High hydroxide conductivity in a chemically stable crystalline metal-organic framework containing a water-hydroxide supramolecular chain

Article abstract of DOI:10.1039/c6cc04436k

A chemically stable cationic MOF encapsulating an in situ formed water-hydroxide supramolecular anionic chain is realized for high hydroxide (OH^-) ion conductivity in the solid-state (Type A). High OH^- ion conductivity and low activation energy of the MOF demonstrate the advantage of the in situ incorporation of OH^- ions to achieve efficient OH^- ion conduction in the solid-state.

Full text of DOI:10.1039/c6cc04436k

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High Hydroxide Conductivity in a Chemically Stable Crystalline
Metal-Organic Framework Containing Water-Hydroxide
Supramolecular Chain
Received 00th January 20xx,
Accepted 00th January 20xx
a
b,c
a
d
DOI: 10.1039/x0xx00000x
Sanjog S. Nagarkar, Bihag Anothumakkool, Aamod V. Desai, Mandar M. Shirolkar, Sreekumar
b,c
a,e
Kurungot and Sujit K. Ghosh *
www.rsc.org/
A chemically stable cationic MOF encapsulating in-situ formed conducting species in MOF matrix is known to provide
6
water-hydroxide supramolecular anionic chain is realized for high enhanced ionic conductivity. However, till now only post-
g
-
hydroxide (OH ) ion conductivity in solid-state (Type A). High OH synthetic modification approach has been utilized to achieve
-
-
-
ion conductivity and low activation energy of MOF demonstrates hydroxide (OH ) and chloride (Cl ) ion conduction in MOFs
-
the advantage of in-situ incorporation of OH ion to achieve (Type B).
6a,7
-
Especially, the OH ion conductors are getting
-
efficient OH ion conduction in solid-state.
increased attention for the development of low cost and
8
efficient alkaline fuel cells.
-
In organic polymers, the high OH conductivity is achieved
Metal-organic frameworks (MOFs) are porous crystalline solid,
which combine the properties arising from both inorganic and
1
organic building units in a single material. The designable
-
by covalently bound onium-class cations and free OH anions
8
under humid conditions. Thus we hypothesize that, the high
,9
-
OH conductivity in MOFs might be achieved if one can
architecture, high-surface area, host-guest chemistry,
crystalline nature and responsiveness make MOFs
synthesize cationic MOF framework with in-situ incorporated
-
free OH as counter ions hydrogen bonded with water
2
indispensable material for future smart technology. MOFs
have already been employed in diverse areas including gas
molecules inside the MOF matrix and will provide optimum
-
concentration and path for efficient OH ion transport through
storage/separations,
catalysis,
sensing,
biomedical
electrical
applications, magnetism,
crystallography,
3
matrix (Scheme 1). Despite the advantages, to the best of our
-
knowledge in-situ incorporation of OH ion (Type A OH ion
-
conductivity, and clean energy applications. In recent past,
MOFs have developed as new class of solid-state ion
7
conductor) for synthesis of efficient OH conducting MOF is
a
-
4
conducting material. The design flexibility of MOFs along with
7
yet to be realized.
cheap starting materials, good thermal stability, and feasibility
in hybridization offers several advantages for development of
solid-state ion conductor. Also, owing to crystalline nature in
combination with design flexibility, MOFs can serve as
promising model compound for better understanding of ion
transport mechanism and optimizing the conduction path on
5
nano-scale. The MOFs have shown great potential as proton
conducting material working in humid and/or anhydrous
6
conditions. Unlike, proton conducting MOFs, the anion
conducting MOFs are still rare. The in-situ incorporation of
Scheme 1 Schematic representation of cationic MOF with anionic supramolecular chain
of hydroxide anions and water molecules inside the MOF pore for efficient hydroxide
ion conduction.
a.
Indian Institute of Science Education and Research (IISER) Pune,
Dr. Homi Bhabha Road, Pune - 411008 (India).
E-mail: sghosh@iiserpune.ac.in
Physical and Materials Chemistry Division,
National Chemical Laboratory (NCL), Pune - 411008 (India).
Academy of Scientific and Innovative Research (AcSIR),
Anusandhan Bhawan, New Delhi - 110001 (India).
Hefei National Laboratory for Physical Science at the Microscale, University of
Technology of China, Hefei, Anhui - 230026 (People’s Republic of China).
Centre for Research in Energy & Sustainable Materials, IISER Pune.
b.
Regardless of designable nature of MOF framework, the
tailored arrangement of ions and/or guest molecules in MOF
matrix is difficult. Also owing to the large number of possible
MOF structures, the synthesis and characterization of every
possible MOF is not feasible. In this regard, identification of
c.
d.
e.
Electronic Supplementary Information (ESI) available: [Details of synthetic potential MOF structures reported in literature using screening
protocols, SEM images, TGA profiles, PXRD patterns, Gas adsorption isotherms,
Rietveld refinement details]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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was determined via Rietveld refinement analysis of powder
pattern (see supporting information). The Rietveld refinement
gave good fit with Rwp = 3.2 (Fig. 1a, Table S1).
The compound
1 crystallizes in space group P31m same as
reported compound. The central Ni(II) exhibit distorted
1
-
octahedral geometry with N
3 3
O donor set from three pymca
1
+
ligands forming tris-chelated cationic [Ni
2
+
(μ-pymca)
3
]
subunit
unit forms propeller
like chirality connecting three adjacent subunit forming(6,3)
1
2 3
(Fig. 1b). The cationic [Ni (μ-pymca) ]
2D cationic honeycomb structures in ab plane (Fig. 1c, d). The
2D honeycomb sheets are arranged one above the other in AA
fashion with inter layer distance of ~6 Å forming 1D channel
Fig. 1d; S8). These channels must be filled with anions and/or
solvent molecules to balance the overall charge of cationic
(
-1
framework. The strong peak at 3641 cm in FT-IR spectra of
MOF was assigned to stretching vibration ʋ(OH) of hydrated
Fig. 1 (a) Fitting of raw PXRD data of compound 1by Rietveld analysis. The black and
1
redlines represent experimental and fitted data respectively. The residual discrepancy
-
14
is shown in blue. (b) Tris-chelated cationic [Ni2(μ-pymca)3]1+ subunit with propeller OH ions (Fig. S5). The temperature-programmed desorption
like structure. (c) 2D cationic honeycomb sheets of MOF 1 arranged in AA fashion mass spectrometry analysis of multiple batches of MOF
forming 1D hexagonal channel filled with OH- and water molecules. (d) Electron density
1
2
showed release of water molecules (H O m/z = 18), however
distribution for MOF 1 derived from MEM analysis in ab plane (002). Contour lines are
drawn from 0 to 0.5 e/Å3 at interval of 0.05 e/Å3.
2
no CO (m/z = 44) release was observed from the MOF 1
-
confirming the existence of free OH ion in MOF matrix (Fig.
S9). Thus the overall molecular formula can be assigned as
based approach is extremely useful to get compounds with
1
0
[Ni
central metal atom is saturated the hydroxide anion must be
present inside the pore. To further confirm the structure of
2 3 2
(μ-pymca) ]OH∙nH O. As the coordination number of
desired structure and/or property. Further the knowledge
gained from these compounds can be used for design and
development of efficient solid-state ion conducting materials.
1
and arrangement of guest molecules by electron density
visualization we performed maximum entropy method (MEM)
analysis via Rietveld refinement of PXRD data. Fig. 2d shows
The [M
2
(μ-pymca)
3
]OH∙nH
2
O
MOF composed of
2
dimentioanal (2D) honeycomb cationic framework [M
+
2
(μ-
1
]
pymca)
-
3
forming 1D channel filled with in-situ formed free
iso-density contour maps of 1. The MEM analysis of 1 also
OH ions and water molecules creating 1D anionic
supramolecular chain, which can provide an efficient path for
confirmed the formations of 2D honeycomb sheet structure
with alternate arrangements of pyrimidine rings (Fig. S8). The
charge localization at the centre of hexagonal ring suggests the
arrangements of hydroxide anions along the barycentre of
hexagonal rings as expected.
-
11
OH transport (Type A). However the MOFs were never
realized for ionic conductivity previously.
We synthesized Ni(II) based new isostructural MOF [Ni
pymca) ]OH∙nH O ( ) via hydrothermal reaction between
pymcaH and NiCl at 160 °C for 20 h as greenish crystalline
2
(μ-
3
2
1
Thermogravimetric analysis (TGA) of
1
under
N
2
2
atmosphere showed thermal stability up to 300 °C with ~10 %
weight loss is assigned to removal of water molecules (Fig.
S10). Above 300 °C the compound starts decomposing slowly
with 70% weight loss. The variable temperature PXRD also
powder. The solid was insoluble in common organic solvents
and water. The elements present in bulk sample was
determined using energy dispersive X-ray spectroscopy (EDX)
analysis of multiple particles of MOF over wide area and
multiple synthesis batches (Fig. S1-S4). The EDX analysis of
confirmed the thermal stability of
heating and cooling cycles without alteration of overall
structure (Fig. S11). To assess the porosity of , N adsorption
isotherm at 77 K was measured. The N adsorption showed
negligible gas uptake at 77K indicating nonporous nature of
(Fig. S12). Further to determine the chemical stability of , we
1 up to 300 °C in both
multiple hexagonal particles and multiple batches of
displayed the presence of Ni, C, N and O in in bulk sample.
FT-IR spectrum of as-synthesized MOF afforded aromatic C-H
1
1
2
1
2
-1
1
stretching frequency around 3090 cm and decrease in
-
1
-1
ʋ(COO)as frequency 1654 cm of pymcaH to 1631 cm in
1
1
also
1
supported the bond formation (Fig. S5). The Raman spectra
2
treated ~50 mg of as-synthesized compound with 25 mL of
boiling water overnight. The compound remained highly stable
in boiling water for overnight without any loss in crystallinity
or peak shifting as confirmed from PXRD (Fig. S13). The FT-IR
spectrum of water treated sample stayed unaltered indicating
no change in coordination environment upon boiling water
treatment (Fig. S14). The Rietveld refinement of water treated
sample also confirmed the stability of MOF (Fig. S15). In
addition to water, base stability is very crucial for successful
performance of hydroxide ion conducting material. We
-1
of
1 exhibited strong peak at 3083 cm corresponding to
aromatic ʋ(C-H) vibrations, which also confirmed the ligand
incorporation (Fig. S6). This conclusion was further supported
1
1
by solid-state H-NMR (ss- H-NMR) of
of displayed the peak ~3.0 ppm assigned to aromatic protons
Fig. S7).
crystal suitable for single crystal X-ray diffraction analysis were
unsuccessful. However, the as-synthesized powder of was
sufficiently crystalline to give intense diffractions identical to
(μ-pymca) ]OH∙nH O diffraction peaks. The structure of
1, in which the spectra
1
7
b,13
(
The numerous attempts to obtain 1 as a single
1
checked the base stability of
1 in pH range 7 to 14. Compound
[M
2
3
2
1
1
showed an excellent base stability and remained highly
2
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stable up to pH 14 as determined form PXRD and FT- IR (Fig. concluded that, upon increasing humidification the water
S16-S17). Encouraged from this we further investigated the uptake in hydrophilic 1D hexagonal channels increase and the
stability of
compound
1
upon treatment with NaOH (1 Normal). The arrangement of these adsorbed water molecules is strongly
-
also exhibited high stability towards 1 Normal related to the observed high OH conductivity. The water
1
NaOH and remained highly crystalline (Fig. S13). Similar to adsorption isotherm of dehydrated sample showed adsorption
water treated MOF sample, the Rietveld refinement of NaOH of water molecules at very low relative pressure (Fig. 2c). This
treated sample also confirmed the base stability of MOF (Fig. clearly indicates that the dehydrated compound has high
S15). The ICP analysis of
.30% degradation after 8h and 0.31% after 24h (Table S3). humid condition. We also measured conductivity of
The SEM analysis of as-synthesized and NaOH treated sample exposing it to D O vapours (Fig. 2d). The D O exposed sample
revealed that compound morphology remained unaffected by showed conductivity of 4.6 × 10 Scm which is less than H
base treatment (Fig. S18). The FT-IR spectra of NaOH treated exposed sample as expected due to isotope effect. This also
sample established the unaltered coordination environment confirms the vital role of H O in conduction behaviour of MOF
around central metal atom in compound (Fig. S14).
1
treated with 1N NaOH showed affinity for water and regains water of crystallization under
0
1
by
2
2
-5
-1
2
O
2
1
1.
-
Fig. 2 (a) Nyquist plot for MOF
conductivity of MOF upon increasing humidification. (c) Water sorption
isotherm of MOF at 298K (filled symbol adsorption, hollow symbol desorption).
d) Nyquist plot for MOF at 27 °C and 99 % RH upon D O exposure.
1
at 27 °C and 99 % RH. (b) Increase in OH ion
Fig.
3
(a) Arrhenius plot for the hydroxide conducting MOF
at 27 °C and 99 % RH. (c)
at 27 °C between 50 to 99 % RH.
1. (b) Time
1
dependent conductivity measurements of MOF
1
1
Humidity cycling study of MOF
1
(
1
2
-
The OH conductivity measurements were also performed
at different temperatures and constant humidity (95% RH)
which showed increase in hydroxide conductivity from 2.5 ×
To evaluate the hydroxide ion conducting ability of MOF
we performed AC impedance measurements using compacted
pellet of powder sample under atmosphere. The
conductivity was determined from Nyquist plot. Fig. 2a shows
Nyquist plot for compound at 27 °C 99% relative humidity
RH). Similar to literature reports, the exhibit single
1,
-5
-1
-5
-1
N
2
1
0
Scm at 30 °C to 5.6 × 10 Scm at 90 °C (Fig. 3a, S22).
The activation energy E was calculated to be 0.19 eV which is
quite low. The observed activation energy is comparable to the
a
1
-
17
(
1
hydrated OH ions in liquid and suggests the favourable and
-
efficient transport of OH ions through 1D channels of MOF 1.
semicircle with tail at low frequency in Nyquist plot indicating
3
q,15
-
-
The transport mechanism of OH ions in presence of water has
ionic conductivity through bulk material.
The OH
-6
-1
was found to be 1.3 × 10 Scm at 27 °C and
1
been supported by charge-migration model. Similar to
8
conductivity of
1
-
+
moderate humidity (~50 % RH). The OH conductivity was
found to be increasing with increasing humidification and
3
Grotthuss mechanism observed for hydrated H O ions it is
-
expected that the charge on OH ions migrates through
protons transferred from adjacent water molecule via
hydrogen bonding network resulting in low activation energy.
Thus the formation of extended hydrogen bonded
-4
-1
reaches maximum conductivity value of 0.8 ×10 Scm at 27
-
C and 99 % RH (Fig. 2a,b, S19). The present OH ion
°
conductivity value is highest amongst Type A anion conducting
-
MOFs and ~4 orders higher than previously reported OH
-
supramolecular chain of OH and water molecules improve the
-
OH ion conductivity of the material. The detailed investigation
7
conducting MOFs, with only exception being the post
7
d
synthetically modified (Type B) Ni based MOF. Although the
of mechanism and structure property relation for further
-
improvements in the OH conducting ability of the materials
-
present conductivity is lower than best known inorganic OH
1
6
conducting materials, the high base stability as against onium
class organic polymer is an important advantage for real time
are underway. Importantly, the time dependent conductivity
measurement did not show any loss in conductivity
performance even after 40 h (Fig. 3b). Also, the humidity
cycling study between 50 to 99 % RH also revealed that the
compound is resistant to the high humidity changes (Fig. 3c).
application. The overlapping PXRD and FT-IR patterns of MOF
before and after impedance analysis confirm the integrity of
the MOF during impedance analysis (Fig. S20-S21). We
1
1
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The nonporous nature of
1
towards feed gases like H
2
and O
2
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gases at RT is also advantageous to avoid possible fuel mixing,
however the detailed investigation is required (Figure S23).
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In conclusion, we report here a highly hydroxide
5
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2
2
3
-
-
incorporated OH anions (Type A, OH ion conductor) for the
first time. The MOF exhibits excellent chemical stability
towards boiling water and highly basic conditions and showed
-4
-1
hydroxide conductivity of 0.8 × 10 Scm at 27 °C and 99 % RH
-
which is comparable to the best known OH conducting MOF
reports. Further the activation energy for hydroxide
conduction was found to be 0.19 eV which is comparable to
-
free OH ions in liquid suggest the interference free transport
Kurungot and S. K. Ghosh, Angew. Chem. Int. Ed., 2014, 53
,
-
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materials.
7
8
S. S. N. and B. A. thank CSIR India for research fellowship. A. V.
D. thanks IISER Pune for research fellowship. This work was
partially supported by MHRD-FAST.
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