magnetochemistry

Article
Local and Average Structural Changes in Zeolite A
upon Ion Exchange
Lisa Price 1 , Ka Ming Leung 2 and Asel Sartbaeva 1, * ID

1 Department of Chemistry, University of Bath, Bath BA2 7AY, UK; [email protected]

2 Inorganic Chemistry Lab, South Parks Road, University of Oxford, Oxford OX1 3QR, UK;
[email protected]
* Correspondence: [email protected]; Tel.: +44-(0)-1225-38-5410

Received: 21 August 2017; Accepted: 7 December 2017; Published: 12 December 2017

Abstract: The infamous ‘structure–property relationship’ is a long-standing problem for the design,
study and development of novel functional materials. Most conventional characterization methods,
including diffraction and crystallography, give us a good description of long-range order within
crystalline materials. In recent decades, methods such as Solid State NMR (SS NMR) are more widely
used for characterization of crystalline solids, in order to reveal local structure, which could be
different from long-range order and sometimes hidden from long-range order probes. In particular
for zeolites, this opens a great avenue for characterization through studies of the local environments
around Si and Al units within their crystalline frameworks. In this paper, we show that some
structural modifications occur after partially exchanging the extraframework Na+ ions with
monovalent, Li+ , K+ , Rb+ and NH4 + and divalent, Ca2+ cations. Solid state NMR is deployed to
study the local structure of exchanged materials, while average stricture changes can be observed by
powder diffraction (PXRD). To corroborate our findings, we also employ Fourier Transform Infrared
spectroscopy (FT-IR), and further characterization of some samples was done using Scanning Electron
Microscopy (SEM) and Energy-Dispersive X-ray spectroscopy (EDX).

Keywords: zeolite; solid state NMR; ion exchange; synthesis; characterization

1. Introduction
Zeolites are aluminosilicate porous minerals. Many zeolites occur in nature as aluminosilicate
minerals. To date, we can make more than 200 synthetic zeolites in the laboratory [1,2]. They are
classed as porous materials as they possess cages, channels and open void spaces within their highly
crystalline frameworks. Each zeolite framework has a unique structure, and because there is such a
variety of zeolite structures, there is also a very wide diversity of zeolite applications. Synthetic zeolites
are used as green, re-usable catalysts in industrial processes as heterogeneous catalysts for processes
that involve hydro-cracking, acrylation, oxidation and reforming. Most zeolite syntheses employ
Organic Structure Directing Agents (OSDAs), such as TMA-OH (Tetramethylammonium Hydroxide)
or crown-ether, which act as templates to guide the formation of particular types of zeolite pores and
channels [3–6]. This reduces the chance of producing competing zeolite phases. However, due to
the high manufacturing costs of producing these organic materials, which cannot be recovered after
calcination, current research is becoming more concerned with optimising synthesis conditions in
order to produce pure zeolites in the absence of OSDAs [3,7]. Here, we performed a low temperature
synthesis of small zeolite A (Na-A) crystals without the use of OSDAs, and the corresponding LTA
framework (Linde Type A) is shown in Figure 1.

Magnetochemistry 2017, 3, 42; doi:10.3390/magnetochemistry3040042 www.mdpi.com/journal/magnetochemistry

Magnetochemistry 2017, 3, 42 2 of 16

Figure 1. Linde Type A (LTA) framework with the α cage as the unit cell in the middle (black square).
Red spheres: oxygens; blue: Si/Al atoms.

Na-A is a commercially important zeolite used in industry for catalysis, adsorption and industrial
gas separations [8]. More recently, its sustainability as a drug delivery system has been investigated [9].
One of its greatest applications, however, is ion exchange; in particular, rapid Na+ /Ca2+ exchange.
Consequently, Na-A is very effective in water softening, and one of its main functions is in washing
powders as a detergent builder [10].
Ion exchange can also produce zeolites with different properties. For example, K-A is commonly
used in the ethanol drying processes [11] and partially-exchanged K/Na-A is used to separate CO2 from
CO2 /N2 dry mixtures [12]. Ca-A zeolites are important in industry, where they selectively adsorb linear
alkanes from a mixture of branched alkanes [13], and Na+ /NH4 + exchange is useful in minimising
environmental pollution and eutrophication [14–17]. Li-A was proposed as a possible delivery material
for pharmacological studies [18]. Li-exchanged zeolites are also used for the separation of nitrogen
from air [19]. In this work, we carried out aqueous ion exchange of monovalent alkali metals: Li+ ,
K+ , Rb+ and NH4 + and divalent Ca2+ into zeolite A crystals produced from a low temperature and
organic template-free synthesis and performed analysis using solid state NMR and other methods to
determine the structural effects of the exchange. Previously, solid state NMR has been used to study
other zeolites [20–28].

2. Results and Discussion

2.1. Na-A, Li-A, K-A and Rb-A

The powder patterns of the hydrated Na-A samples are consistent with those recorded in the
literature for pure phase zeolite A crystals [29,30]. Figure 2 shows the indexed pattern for Na-A,
synthesised at 40 ◦ C for 24 h. Reflection peaks corresponding to both Na-A and Faujasite (FAU)
phases [30] were observed when the zeolites were synthesised at 50 ◦ C for 24 h and at 40 ◦ C for 48 h,
as shown in Figure 3. It is evident that, if given enough time or if heated above a certain temperature,
there is a tendency for the metastable LTA framework structure to subsequently transform into the
FAU framework [7,31]. Careful control of the synthesis conditions is, therefore, necessary to avoid the
formation of the unwanted polymorph, which is a ubiquitous problem in synthesising zeolites in the
absence of OSDAs. The low temperature of 40 ◦ C limits the presence of these competing phases.
Magnetochemistry 2017, 3, 42 3 of 16

Figure 2. PXRD pattern for Na-A synthesised at 40 ◦ C for 24 h, indexed as the LTA framework.

Figure 3. PXRD pattern for Na-A synthesised at 40 ◦ C for 48 h. Characteristic Faujasite (FAU)
framework peaks are indexed with black dots.

In this investigation, we decided to study all samples after one ion exchange only. The extent of
exchange was quantified from the filtrates using a sodium ion selective electrode (ISE). For each sample,
even after one exchange, we see good, although not complete, ion exchange. This is not surprising as
sometimes as many as 8–10 steps are required for a complete exchange to occur [32]. Results show that
the extent of exchange decreases with increasing cation size, Li+ > K+ > Rb+ . The steric restrictions
of the zeolite pores make full exchange difficult to obtain, particularly for those ions with large ionic
radii. Energy Dispersive X-ray (EDX) elemental analysis was also carried out. In all samples, it was
evident that partial exchange had taken place, as residual Na+ ions were detected.
PXRD and FT-IR analyses show that there is no significant alteration to either the long-range
crystal order or the local framework structure of Na-A after exchange with Li+ , K+ and Rb+ ions.
These monovalent alkali cations vary in their ionic radii, and changes in the PXRD peak intensities
are expected to occur as a result of these cations occupying slightly different sites in the pores.
Figure 4 shows the PXRD patterns for the alkali metal exchanged zeolites. For K-A, the (4,4,0) reflection
almost disappears, whereas the (4,2,2) and (8,0,0) peaks increase in intensity. These results are in
agreement with those observed by Lührs et al., where complete exchange with K and Ca was studied
using diffraction and structure refinement [33]. The PXRD pattern for Rb-A is also slightly different.
The characteristic intensities of the first four Na-A reflections are altered; most noticeable is the increase
in the intensity of the (2,2,0) reflection.
Magnetochemistry 2017, 3, 42 4 of 16

Figure 4. PXRD patterns for Na-A, Li-A, K-A and Rb-A.

The unit cell parameters (a) for the exchanged zeolites were calculated from the PXRD peak
positions and Miller indices using the program UnitCell [34] and are shown in Table 1. All samples have
cubic symmetry, and it can be seen that the unit cell size decreases by about 1% on exchanging larger
Na+ (1.02 Å) for smaller Li+ (0.59 Å) ions and increases slightly on exchange with larger K+ (1.38 Å)
and Rb+ (1.49 Å) ions [35]. Correspondingly, an increase in the lattice parameter is progressive from
Li < Na < K < Rb-A, in accordance with the increasing ionic radii of the monovalent cations.

Table 1. Unit cell parameters for the exchanged zeolites.

Li-A Na-A K-A Rb-A

Unit cell parameter, a (Å) 24.151 (2) 24.435 (2) 24.454 (2) 24.486 (3)

The FT-IR spectra for Li-A, Na-A, K-A and Rb-A all display the fundamental zeolite framework
vibration νmax /cm−1 at 959, 968, 972 and 969, respectively, corresponding to the asymmetric ν(O−T −O)
stretch, shown in Figure 5. In addition, the framework symmetric ν(O−T −O) stretch occurs at ν/cm−1
684, 664, 663 and 666 for Li-A, Na-A, K-A and Rb-A, respectively. The broad peaks at 3350–3450 cm−1
and the weaker peaks at 1650 cm−1 observed in all spectra correspond to the ν(O− H ) stretching
and δ( H −O− H ) bending vibrations of water molecules in the hydrated samples. The only noticeable
differences in the spectra are that the framework ν(O−T −O) asymmetric stretch shifts to slightly a
higher wavenumber and the ν(O−T −O) symmetric stretch shifts to slightly a lower wavenumber, with
increasing cation size, Li+ < Na+ < K+ .
Magnetochemistry 2017, 3, 42 5 of 16

Figure 5. FT-IR spectra for Na-A (blue line) and cation-exchanged Li-A (orange line); K-A (grey line)
and Rb-A (green line).

For the parent Na-A zeolites, 29 Si and 27 Al MASNMR spectra contain one peak at δ −89.54 ppm
and δ 58.41 ppm, respectively, confirming that the Si/Al ratio of the framework is one. This is in
agreement with data reported by Thomas et al. [24] for a single silicon, Si(OAl)4 , and aluminium
environment, Al(OSi)4 , in Linde Type A zeolites. 27 Al MAS NMR spectra for the exchanged zeolites
also display one sharp peak between δ 57 ppm and 60 ppm, pertaining to Al(4Si) units. Likewise,
29 Si spectra for Li-A, K-A and Rb-A are also dominated by a single sharp peak at δ −87.23 ppm,

−89.83 ppm and −89.87 ppm, respectively. These peaks all lie within the chemical shift range for
which Si(4Al) units can occur (δ −80.0 ppm–−90.5 ppm from TMS) [28]. Some small, low intensity
peaks at δ −84.02 ppm, −87.96 ppm and −85.03 ppm are observed in the Li, K and Rb-A samples,
respectively. These are identified as silanol peaks. From deconvolution of the Li, K and Rb-A 29 Si NMR
spectra as shown in Figure 6, the Si/Al ratios were calculated to be one using Equation (1) [22,28]:

Si ∑nn= 4
=0 I Si (nAl )
= n =4 n (1)
Al ∑n=0 ( 4 ) I Si(nAl )

Figure 6. Cont.
Magnetochemistry 2017, 3, 42 6 of 16

Figure 6. 29 Si NMR spectrum of the as-synthesised Na-A and monovalent cation-exchanged Li-A, K-A
and Rb-A.

It is also interesting to note that the Si(4Al) peak for Li-A is significantly shifted to a lower field,
centred at δ −87.23 ppm, in comparison to that of the parent Na-A peak, at δ −89.54 ppm. The linear
relationship between the average Si-O-T framework bond angles, (α) and 29 Si chemical shifts can offer
an explanation for this difference. Table 2 shows the Si/Al ratios and average T-O-T bond angles that
were calculated from the deconvoluted 29 Si NMR spectra using Equation (2) [36].

δ = 29 Si(ppm) = −5.230 − 0.570α (2)

Magnetochemistry 2017, 3, 42 7 of 16

Table 2. 29 Si NMR data: Si/Al ratios and average T-O-T bond angles for Li, Na, K and Rb-A.
The angular values are estimated based on NMR data using the regression relationship from [36], and
we estimate the accuracy on angles up to ±2 degrees.

Li-A Na-A K-A Rb-A

Si/Al 1 1 1 1
6 T-O-T [α (◦ )] 143.9 147.9 148.6 148.4

Na-A zeolites, synthesised at 40 ◦ C for 24 h, are shown to have good cation exchange ability
with Li+ , K+ and Rb+ ions. The only noticeable differences between these exchanged zeolites are the
sizes of the unit cells and average framework T-O-T bond angles, which increase accordingly with
increasing cation size Li < Na < K < Rb.

2.2. NH4 -A
Exchange with NH4 + ions compromises some of the long-range order of the zeolite A crystals,
inferred by the broad PXRD peaks and low signal to noise ratio, as seen in Figure 7. NMR and
FT-IR spectra also indicate that the local framework environment is affected. Figure 8 shows a weak
peak at ν( NH ) /cm−1 1453 in the FT-IR spectrum, which confirms that exchange has taken place.
The asymmetric ν(O−T −O) stretch is, however, weaker and broader than that of the parent spectrum
and is shifted toward a higher wavenumber, occurring at νmax /cm−1 987 [37,38]. As Si-O bonds (1.64 Å)
are shorter than Al-O bonds (1.73 Å) [35], the force constant is higher for the former. Therefore, the shift
to higher frequencies indicates that a loss of some aluminium from the framework has occurred.

Figure 7. PXRD pattern for NH4 -A.

Figure 8. FT-IR spectra for the parent Na-A zeolite (orange line) and NH4 -A (blue line).
Magnetochemistry 2017, 3, 42 8 of 16

Furthermore, deconvolution of the 29 Si MAS NMR, as shown in Figure 9, confirms the presence
of both Si(3Al) and Si(4Al) environments in the framework, with peaks occurring at characteristic
chemical shifts of δ −91.41 ppm and −89.08 ppm, respectively. Another peak at δ −85.04 ppm is
present in the spectrum due to silanol species. This is in line with the appearance of the ν(T −O− H )
stretch at 868 cm−1 in the FT-IR spectrum. Using Equation (1), the Si/Al ratio of NH4 -A was calculated
to be 1.04. The loss of some aluminium from the framework is further confirmed in the 27 Al MAS
NMR spectrum, which displays a resonance signal at δ 1.29 ppm, attributed to extraframework
octahedrally-coordinated aluminium [23,28]. This peak is broad and overlaps with the main signal
at δ 58.89 ppm (for a tetrahedral Al coordination). The broadening and overlapping of these peaks
can be attributed to severely distorted six coordinated and four coordinated aluminium environments.
The presence of six coordinated extraframework Al species in NH4 -exchanged zeolite A has been
previously reported by Klinowski et al. [22,24], Sartbaeva et al. [15] and M. Dyballa et al. [39]. It is
evident that some dealumination of the zeolite A framework occurs upon exchange with NH4 + ions.

Figure 9. 29 Si (top) and 27 Al (bottom) NMR spectrum of the monovalent cation-exchanged NH4 -A.

2.3. Ca-A
There is no considerable alteration to the long-range crystal order of zeolite A after exchange
with Ca2+ . The increase in intensity of the (4,0,0) reflection and the decrease of the (4,4,0) reflection
is consistent with the results obtained by Lührs et al. [33]. The peak in the PXRD pattern at 2θ 29.57◦ ,
as shown in Figure 10, is characteristic of calcite (CaCO3 ), which must have formed from the Ca(OH)2
exchange solution. Further characterisation with 13 C Cross-Polarisation (CP) NMR (Figure 11) shows a
distinct peak centred at δ 168 ppm, which confirms the presence of CO3 2− [26]. Furthermore, the split
Magnetochemistry 2017, 3, 42 9 of 16

bands in the FT-IR spectrum at 1413 cm−1 and 1459 cm−1 identify the carbonate as a monodentate
species, as shown in Figure 12 [40].

Figure 10. PXRD pattern for Ca-A. The characteristic calcite peak is identified.

Figure 11. 13 C CPNMR of Ca-A.

Figure 12. FT-IR spectra for the parent Na-A zeolite (orange) and Ca-A (blue).
Magnetochemistry 2017, 3, 42 10 of 16

Exchange with Ca2+ has a small effect on the local framework environment of zeolite A.
The asymmetric ν(O−T −O) stretch in the FT-IR spectrum is less intense and is shifted toward a higher
wavenumber, occurring at νmax /cm−1 999 [37,38]. The 29 Si MAS NMR spectrum, as shown in Figure 13,
is dominated by an intense peak at δ −91.41 ppm, due to the expected Si(4Al) units of the framework.
However, deconvolution of the spectrum also confirms the presence of Si(3Al), with a very small
peak occurring at δ −96.35 ppm. Another peak at δ −85.55 ppm is also present due to some silanol
species. Using Equation (1), the Si/Al ratio of Ca-A was calculated to be 1.01. Similar to the exchange
with NH4 + ions, it is evident that some dealumination of the zeolite A framework has occurred
upon exchange with Ca2+ ions. This loss of aluminium is confirmed in the 27 Al NMR spectrum,
which displays a broad peak centred at δ 50.11 ppm, characteristic of Al(4Si) units and also a slight
peak centred at δ 9.10 ppm, which can be attributed to a distorted octahedral aluminium environment.
The broadness of the peaks in the spectra can be attributed to quadrupolar interactions of 27 Al nuclei
in these distorted environments.

Figure 13. 29 Si (top) and 27 Al (bottom) NMR spectrum of the divalent cation-exchanged Ca-A.

2.4. SEM
The surface morphologies of the zeolite crystals were observed using Field Emission Scanning
Electron Microscopy (FESEM). Particle sizes were calculated from the scale bars on the FESEM
micrographs, using the ImageJ processing and analysis program. The crystallite sizes were also
calculated from the broadening of the most intense PXRD peaks, in this case the (6,2,2) and (6,4,4)
reflections, using the Scherrer Equation (3), where L is the crystallite size, β (hkl ) is the full width at half
Magnetochemistry 2017, 3, 42 11 of 16

maximum for the major peak of the PXRD pattern subtracting the instrumental contribution to the
broadening, K is the Scherrer constant, which is 0.9, λ is the wavelength of the X-rays in nm and θ is
the Bragg angle of the incident X-rays [41].

Kλ
L= (3)
β(hkl ) cos θ
Table 3 shows the average zeolite particle sizes. For Na-A and Ca-A zeolites, there is good
consistency between the sizes calculated from the Scherrer equation and FESEM data.
Figure 14 shows the FESEM micrograph for the parent Na-A zeolite. A variety of crystallite
shapes and sizes can be observed, somewhere in between cubic and spherical and ranging from
122–354 nm. The visibly larger crystals with well-defined edges display the typical cubic morphology
of LTA zeolites [42,43]. However, the low temperature conditions employed in this synthesis appear
to slow down crystal growth, instead favouring nucleation in the initial stages [44]. Particles that
are more rounded in shape and significantly smaller in diameter are evident in the FESEM images,
indicating that some of the crystals have not had enough time to form completely. These results are
in agreement with those reported by Dimitrov et al. [45] and Smaihi et al. [46]. The introduction of
Ca2+ into the zeolites is accompanied by noticeable changes in the surface morphology, as shown in
Figure 15.

Table 3. Crystallite sizes (nm) calculated from FESEM data using Equation (3) compared to crystal
size observed by FESEM. Statistical analysis shows a large spread of values from the Scherrer equation
up to ±28 nm; for FESEM data, the standard deviation is up to ±14 nm.

Na-A Ca-A
Scherrer Equation (nm) 242 270
FESEM (nm) 241 290

Figure 14. FESEM Na-A.

Magnetochemistry 2017, 3, 42 12 of 16

Figure 15. FESEM Ca-A.

3. Materials and Methods

3.1. Synthesis of Na-A: Low Temperature and Organic Template-Free

Zeolite A, with chemical composition [Na12 [(AlO2 )12 (SiO2 )12 ]·27H2 O, was prepared using a
method described by Leung et al. [4]. The crystallisation process was carried out at 40 ◦ C in the absence
of an organic template. Six-point-seven-five grams of NaOH pellets (100% NaOH, Fischer, Ried im
Innkreis, Austria) were dissolved in 40 cm3 of deionised water, and the solution was divided into
two equal volumes. Zero-point-nine-eight-eight grams of NaAlO2 (100% Al, Aldrich, St. Louis, MO,
USA) were added into one bottle, and 2 cm3 of colloidal silica (Ludox HS-30, 30 wt % SiO2 , Aldrich,
St. Louis, MO, USA) were added to the other. Both solutions were left to stir at room temperature
for 90 min until clear. The silica solution was then poured slowly into the aluminium solution with
gentle stirring. A thick gel with batch composition of 2SiO2 :Al2 O3 :15Na2 O:400H2 O formed, and this
was shaken or stirred vigorously for 15 min, either by hand or with a magnetic stirrer, and was put
in the oven at 40 ◦ C for 24 h. The zeolite crystals were filtered three times with deionized water,
until the pH of the filtrate was 7. The product was then dried in an oven at 100 ◦ C for a further 24
h. In order to see the effect of temperature and time on the synthesis, the method above was varied
slightly. For some samples the crystallisation temperature was increased to 50 ◦ C for 24 h, and for
other samples, the crystallisation time was increased to 48 h at 40 ◦ C.

3.2. Ion Exchange

The cation sources used for ion exchange were LiOH, KCl, RbOH, Ca(OH)2 and NH4 Br. The mass
of each cation source was calculated so that the exchange solutions contained a surplus of the
exchanging cation that was twice the theoretical amount of Na+ in the pores of 1 g of Na-A.
The appropriate cation source was dissolved in 50 cm3 of deionized water. One gram of the parent
Na-A zeolite was added, and the solution was stirred for 6 h at 65 ◦ C. This was then filtered and
washed with deionized water and the exchanged zeolite left in an oven to dry overnight at 100 ◦ C.
The filtrates were kept in order to quantify the amounts of exchange that had taken place using the
sodium ion selective electrode.
Magnetochemistry 2017, 3, 42 13 of 16

3.3. Product Characterisation

3.3.1. Powder X-ray Diffraction

PXRD patterns were recorded at room temperature using a BRUKER AXS D8 Advance
diffractometer equipped with a Vantec-1 detector using Cu-Kα radiation (λ = 1.54) in flat plate mode.
The scan range was from 3◦ < 2θ < 60◦ over 20 min. The unit cell parameters for the samples were
calculated using the program UnitCell [34].

3.3.2. Solid State Nuclear Magnetic Resonance

29 Si, 27 Al, 23 Na
and 13 C NMR spectra were measured by a VARIAN VNMRS 400 spectrometer
using the Direct Excitation (DE) method, with neat tetramethylsilane (TMS), 1 M aqueous Al(NO3 )3
and 1 M aqueous NaCl as references. 13 C Cross-Polarisation (CP) MAS-NMR was used for Ca-A to
enhance the signal. The spinning rates of 29 Si and 13 C NMR were 6.0 kHz and for 27 Al and 23 Na NMR
were 12 kHz. The frequency of 29 Si NMR was 79.438 MHz and for 27 Al 104.199 MHz. The spectral
width of 29 Si NMR was 40,322.6 Hz and for 27 Al 416.7 Hz. Solid-state NMR spectra were obtained at
the EPSRC U.K. National Solid-state NMR Service at Durham.

3.3.3. Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy

Low resolution micrographs were taken using a JEOL SEM6480LV scanning electron microscope.
EDX data were acquired using an Oxford INCA X-ray analyser attached to the microscope with an
acceleration voltage of 20 kV.
High resolution micrographs were taken using a JEOL FESEM6301F field emission scanning
electron microscope (FESEM). The powder samples for FESEM were coated with 5 nm chromium to
prevent surface charging after EDX data were collected.

3.3.4. Fourier Transform Infrared Spectroscopy

FT-IR spectra for the powder samples were recorded using a Perkin Elmer 100 FT-IR Spectrometer
in the range of 4000–600 cm−1 .

3.3.5. Sodium Ion Selective Electrode

The concentration of Na+ in the exchange filtrates was calculated using a Cole-Parmer double
junction, combination sodium Ion Selective Electrode (ISE) filled with a reference solution of
0.1 M NH4 Cl and connected to a pH/mV meter.

4. Conclusions
Solid state NMR revealed changes to the local structure of the LTA framework upon ion exchange
with NH4 + and Ca2+ . Exchange with Li+ , K+ and Rb+ ions does not significantly affect the long-range
crystal order. Exchange with NH4 + ions compromises some of the long-range order of the zeolite A
crystals due to the loss of some framework aluminium as can be seen from X-ray data. Exchange with
divalent Ca2+ ions introduces some monodentate carbonate species into the framework, but no
alteration to the long-range crystal order is observed. This study confirms that using a local probe such
as SS NMR alongside PXRD and other long-range methods to study zeolites can reveal an extra level
of information about the structure of those useful minerals, which will further their use as potential
catalysts and ion exchange materials.

Acknowledgments: A.S. would like to acknowledge the Royal Society for funding of URF. We thank John Mitchel
and Ursula Potter for help with collecting SEM data and Fraser Markwell for collecting SS NMR data at the
EPSRC-funded SS NMR facility at Durham University.
Author Contributions: A.S. conceived the study. K.M.L. designed experiments. L.P. and K.M.L. have collected
data and performed data analysis. All authors contributed to writing and editing the manuscript.
Magnetochemistry 2017, 3, 42 14 of 16

Conflicts of Interest: The authors declare no conflict of interest.

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