Electronic Supplementary Material (ESI) for RSC Advances.

This journal is © The Royal Society of Chemistry 2014

Supporting Information

Intrinsic and Extrinsic Proton Conductivity

in Metal-Organic Frameworks

S. Tominaka,a,b* and A. K. Cheethama*

a
Department of Materials Science and Metallurgy, University of Cambridge, Charles Babbage Road, Cambridge CB3
0FS, United Kingdom. Fax: +44 1223 334567; Tel: +44 (0)1223 767061; E-mail: [email protected].
b
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS),
Ibaraki 305-0044, Japan. Tel: +81 (0)29 860 4594; E-mail: [email protected]

Contents

S1. Experimental details

S2. Single crystal diffraction data

S3. Pawley fitting of PXRD patterns

S4. Crystal structure of TTF nitrate

S5. Single-crystal AC impedance data

S6. Hydrogen bond networks in [Fe(ox)(H2O)2]

S7. Powder AC impedance data and analyses

S8. Data for plotting Figure 4

S9. Thermogravimetric analyses

1
S1. Experimental details
Structure determinations. The crystal structure was determined by single crystal
diffractometry using an Oxford Diffraction Gemini A Ultra X-ray diffractometer with Mo Kα
radiation (λ = 0.71073 Å) operated at 50 kV and 40 mA. Data were collected under ambient
conditions. Data collection, unit cell determination and refinement, absorption correction and data
reduction were performed using the CrysAlisPro software from Agilent Technologies. An analytical
absorption correction was performed by applying a face-based absorption correction as well as a
spherical absorption correction.
The unit cell of 1 was indexed using twin finding function of the CrysAlisPro software. Then,
the best matched cell was used for structure solution. The unit cell of 2 was indexed according to the
reported lattice values of [Fe(ox)(H2O)2].1 Then, the data was reduced on the basis of the C2/c space
group.
The Alert level A of the cif file of 2 is due to the presence of stacking faults (low quality data).
The Alert level B of 1, the big uncertainty in beta angle, is due to the presence of overlap peaks
between twins.

Conductivity measurements. Conductivities were measured by the AC impedance method

using an electrochemical instrument (Gamry Interface 1000) in the frequency range of 1 MHz to 0.01
Hz at an AC amplitude of 100 mV. For the single crystal measurements, the crystals were physically
contacted with two Au microelectrodes (200 nm thick) having a 80 μm gap deposited on a SiO 2 chip
as reported previously.2 Using pressure sensitive silicone adhesive polyimide film (CMF-100-020W
from MicroNova), crystals were gently picked up and mounted on the electrodes with their surface
exposed to moisture. Humidity was controlled by mixing a water-saturated nitrogen gas and a dry
nitrogen gas. The conductivity was measured along the long axis of crystals.
For the powder conductivity measurements, 100–130 mg of powder was gently ground using a
pestle and mortar, and then was pressed into a pellet (1 cmϕ, 0.6–0.7 mm thick) at 0.5 GPa with a few
drops of water. After drying under ambient conditions, the pellet was mounted in a closed powder
conductivity measurement cell with stainless steel electrodes (EQ-STC 10 mm, MTI Corporation,
USA) under saturated water vapour. Considering the pH value of the [Fe(ox)(H 2O)2]-saturated
solution (pH = 6.5–6.8 at 22°C), these electrodes are considered to work as blocking electrodes. The
temperature was controlled by keeping the cell in an oven. AC impedance spectra were collected after
equilibration time of >8 h with monitoring impedance spectra. At the first point, 90°C, resistance
decreased for more than 2 days and the impedance spectra became stable.

AC impedance analyses. Impedance spectra were analyzed by curve fitting with equivalent
circuits using the EchemAnalyst software from Gamry using equivalent circuits. The capacitance is
calculated from constant phase element (Z = Y –1(jω)–α), which is in general used for representing
inhomogeneous response to the external electrical field. In order to obtain accurate conductivity
values, impedance spectrum of the blank cell was measured (a resistance of 1.8 Ω with a series
inductance of 1.7 μH).
In the powder impedance data, the complicated features found in the range of 10–2–104 Hz
have a big capacitance of >10 –5 F (cf. the dry state has 1.6 × 10–10 F), these low frequency phenomena
are attributable to electrode reactions, probably pseudo-capacitance of stainless steel electrodes. Thus,
the impedance in the range of 104–106 Hz is attributable to the bulk ion conduction. Since inductance
originating from wires etc. has influence on this frequency range, in order to measure the resistance
accurately, the spectra were analyzed by curve fitting using an equivalent circuit having a series
inductance (Fig. S7).
Though the pressure does not affect, after the measurements, PXRD measurement indicates
that 2 partially converted into 1, as expected from the synthetic procedure (data not shown).

2
 Powder diffraction. The PXRD samples were prepared by grinding the crystals gently
using mortar and pestle for 1 min. The data was collected using a Bruker-AXS D8 diffractometer with
Cu Kα radiation (λ = 1.5418 Å) in the Bragg–Brentano geometry. The patterns were analyzed by the
Pawley fitting using the GSAS-II software,3 and plotted with zero-shift correction and background
subtraction.

Thermal analyses. Thermogravimetric analysis and differential scanning calorimetry were

performed simultaneously using a TA Instruments Q600 SDT instrument with a nitrogen flow of 100
mL min−1 at a heating rate of 5 °C min −1, from room temperature to 600°C.

Solubility test. 10 mg of 1 was soaked in 45 mL H2O at RT or 90°C for 20 hours, then 40

mL of supernatant was dried at 90°C in air. 2 mg of black precipitate was recovered from the 90°C-
treated one, while negligible yellow precipitate could be recovered from RT-treated one (the
supernatant pH = 6.5–6.8 at 22°C, probably dominated by carbonate in air).

Synthesis of TTF nitrate. The tetrathiafulvalene (TTF) nitrate crystals were prepared by the
oxidation reaction of TTF (97%, Sigma-Aldrich) by nitric acid (50 μL, 70%, Fisher) in N,N-
dimethylformamide (DMF) (Fisher). In detail, TTF (20.5 mg) was dissolved in N,N-
dimethylformamide (5 mL), and then was cooled down in a fridge (~6°C). Cooled nitric acid (~6°C)
was gradually added to the solution, and then the solution was kept in the fridge for several days.
Deep red needles, prisms and hexagonal plates were recovered by vacuum filtration, and rinsed with
ethanol and chloroform. Though the morphologies are different, they have the same crystal structure,
which was confirmed by single crystal X-ray diffraction and powder X-ray diffraction. The chemical
composition was determined by elemental analysis at the Department of Chemistry, University of
Cambridge (found, calcd., for C12H8N2O6S8): C (27.15, 27.06), H(1.59, 1.51) and N (4.98, 5.26). CIF
files are available (CCDC 1020095 and 1020096).

3
S2. Single crystal diffraction data

Figure S1 | Ewald sphere images obtained by single crystal diffraction. Top, sample 1.
Middle, sample 2 with twin removal. Bottom, sample 2 (raw).

4
Figure S2 | Atom connectivity of 2 determined by the single crystal diffraction.

5
S3. Pawley fitting of PXRD patterns

Figure S3 | Pawley fitting of PXRD patterns of [Fe(ox)(H2O)2] 1 and 2.

Table S1 | Unit cells of [Fe(ox)(H2O)2] determined by X-ray diffraction

Sample 1 1 2 2 Literature1
Measurements SXRD (Mo Kα) PXRD (Cu Kα) SXRD (Mo Kα) PXRD (Cu Kα) SXRD (Mo Kα)
Crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic
Space group C2/c – C2/c – C2/c
a/Å 12.065(12) 12.0391(1) 12.209(4) 12.2113(4) 12.011(11)
b/Å 5.559(2) 5.5692(4) 5.5526(7) 5.5527(1) 5.557(5)
c/Å 9.817(9) 9.9393(1) 9.865(3) 9.8658(2) 9.920(9)
β (°) 128.03(15) 128.5353(6) 128.20(6) 128.207(2) 128.53(3)
V / Å3 518.6(13) 521.29(4) 525.6(5) 525.65(2) 518.0(8)
d / g cm–3 2.304 2.292 2.274 2.273 2.307
Temperature 293 RT 297 RT 293
Goodness of fit R1 = 8.79%, Rw = 4.27%, R1 = 10.9%, Rw = 3.23%, R1 = 3.74%,
wR2 = 24.06%, Pawley fitting wR2 = 25.78%, Pawley fitting wR2 = 9.31%,
GOF = 1.307 GOF = 1.246 GOF = 1.387

6
S4. Crystal structure of TTF nitrate

Figure S4 | Crystal structure of TTF nitrate at 120 K.

7
S5. Single-crystal AC impedance data

Figure S5 | Single-crystal impedance data. Complex-plane impedance diagrams of (a)

[Fe(ox)(H2O)2] 1, (b) [Fe(ox)(H2O)2] 2, and (c) Blank cell. (d) Bode plot of 1.

8
S6. Hydrogen bond networks in [Fe(ox)(H2O)2]

The negligible conductivity through the framework of 1 can be accounted for by

considering hydrogen bond networks as follows. The frequencies of O–H stretching bands in
infrared spectra are an indicator of the strength of hydrogen bonds and can be correlated to
the O–O distances in the O–H···O hydrogen bonds.4 In broad terms, O–O distances in the
range 2.7–2.95 Å are preferred for proton conduction, 5 and these show O–H stretching bands
around 3200–3500 cm–1.4 1 contains such preferred hydrogen bonds having an O–O distance
of 2.74 Å (Fig. S10a), to which the main sharp peak of O–H stretching at 3320 cm–1 (Fig. S10b)
can be assigned. However, they are localized between water molecules and oxalate
molecules in different [Fe(ox)(H2O)2] chains as ox–H2O–ox units. For long-range conduction,
proton transport through ox–H2O–ox units in the same chain is required. The O–O distance
between water molecules and oxalate molecules in the same chains is 2.97–3.03 Å, to which
the 3500 cm–1 shoulder can be assignable. This distance is far longer than the requirements
for good proton mobility, thus the protons are localized in the interchain hydrogen bonds, as
indicated by the IR intensity.

Figure S6 | Potential proton conduction paths in the [Fe(ox)(H2O)2] framework. (a) The
O–O distances in 1 determined by single crystal diffraction (in Å). (b) FT-IR spectrum of 1
and 2.

9
S7. Powder AC impedance data and analyses

Figure S7 | Powder impedance data of [Fe(ox)(H2O)2] 1. a,b Complex-plane impedance

diagrams. c, Bode plot, temperature dependence at 100%RH. d, Bode plot (20°C, 0%RH
and 100%RH).

10
Figure S8 | Powder impedance data of [Fe(ox)(H2O)2] 2. a,b Complex-plane impedance
diagrams. c, Bode plot (20°C, 0%RH and 100%RH).

11
Figure S9 | Impedance data analysis of [Fe(ox)(H2O)2] 2 powder. (a) Equivalent circuit for
representing bulk resistance Rbulk and capacitive behaviour CPEbulk (CPE = constant phase
element), two electrode reactions (Rct1, CPEct1, Rct2 and CPEct2) probably attributable to
pseudo-capacitive reactions on stainless steel surface, and a Warburg Impedance for the
diffusion term associated with the electrode reactions. A inductance is used for representing
parasitic inductance from cables and cells. Curve fitting in the Bode plots (b) and in the
complex-plane impedance diagram (c). The high frequency region is often deformed due to
the presence of the parasitic inductance, thus the use of inductance is important to obtain
bulk resistance. The behaviour in this high frequency region, >10 kHz, depends on the
capacitance or CPEbulk and L, it is better to include L even when the behaviour looks a
semicircle.

12
S8. Data for plotting Figure 5 and S8
There are two different Arrhenius equations,

σT = σ01 exp(–Ea1/RT) …(1)

σ = σ02 exp(–Ea2/RT) …(2)

Where σ is conductivity, T is absolute temperature, Ea is activation energy, and R is the gas constant.
The equation 1 is based on random theory, while equation 2 has not theoretical justification though it
has been used widely.6 Recently, equation 1 seems used more widely, especially in MOF community.
In order to estimate σ0 and Ea, the following Arrhenius plots are used.

Log(σT) = Log(σ01) –Ea2/(2.303RT) …(1’)

Log(σ) = Log(σ02) –Ea2/(2.303RT) …(2’)

By linear approximation of these plots, values of σ0 and Ea are obtained, but the values
obtained using different plots are not exactly the same. The difference is the quasi-linear relation of
Log(T) vs 1/T, which can be approximated as linear in narrow temperature range. Table S2
summarizes the difference of σ0 and Ea in the different temperature range.
Using the values in Table S2, the σ0 and Ea values obtained using equation 2’ were converted
and summarized in Table S3 and S4.

Table S2 | Parameters for converting σ0 and activation energy obtained by two different styles of Arrhenius
plots
Temperature range (°C) Log(σ01)– Log(σ02) (Ea1– Ea2) / meV R2
0–30 2.893 24.8 0.9998
0–60 2.917 26.2 0.9993
0–90 2.934 27.1 0.9986
0–100 2.940 27.5 0.9983
0–150 2.968 29.2 0.9967
0–200 2.994 30.9 0.9949
10–60 2.922 26.5 0.9995
10–90 2.941 27.6 0.9989
10–100 2.955 28.5 0.9987
10–150 2.983 30.3 0.9972
10–200 3.001 31.5 0.9955
20–60 2.929 26.9 0.9997
20–80 2.948 28.1 0.9994
20–90 2.948 28.1 0.9992
20–100 2.955 28.5 0.9990
20–150 2.893 30.3 0.9977
20–200 3.009 32.0 0.9961

13
Table S3 | σ0 and Ea of MOF-based proton conductors.
Log(σ0
Name Type Ea / eV σ / S cm–1 T/K Reference (DOI)
/ S cm–1K–1)
[Fe(ox)(H2O)2](1) Dense 2.31 0.17 5.7 × 10–4 293 This work
–3
[Fe(ox)(H2O)2](2) Dense 2.05 0.14 1.5 × 10 293 This work
–3
[Fe(ox)(H2O)2] Dense 5.84 0.37 1.3 × 10 298 10.1021/ja808681m
–5
[Mn(dhbq)(H2O)2] Dense 2.45 0.26 4.0 × 10 300 10.1246/cl.2009.654
–6
(HOC2H4)2-dtoa-Cu Dense 0.01 0.19 2.2 × 10 300 10.1246/bcsj.52.3296
–3
(NH4)2(adp)[Zn2(ox)3]·3H2O Layered 11.03 0.63 8.0 × 10 298 10.1021/ja9040016

PCMOF3 Layered 1.31 0.19 3.5 × 10–5 298 10.1021/ja107035w

Ca-SBBA Layered 1.30 0.23 8.6 × 10–6 298 10.1039/c2cc31135f

–5
Sr-SBBA Layered 7.59 0.56 4.4 × 10 298 10.1039/c2cc31135f
–8
[Al(OH)(14bdc)]·H2O, MIL-53(Al) Porous 2.78 0.47 2.3 × 10 298 10.1021/ja109810w
–8
[Al(OH)(14bdc-NH2)]·H2O, MIL-53(Al)-NH2 Porous 2.45 0.45 2.3 × 10 298 10.1021/ja109810w
–7
[Al(OH)(14bdc-OH)]·1.5H2O, MIL-53(Al)-OH Porous 0.66 0.27 4.2 × 10 298 10.1021/ja109810w
[Fe(OH)(14bdc-(CO2H)2)]·H2O,
Porous 0.33 0.21 2.0 × 10–6 298 10.1021/ja109810w
MIL-53(Fe)-(CO2H)2
[Mo5P2O23][Cu(phen)(H2O)]3·5H2O Porous 1.67 0.23 2.2 × 10–5 301 10.1039/c1cc15162b
–5
[In(5TIA)2]·(NH2(CH2)2)(H2O) Porous 0.50 0.137 5.35 × 10 301 10.1039/c2cc31527k

[In(13bdc)2]·N(CH3)4 Porous 6.69 0.47 2.2 × 10–4 301 10.1039/c2cc31527k

[Cd(5TIA)2]·2(NH2(CH2)2)(H2O) Porous 2.76 0.163 3.61 × 10–3 301 10.1039/c2cc31527k

–3
(NH4)4[MnCr2(ox)6]·4H2O Porous 3.40 0.23 1.1 × 10 298 10.1021/ja206917z
–3
PCMOF-5(98%RH) Porous 2.75 0.19 2.5 × 10 333 10.1021/ja310435e
–5
PCMOF-5(90%RH) Porous 3.75 0.35 2.0 × 10 293 10.1021/ja310435e

Prussian blue Porous 3.33 0.22 1.2 × 10–3 293 10.1021/ja1003851

[Zn(l-LCl)(Cl)]·2H2O Porous 3.77 0.34 4.45 × 10–5 304 10.1021/ja2078637

–3
[La(dtmpH5)]·7H2O Porous 4.98 0.275 8.0 × 10 301 10.1039/c2dt11992g
[Ca(135btcH)(H2O)]·H2O
Porous 1.60 0.18 1.2 × 10–4 298 10.1039/c2cc34006b
Ca-BTC-H2O
Ca-PiPh-tA-I Porous 3.13 0.23 5.7 × 10–4 297 10.1021/ja500356z

Ca-PiPh-tA-II Porous 4.46 0.32 3.6 × 10–4 297 10.1021/ja500356z

–5
Im@[Al(OH)(14ndc)] Anhydrous 5.63 0.6 2.2 × 10 393 10.1038/nmat2526
–7
Im@Al[OH)(14bdc)], Im@MIL-53(Al) Anhydrous 7.13 0.9 1.0 × 10 393 10.1038/nmat2526
–3
His@Al[OH)(14ndc)] Anhydrous 2.83 0.25 1.7 × 10 423 10.1002/anie.201102997
–4
Tz@βPCMOF2 Anhydrous 5.36 0.54 2.0 × 10 423 10/1038/NCHEM.402
–4
[Zn(H2PO4)2(Tz)2] (Tz = 1,2,4-Triazole) Anhydrous 6.21 0.63 1.2 × 10 423 10.1021/ja304693r

14
Table S4 | σ0 and Ea of classical solid-state proton conductorsa

Log(σ0
Name Type Conduction path Ea / eV σ / S cm–1 T/K Reference (DOI)
/ S cm–1K–1)
H2O (ice) Dense Defect 6.57 0.576 1.0 × 10–7 260 10.1017/CBO9780511524806.004
–8
KH2PO4 Dense Defect 4.48 0.596 1.0 × 10 300 10.1017/CBO9780511524806.004
–8
KH2AsO4 Dense Defect 5.99 0.686 1.0 × 10 300 10.1017/CBO9780511524806.004
BYZ = BaZr0.8Y0.2O3-δ Dense Defect 6.47 0.696 1.1 × 10–1 773 10.1038/NMAT2837
–6
β-Alumina (NH4 ) +
Dense Cation sites 5.48 0.526 1.5 × 10 300 10.1017/CBO9780511524806.004
–10
β-Alumina (H3O ), +
Dense Cation sites 6.34 0.826 1.0 × 10 300 10.1017/CBO9780511524806.004
dried
H3O·[Zr2(PO4)3], Dense Cation sites 6.31 0.586 1.0 × 10–6 300 10.1017/CBO9780511524806.004
NASICON
(H3O)5[GdSi4O12] Dense Cation sites 4.97 0.506 1.0 × 10–6 300 10.1017/CBO9780511524806.004
–4
H3O·ClO4 Dense Rotational 4.31 0.316 3.4 × 10 300 10.1017/CBO9780511524806.004
disorder
CsHSO4 (420K) Dense Rotational 4.89 0.356 1.0 × 10–2 420 10.1017/CBO9780511524806.004
disorder
[H3PW12O40]·21H2O, Dense H2O network 7.40 0.426 6.0 × 10–3 300 10.1017/CBO9780511524806.004
Polyoxometalate
[H3SiW12O40]·28H2O, Dense H2O network 8.10 0.426 3.0 × 10–2 300 10.1017/CBO9780511524806.004
Polyoxometalate
[H3PMo12O40]·29H2O, Dense H2O network 4.66 0.176 1.7 × 10–1 300 10.1017/CBO9780511524806.004
Polyoxometalate
H3O·[UO2PO3]·3H2O Layered Interlayer, 6.46 0.376 5.0 × 10–3 301 10.1017/CBO9780511524806.004
water-assisted
α-Zr(HPO4)2·H2O Layered Interlayer, 2.98 0.326 1.0 × 10–5 298 10.1002/9781119962502.ch10
water-assisted
Ce(HPO4)·3.8H2O Layered Interparticle phase 2.08 0.196 2.0 × 10–4 298 10.1017/CBO9780511524806.004
4+ –5
Zeolite A (NH ), Porous Micropores 8.08 0.63 1.1 × 10 300 10.1016/0025-5408(82)90106-4
10.8 wt% H2O
NafionTM Polymer Water channel 5.30 0.246 5.0 × 10–2 300 10.1017/CBO9780511524806.004
–1
BMITf@Nafion Anhydrous Ionic liquid 4.26 0.231 1.1× 10 453 10.1149/1.1393153
polymer network
Imidazole@SPEK Anhydrous Imidazole network 3.80 0.282 1.3× 10–1 473 10.1016/S0013-4686(97)10031-7
polymer
SnO2·2H2O Gel Interparticle phase 2.87 0.226 4.0 × 10–4 300 10.1017/CBO9780511524806.004
–3
Sb2O5·5.4H2O Gel Interparticle phase 3.47 0.186 7.5 × 10 300 10.1017/CBO9780511524806.004
HClO4·5.5H2O Liquid H2O network 3.72 0.046 3.0 300 10.1017/CBO9780511524806.004
(liquid)

BMITf = 1-butyl, 3methyl imidaxolium trifluoromethane sulfonate (ionic liquid). SPEK = sulfonated polyetherketone.

15
Figure S10 | Comparison of proton conductivity in metal-organic frameworks (MOFs) and
classical solid-state materials. Relationship between the pre-exponential factor σ0 of the
Arrhenius Equation and the activation energy Ea are plotted. The top left dotted lines show the
gradients where conductivity values of different materials are the same (302, 403 and 504 K). MIL-
53(M) is [M(OH)(14bdc)], where bdc is benzenedicarboxylic acid. Im@, His@ and Tz@ mean
incorporation of imidazole, histamine and 1,2,4-triazole molecules, respectively. -NH3, -OH and -
CO2H mean functional groups of modified bdc molecules. 14ndc = 1,4-naphthalenedicarboxylic acid.
dtmp = hexamethylenediamine tetra(methylenephosphonic acid). adp = adipic acid. POM =
polyoxometalate (H3PMo12O40•29H2O or H3SiW 12O40•28H2O). YBZ = yttrium-doped barium zirconate.

16
S9. Thermogravimetric analyses

Figure S11 | Thermogravimetric analysis of [Fe(ox)(H2O)2] 1 and 2. Simultaneous

differential scanning calorimetry (DSC)-thermogravimetric analysis (TGA) recorded with N2
flow of 100 mL min–1 at scan rate of 5 °C min–1.

17
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2. Tominaka S, Henke S, Cheetham AK. Coordination polymers of alkali metal trithiocyanurates: structure determinations
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3. Toby BH, Von Dreele RB. GSAS-II: the genesis of a modern open-source all purpose crystallography software package.
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4. Novak A. Hydrogen bonding in solids correlation of spectroscopic and crystallographic data. Large Molecules, vol. 18.
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