molar ratio of S:GeO2 = 14.17, 16.17, 18.17 and 20.17, respectively.
Figure S3: PXRD patterns of the samples with different molar ratios of S:GeO2 (=
14.17, 16.17, 18.17 and 20.17), indicating that the high pure phase of 1 could be harvested.
Figure S4: (a) Temperature dependent PXRD patterns of 1 in 298473 K in the air (b) PXRD patterns of the samples as-prepared and soaked in 2 M H2SO4 for five days for 1.
Figure S5: EPR spectrum of the sulfuric acid solution used to soak crystalline sample of 1.
Figure S6: Comparison of PXRD pattern between the samples as-prepared and used for impedance measurement (a) in 123473 K under N2 atmosphere and (b) in 298343 K under 98% RH of 1.
Figure S7: (a) Comparison of PXRD patterns of as prepared and ball milled samples of 1 (b, c) SEM images of the ball milled sample of 1 in different magnifications. The sample used for PXRD and SEM measurements was ball milled for three hours.
Figure S8: XPS of C1s peak in the measurement for the samples of (a) grounded and (b) as prepared crystals of 1.
Figure S9: Plots of conductivity against temperature in (a) the first heating process from 298 to 473 K (b, c) the first cooling process from 473 to 123 K (d, e) the second heating process from 128 to 473 K (f) the second cooling process from 468 to 298 K.
Figure S10: Real part of impedance spectra of 1 at the selected temperatures in
Figure S11: Real part of impedance spectra of 1 at the selected temperatures in 123473 K and 1106 Hz under N2 atmosphere in the first cooling process.
Figure S12: Real part of impedance spectra of 1 at the selected temperatures in 123473 K and 1106 Hz under N2 atmosphere in the second heating process.
Figure S13: Real part of impedance spectra of 1 at the selected temperatures in 298473 K and 1106 Hz under N2 atmosphere in the second cooling process.
Figure S14: Frequency dependent AC conductivities in N2 atmosphere at (a) 298 K (b) 353 K (c) 373 K (d) 468 K in four sequential heating-cooling cycles.
Figure S15: (ac) Nyquist plots at the selected temperatures (d) curve of conductivity against temperature in the form of ln vs. 1000/T for 1 under N2 atmosphere in the first heating run.
Figure S16: Images of (a) as-prepared and (b) heated at 105 C for 1 hour samples.
Figure S17: Current against time Plots and Ie-V curves of 1 at 298, 303, 308 and 313 K under 98% RH.
Figure S18: Current against time Plots and Ie-V curves of 1 at 318, 323, 328 and 333 K under 98% RH.
Figure S19: Current against time plots and Ie-V curves of 1 at 338 and 343 K under 98% RH.
Figure S20: Ie-V curves of 1 at 298 K under Argon atmosphere.
Figure S21: Experimental and fitted Nyquist plots at the selected temperatures and 98%
RH for 1, and the fits were performed using the equivalent circuit shown in the inset.
Figure S22: (a) I-V Plots at the selected temperatures and the I and V values were obtained from the Chronoamperometry measurements under 98% RH (b) temperature dependent electron conductivities at the selected temperatures in 298343 K, which were obtained from I-V and EIS analyses under 98% RH, respectively, for 1.
Figure S23: (a) Plot of ln(T) versus 1000/T for ion conduction and (b) ln() versus 1000/T for electron conduction of 1 at the selected temperatures in 298343 K and under 98% RH.
Figure S1: (a) Coordination environments of Cu1/Ge1 and Cu2 (b, c) coordination sphere of K+ viewed along c- and b-axis directions, respectively (d, e) O atoms of hydroniums in the channels viewed along c- and b-axis directions, respectively (f) the framework of {Cu6Ge2S8}n2n together with K+ and hydronium ions in the channels viewed along c-axis for 1.
(c) (d)
(e) (f)
Figure S2: SEM images of the samples (ad) prepared using the molar ratios of S:GeO2 = 14.17, 16.17, 18.17 and 20.17, respectively.
Figure S3: PXRD patterns of the samples with different molar ratio of S:GeO2 (=
14.17, 16.17, 18.17 and 20.17), indicating that the high pure phase of 1 could be harvested.
(a) (b)
(c) (d)
Figure S4: (a) Temperature dependent PXRD patterns of 1 in 298473 K in the air (b) PXRD patterns of the samples as-prepared and soaked in 2 M H2SO4 for five days for 1.
Figure S5: EPR spectrum of the sulfuric acid solution used to soak crystalline sample of 1.
Figure S6: Comparison of PXRD pattern between the samples as-prepared and used for impedance measurement (a) in 123473 K under N2 atmosphere and (b) in 298343 K under 98% RH of 1.
(a) (b)
Figure S7: (a) Comparison of PXRD patterns of as prepared and ball milled samples of 1 (b, c) SEM images of the ball milled sample of 1 in different magnifications. The sample used for PXRD and SEM measurements was ball milled for three hours.
Figure S8: XPS of C1s peak in the measurement for the samples of (a) grounded and (b) as prepared crystals of 1.
(a) (b)
(a)
(b) (c)
Figure S9: Plots of conductivity against temperature in (a) the first heating process from 298 to 473 K (b, c) the first cooling process from 473 to 123 K (d, e) the second heating process from 128 to 473 K (f) the second cooling process from 468 to 298 K.
(c) (d)
(e) (f)
Figure S10: Real part of impedance spectra of 1 at the selected temperatures in 298473 K and 1107 Hz under N2 atmosphere in the first heating process.
Figure S11: Real part of impedance spectra of 1 at the selected temperatures in 123473 K and 1106 Hz under N2 atmosphere in the first cooling process.
Figure S13: Real part of impedance spectra of 1 at the selected temperatures in 298473 K and 1106 Hz under N2 atmosphere in the second cooling process.
Figure S14: Frequency dependent AC conductivities in N2 atmosphere at (a) 298 K (b) 353 K (c) 373 K (d) 468 K in four sequential heating-cooling cycles.
(a) (b)
(c) (d)
Figure S15: (ac) Nyquist plots at the selected temperatures (d) curve of conductivity against temperature in the form of ln vs. 1000/T for 1 under N2 atmosphere in the first heating run.
Figure S16: Images of (a) as-prepared and (b) heated at 105 C for 1 hour samples.
(c) (d)
(a) (b)
Figure S17: Current against time Plots and Ie-V curves of 1 at 298, 303, 308 and 313 K under 98% RH.
Figure S19: Current against time plots and Ie-V curves of 1 at 338 and 343 K under 98% RH.
Figure S20: Ie-V curves of 1 at 298 K under Argon atmosphere.
Figure S22: (a) I-V Plots at the selected temperatures and the I and V values were obtained from the Chronoamperometry measurements under 98% RH (b) temperature dependent electron conductivities at the selected temperatures in 298343 K, which were obtained from I-V and EIS analyses under 98% RH, respectively, for 1.
Figure S23: (a) Plot of ln(T) versus 1000/T for ion conduction and (b) ln() versus 1000/T for electron conduction of 1 at the selected temperatures in 298343 K and
(a) (b)
Table S1: Coordination number and effective ionic radius of ions in 11
Ion Coordination Number Effective Ionic Radius / Å
S2- 6 1.84
2 0.46
4 0.60
Cu+
6 0.77
4 0.57
5 0.65
Cu2+
6 0.73
4 1.37
6 1.38
7 1.46
8 1.51
9 1.55
10 1.59
K+
12 1.64
Ge2+ 6 0.73
4 0.39
Ge4+
6 0.53
References
1. www.knowledgedoor.com (accessed July 2, 2020).
