Sensors & Actuators: B.

Chemical 298 (2019) 126880

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Feasibility study of Mössbauer spectroscopy as a tool to explore PVC- T

plasticized potentiometric sensor membranes
Vitaly Panchuka,b, Valentin Semenova, Julia Ashinab, Andrey Legina,b, Konstantin Mikhelsona,
⁎
Dmitry Kirsanova,b,
a
Institute of Chemistry, St. Petersburg State University, Universitetskaya nab. 7/9, 199034 St. Petersburg, Russia
b
ITMO University, Kronverkskiy pr., 49, 197101 St. Petersburg, Russia

A R T I C LE I N FO A B S T R A C T

Keywords: There is a serious lack of instrumental studies of polymeric membrane ion sensors that would give reliable
Ion-selective sensors information on the chemistry behind the sensor response. These types of studies are quite challenging due to the
Mössbauer spectroscopy low content of species of interest in the membrane material and due to specific features of plasticized polymeric
polymeric sensor membranes sensor membranes. Mössbauer spectroscopy is a powerful tool for studying local chemical environment of the
probe atom. In this research we explored the forms of iron existence in different PVC-plasticized membranes
containing Fe-binding ligand and cation-exchanger. In order to be able to observe Mössbauer effect we employed
57
Fe-enriched sample solutions to soak the membranes and performed the measurements at 80 K to increase the
recoil-free factor. It was found that the chemical forms of iron are different in membranes containing the ion-
exchanger and those containing both ion-exchanger and the ligand. The relative content of iron in various forms
was estimated. It was also observed that iron ions enter into the «dummy» membranes with no ligand and ion-
exchanger, however in very small amounts.

1. Introduction
Potentiometric sensors based on plasticized polymeric membranes:
ion-selective electrodes (ISEs) have gained wide acceptance as simple
and effective analytical instruments for sensitive and selective quanti-
fications of various ions. These sensors are routinely applied in various
fields like medicine, ecological monitoring, industrial analysis [1–7].
The membranes of such sensors are based on polymers (typically poly
(vinylchloride) – PVC) plasticized with appropriate organic solvents.
Lipophilic ligands (ionophores) and ion-exchangers are added to these
membranes providing for selective extraction of target ions by mem-
branes and promoting potentiometric response.
The theory of potentiometric ion sensors is very well developed
[1,8]. It relies on thermodynamic or kinetical description of the ISEs
response in terms of the respective equilibrium or reaction rate con-
stants. Unfortunately, the values of the latter are (mostly) chosen ar-
bitrarily, and only a limited number of the relevant constants have been
estimated experimentally. For instance, information on ion-ionophore
complex formation (the stoichiometry of complexation and the complex
stability constants) can be obtained by the segmented sandwich mem-
brane method [8–11]. This method, and also chronopotentiometry (the
galvanic step method) allow for the estimation of the association be-
tween ions and ion-exchanger sites in ISE membranes [12,13]. Mea-
surements of the electrochemical impedance of ISEs allow obtaining
data on the kinetics of ion transfer across the membrane/solution in-
terface [11,14,15]. However, these experimental methods rely on the
current theoretical views on the mechanism of the ISE response and are
therefore indirect.
The number of direct instrumental studies giving the insights into
the chemical processes involving target ions in the membrane phase is
quite limited, although such studies would definitely improve our un-
derstanding of response mechanism of the sensors. This is due to spe-
cific features of plasticized polymeric sensor membranes, such as e.g.
inability to withstand high vacuum conditions required by most of the
modern instruments (X-ray photoelectron spectroscopy, electron micro
probe analysis, secondary ion mass-spectrometry) due to evaporation of
solvent-plasticizer. Another reason is the quite low content of species of
interest in the membrane material. There are several works applying
infrared spectrometry to study cation permselectivity [16] and water
uptake [17,18] in PVC-plasticized sensor membranes. X-ray photo-
electron spectroscopy and static secondary ion mass spectroscopy were
employed to explore the surfaces of solvent polymeric membranes

⁎
Corresponding author at: Institute of Chemistry, St. Petersburg State University, Universitetskaya nab. 7/9, 199034 St. Petersburg, Russia.
E-mail address: d.kirsanov@gmail.com (D. Kirsanov).

https://doi.org/10.1016/j.snb.2019.126880
Received 6 May 2019; Received in revised form 4 July 2019; Accepted 25 July 2019
Available online 02 August 2019
0925-4005/ © 2019 Elsevier B.V. All rights reserved.
V. Panchuk, et al.
[19,20]. The morphology of the surface of plasticized PVC membranes,
as well as bovine serum albumin (BSA) adsorption on the membranes
have been studied also by AFM, TOF-SSIMS, impedance and contact
angle measurements [19]. Biofouling of the ISE membranes due to BSA
adsorption was studied also by ellipsometry [21]. These studies pro-
vided information mainly on polymers and plasticizers as membrane
macro components but no information on the chemical state of analyte
ions in polymeric membranes was derived.
Mössbauer spectroscopy is based on recoil-free resonant absorption
or emission of gamma rays by certain nuclei in the studied substance.
The potential of Mössbauer spectroscopy in analytical chemistry is
determined by the sensitivity of the resonant nucleus to its chemical
environment. The nuclear energy states depend on external and internal
electric and magnetic fields [22]. Mössbauer spectra provide informa-
tion on a large number of interactions related to the chemical nature of
the Mössbauer isotope. Among the advantages of the method one can
mention the absolute selectivity (only resonant atoms are “seen” in the
spectra), the absence of sample preparation, non-destructivity.
Mössbauer spectroscopy is widely applied for the studies in material
science [23,24], geology[25], biology [26], corrosion and catalysis
[27]. The method was also applied in sensor studies to elucidate the ion
transport and response mechanisms of chalcogenide glass membranes
[28] and to study magnetite-coated iron wire electrodes as pH sensors
[29]. Several other sensor-related studies can be found in recent lit-
erature all dealing with solid state samples [30–33]. The Mössbauer
effect can be observed with many different isotopes, however only a
few of them have found broad acceptance for laboratory studies. This is
due to the limitations in availability of suitable radioactive sources. The
most available isotopes for Mössbauer studies are 57Fe, 119Sn, 127I
151
Eu. Application of synchrotron radiation significantly enlarges the
list of possible isotopes and such elements as K, Zn, Cs, Ba, and Hg
become available for studies.
The purpose of the present research was to explore the feasibility of
Mössbauer spectroscopy to study the PVC-plasticized sensor mem-
branes. If being successful this could provide for direct chemical in-
formation on the forms of analyte ion existence in membrane phases of
different composition, on the symmetry of chemical environment of the
ions, on relative amount of different chemical forms involving analyte.
As a simple case study we have addressed the membranes containing
Fe-binding ligand and cation-exchanger. An important requirement to
observe the Mössbauer effect is that the resonant atom has to be com-
pletely bound and the sample itself has to be in the condensed state.
Violation of these conditions leads to very low intensities of spectral
signals due to the low recoil free factor. Moreover the significant
amount of resonant atoms should be present in the sample (typically
around 20 mg/cm2 for iron taking into account 2.12% natural occur-
rence of 57Fe). These issues hinder direct registration of Mössbauer
spectra of PVC-plasticized membranes since they are rather viscous li-
quids than solids and since the amount of ions, penetrating into the
membrane is rather small. In order to circumvent these issues in this
study special measures were taken: the 57Fe enriched solutions were
used and the measurements were performed at 80 K.
2. Materials and methods
2.1. Sensor membrane preparation
Sensor membranes with octyl(phenyl)-n,n-di-iso-
butylcarbamoylmethylphosphine oxide (CMPO) ligand were studied.
These membranes have shown the pronounced sensitivity towards Fe3+
ions in acidic media [34]. Three types of membranes were prepared: 1)
«dummy» membrane containing poly(vinyl chloride) (PVC) and sol-
vent-plasticizer o-nitrophenyl octyl ether (NPOE) only; 2) membrane
with 10 mmol/kg of potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]
borate (KTFPB) cation-exchanger; 3) membrane with 10 mmol/kg of
KTFPB and 50 mmol/kg of CMPO. The membranes were prepared using
2
Sensors & Actuators: B. Chemical 298 (2019) 126880
standard procedure: weighted amounts of membrane components were
dissolved in freshly distilled tetrahydrofurane upon stirring and then
were poured in the flat-bottomed Teflon beakers and left overnight for
solvent evaporation. All reagents for polymeric membranes preparation
were from Sigma-Aldrich (Merck). Resulted membranes of ca. 0.5 mm
thickness were cut into smaller disks of 8 mm in diameter. Three disks
of the membrane of each type were put into the 0.001 M solution of
57
Fe(NO3)3 in 0.003 M HNO3. This solution was prepared from α-Fe
enriched with 57Fe up to 90% (AO Izotop, St. Petersburg, Russia). The
solution was made acidic in order to maintain highest possible amount
of ionized Fe3+.
2.2. Mössbauer spectra acquisition
Prior to the measurements the membranes of all three types were
soaked in individual portions of 57Fe(NO3)3 solution for at least
72 hours to ensure complete equilibration of the system. After the
soaking each membrane was flushed with bi-distilled water and pat dry
with filter paper. After the drying three membrane disks of the same
type were put on one another to form a column. This column was
placed between two disks of weighing paper and then between two
aluminum disks having apertures of 5 mm in diameter. The construc-
tion was then placed into the sample holder of the Mössbauer cryostat
(VNIIFTRI, Moscow, Russia) which was installed into the spectrometer.
In principle, one thicker piece of membrane could be employed but its’
conditioning before the measurements would take longer time. The
scheme of the experiment is given in the Fig. 1.
The Mössbauer spectra were obtained by WissEl spectrometer
(Wissenschaftliche Elektronik GmbH, Germany) in constant accelera-
tion mode. The measurements were performed in the absorption geo-
metry at 298 K and 80К temperature with 25 mCi 57Co(Rh) source. Each
spectrum was accumulated during 144 hours. The Mössbauer effect was
not observed in the measurements at 298 K due to the absence of long-
range order of iron forms in the sample. For this reason, the spectra of
the membranes acquired at 80 K were considered. The mobility of iron
species in the membrane phase at room temperature is in a good
agreement with general considerations on these systems (viscous li-
quids).
2.3. Spectral data processing
Fitting of the Mössbauer spectra was done with superposition of
Lorentz functions using the standard Levenberg-Marquardt algorithm.
The fitting resulted in the determination of the following hyperfine
parameters of the spectral components: electric quadrupole splitting
(QS) and isomer shift (IS) values for quadrupole doublets and for the
single spectral line. These parameters allowed the interpretation of the
iron-containing forms in the membrane. Isomer shift is a line (or mul-
tiplet) shift derived from the difference in electron densities on the
resonant nucleus in the sample under study and in the reference nucleus
to the difference in their chemical environment. The IS value depends
on many various parameters and allows judging on the valence state of
the resonant atom, its chemical bonding and coordination number. In
this work, isomer shifts are given with respect to α-Fe foil. The quad-
rupole splitting is derived from the interaction of the nucleus with the
electric field gradient from the electron shell. This gradient is defined
by the presence of incomplete non-spherical electronic shells (p, d, f) of
the resonant atom and the geometry and effective charge of the atoms
in its chemical environment. The interpretation of IS and QS together
allows for reliable identification of the chemical state of the resonant
atom.
Relative content of iron in different forms was estimated from the
area under the corresponding spectral component assuming similar
resonance absorption factors. Relative content of iron in different
membranes was estimated as a total area under the normalized
Mössbauer spectra.
V. Panchuk, et al. Sensors & Actuators: B. Chemical 298 (2019) 126880

Fig. 1. Scheme experimental set-up.

3. Results and discussion

The prepared sensor membranes were characterized by potentio-

metric measurements. The details on the experimental set-up and the
observed sensor responses are provided in Supplementary Material.

3.1. Spectra of the «dummy» sensor membrane

The Mössbauer spectra of the sensor membranes acquired at 80 K

are shown in the Fig. 2.
The Mössbauer spectrum of the «dummy» membrane without ion-
exchanger and ligand after 72 hours of soaking in Fe (III) is given in the
Fig. 2a. The amplitude of the resonance peak is very small compared to
the background noise signal, indicating only a small uptake of iron ions
by this membrane.
Due to the low signal-to-noise ratio the precise processing of the
spectrum is not possible. We have described this spectrum with a
broaden singlet line with isomer shift around 0.3 mm/s which corre-
sponds to trivalent iron in symmetrical chemical surrounding.
According to the total area under the spectrum the amount of iron in
the «dummy» membrane is about 10 times lower than that in the
membrane with ligand (Table 1). These observations are in a good
agreement with the general theory of potentiometric sensors where
inert membrane matrix is not supposed to have pronounced ion-ex-
change with sample solution, although the presence of carboxylic
groups in PVC can provide ion-exchange properties [35], as well as
some functional groups from plasticizers. We suppose that these iron
ions were brought to the membrane phase in microdroplets of water
which were shown to contribute significantly to the water uptake of Fig. 2. Mossbauer spectra of iron in polymeric membranes acquired at 80 K: a –
plasticized polymeric membranes [17,18,36–38]. «dummy» membrane; b – KTFPB membrane; c – KTFPB-CMPO membrane.
«Dummy» membrane spectrum is also shown in figures b) and c).

3.2. Spectra of the ion-exchanger-based sensor membrane

superposition of quadrupole doublet and singlet. This implies that the
iron ions are present in the membrane in two different surroundings,
The spectrum of polymeric membrane containing only ion-ex-
i.e. there are two different chemical forms of iron. The singlet has the
changer is shown in Fig. 2b. The spectrum was described as a

3
V. Panchuk, et al.
Table 1
Mössbauer spectra parameters for the studied membranes at 80 K.
Sample Component IS, mm/s QS, mm/s
«Dummy» Singlet 0.25 ± 0.04 - 100
KTFPB Singlet 0.27 ± 0.01 - 15.4
Doublet 1.43 ± 0.01 1.47 ± 0.01
KTFPB- CMPO Singlet 0.27 ± 0.01 - 8.9
Doublet 0.53 ± 0.01 0.61 ± 0.01
isomer shift similar to that observed in the «dummy» membrane and
can be attributed to Fe3+ in a symmetrical chemical environment. The
area under the singlet is also comparable with the area under the signal
in the «dummy» membrane spectrum. We believe these singlet signals
in both «dummy» and ion-exchanger containing membranes have the
same origin. The largest part of iron quantity in the membrane (84.6%)
is related to the second signal – doublet. We suppose that this part of
iron atoms is associated with ion-exchanger as we did not observe this
contribution in the «dummy» membrane. The doublet signal has the
isomer shift value (1.43) which resembles that of doubly charged iron
cation. We have to emphasize that these results were reproducible in
three independent experiments with three different newly synthesized
membranes. The large value of the quadrupole split of the doublet
(1.47) implies that the iron ions associated with ion-exchanger are in
highly asymmetrical chemical surrounding. Tentatively, one may as-
cribe this surprising observation to reduction of Fe3+ ions to Fe2+ by
FTPB− anions. As an indirect support for this suggestion we have
performed the following simple experiment: approx. 0.1 M aqueous
solution of sodium tetraphenyl borate and 0.01 M Fe(NO3)3 in 0.01 M
HNO3 were mixed in equal volumes and left overnight in tightly closed
test tube. After that several crystals of o-phenanthroline were added
into the solution and this lead to the characteristic red color showing
the presence of Fe2+. However, further dedicated studies are required
in order to clarify this unexpected result.
3.3. Spectra of the membrane with ion-exchanger and ligand
Finally, the Mössbauer spectrum of the membrane containing both
ion-exchanger and ligand (Fig. 2c) contains two asymmetrical lines
around zero velocity value. This spectrum was decomposed into the
superposition of two contributions: doublet with IS = 0.53, and
QS = 0.61, and singlet with IS = 0.27. We attribute the observed
doublet to the Fe3+ bonded by CMPO and the singlet probably has the
same nature as the one in the spectrum of the «dummy» membrane
(Fig. 2a). The relative content in the form described by singlet is around
9% and in terms of total area under this spectral contribution this
content is in a good agreement with the amount of iron observed in the
«dummy» membrane (Table 1). The parameters of the doublet confirm
the trivalent state of the iron in the sample. QS value of this doublet
implies certain asymmetry in the chemical surrounding of the iron
atom. The stoichiometry of CMPO-Fe3+ complexes determined in liquid
extraction [39] was found to be 3:1 (CMPO:Fe). Although the direct
extrapolation of these results to the polymeric membrane system is not
possible, the certain analogy in complex formation can be assumed. The
observed asymmetry is not significant and we can hypothesize that the
stoichiometry of the CMPO-Fe3+ complex in the membrane is the same.
4. Conclusions
We have demonstrated the potential of Mössbauer spectroscopy in
direct identification of various chemical states of target ions in PVC-
plasticized sensor membranes. We have identified two possible ways of
ion penetration into polymeric membrane – the first one is associated
with direct extraction of Fe3+ ions with water uptake (minor amount);
the second one is associated with ion-exchange extraction by TFPB−
lipophilic anion. Two different forms of iron ions in membranes were
4
Sensors & Actuators: B. Chemical 298 (2019) 126880
Rel. area, % Abs. area, rel. un. Proposed iron form
0.074 Fe in aqueous microdroplets
0.089 Fe in aqueous microdroplets
84.6 0.490 Fe associated with TFPB anion
0.082 Fe in aqueous microdroplets
91.1 0.842 Fe bonded with CMPO ligand
observed: Fe2+ (presumably) in association with TFPB−, and Fe3+ in
«dummy» membranes (apparently, in water droplets) and also in Fe-
CMPO complexes. This is consistent with our tentative explanation of
the presence of Fe2+ in membranes: complexation with CMPO should
prevent from close contact between Fe3+ with TFPB−, and therefore
from reduction of Fe3+ to Fe2+. This issue, however, requires further
dedicated studies.
The applicability of Mössbauer spectroscopy is limited by the
availability of appropriate isotopes. No suitable isotopes for laboratory
studies are available for most of the typical target ions.
The applicability of Mössbauer spectroscopy appears to be limited
by the availability of appropriate isotopes. However, synchrotron ra-
diation sources significantly extend the number of suitable elements
and e.g. the studies with potassium can be performed [40]. Another
limitation is that the analyzed sample has to be in the solid state and in
case of polymeric sensor membranes, this requires the measurements to
be performed at low temperatures. In spite of these restrictions, the
unique capabilities of Mössbauer spectroscopy in analyzing local che-
mical environment of resonant atoms can make it a powerful tool for
exploration of polymeric sensor membranes.
Acknowledgements
This study was supported by Russian Science Foundation grant #18-
19-00151. AJ acknowledge financial support of her work with sample
preparation for Mössbauer spectroscopic measurements from the
Government of Russian Federation grant 08-08.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.snb.2019.126880.
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