Talanta 101 (2012) 128–134

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Talanta
journal homepage: www.elsevier.com/locate/talanta

A novel fluoride-selective electrode based on metalloporphyrin

grafted-grapheneoxide
T. Poursaberi a, M.R. Ganjali b,n, M. Hassanisadi a
a
Research Institute of Petroleum Industry, Tehran, Iran
b
Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Enqelab Street, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this work, the unique properties of graphene oxide were combined with the anion selectivity of
Received 25 June 2012 metalloporphyrin to fabricate a novel fluoride-selective sensor. The electrode made of 27% PVC, 54%
Received in revised form NPOE, 4% NaTPB and 15% NbTPP–GO was found to show the most favorable behavior. The sensor shows
26 August 2012
a Nernstian response (58.3 mV decade  1) in the concentration window of 5.0  10  1–
Accepted 27 August 2012
5.0  10  7 mol L  1with detection limit of 8.0  10  87 mol L  1. The response of the sensor was found
Available online 3 September 2012
to be stable in the pH range of 3.0–7.0 and the metalloporphyrin grafted-GO based F  sensors displayed
Keywords: very good selectivity with respect to a number of anions. The proposed sensor displays a long life time
Graphene oxide (more than 12 weeks) with a short response time of about 20 s.
Fluoride
& 2012 Elsevier B.V. All rights reserved.
Selective electrode
Metalloporphyrin
Potentiometry

1. Introduction ionophores which induce unique anion selectivities [30–38].

Observed selectivity pattern for such membrane electrodes,
Since the start of the graphene revolution in 2004, it has e.g. chloride (In(III)-porphyrin [39] ), thiocyanate (Mn(III)-porphyrin
captured increasing attention and has shown great promise in [40]), nitrite (Co(III)-porphyrin [41]), fluoride (Ga (III), Al(III) and
many applications [1–17], arising from its unique physicochem- Zr(IV)-porphyrins [42–50]), which often deviate significantly
ical properties such as high surface area, excellent thermal and from the classical Hofmeister sequence, results from selective
electrical conductivity, electron mobility at room temperature, interaction of analyte anion with the metal center of the por-
strong mechanical strength and flexibility [18–23]. The special phyrin structure. To the best of our knowledge, there is no report
properties of graphene may provide insight to fabricate novel of the use of metalloporphyrin-grafted graphene for anion recog-
potentiometric sensors for virtual applications. The excellent nition in the literature, so fabrication of a new kind of sensor is
conductivity and small band gap are favorable for conducting possible through combination of the advantages of metallopor-
electrons [23]. Graphene-based sensors can also have a much phyrins and graphene.
higher sensitivity because of the low electronic noise from In this paper, the niobium (V)-metalloporphyrin grafted-
thermal effect [24,25]. Furthermore, compared with CNTs, gra- graphene oxide was prepared and coated on platinum wire.
phene can be obtained easily by chemical conversion of the An exciting advance was made in the field of ISEs by Freiser [51]
inexpensive graphite [26]. Graphene oxide (GO) sheets are che- when they developed coated wire electrodes (CWEs). Potentio-
mically exfoliated graphite oxide sheets with carboxylic groups at metric sensors prepared by coating electroactive species on
the edges and phenol, hydroxyl and epoxy groups on the basal metallic or graphite conductors [52,53], with no internal electro-
planes [27]. Chemically functionalized graphene can be readily lyte solution. They have been shown to be very effective for a
mixed with polymers in solution to form a stable dispersion and wide variety of inorganic and organic anions and cations. These
yield novel types of electrically conductive nanocomposites kinds of electrodes are very simple, durable, inexpensive and
[28–30]. provide a reliable response over a wide concentration range [54].
When incorporated into plasticized PVC membranes, metallo- The proposed electrode which is used for fluoride sensing,
porphyrins become one of the most important classes of exhibited a great sensitivity as compared with the previously
reported ones. Fluoride is one of the most hydrophilic anions
(DGhyd ¼  465 kJ/mol [55]), therefore design of an ionophore
n
Corresponding author. Tel.: þ98 21 61112788; fax: þ98 21 66495291. which is selective towards fluoride ion is quite challenging.
E-mail address: [email protected] (M.R. Ganjali). Compared to other anions selection of an ionophore for its

0039-9140/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.talanta.2012.08.039
 T. Poursaberi et al. / Talanta 101 (2012) 128–134 129

successful detection is central, since it has to form a very strong

complex with F  . To obtain a non-Hofmeister selectivity pattern,
this hydration energy should be overcome. In this way we open
up a new avenue for fabricating excellent potentiometric sensors.

2. Experimental

2.1. Materials

Reagent grade o-nitrophenyl octyl ether (NPOE), dibutyl

phthalate (DBP), diethyl sebacate (DES), sodium tetraphenylbo-
rate (NaTPB), hexadecyltrimethylammonium bromide (HTAB),
tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and high
relative molecular weight PVC (all from fluka) were used as
received. Nature flake graphite was purchased from Sigma-
Aldrich. Nb (V)-5-4 (aminophenyl)-10, 15, 20-triphenyl porphyrin
was synthesized and purified as described elsewhere [56–58].
H2SO4, KMnO4, NaNO3, NaF, H2O2, SOCl2, triethylene amine and
CHCl3 were purchased from Sigma-Aldrich. Triply distilled de-
ionized water was used throughout.

2.2. Equipments

XRD patterns of the solid products were obtained in the 2y

range of 51–801 using a PW-1840 diffractometer from Philips Co.
with Cu-Ka radiation (l ¼1.54178 Å). The thermograms of the Fig. 1. Schematic representation of the NbTPP–GO.
samples were carried out between 25 and 700 1C at a heating rate
of 10 1C/ min, using Mettler Toledo TGA/SDTA 851 instrument. filtration on a membrane (0.22 mm). The excess NbTPP and other
FTIR spectra were obtained using a Vertex 70 FT-IR spectro- impurities were removed through five washing cycles, which
photometer from Bruker Co. to identify the functional groups included sonication, filtration (discarding the filtrate), and
and chemical bonding of the materials. UV–vis spectra were re-suspension of the solid in THF. Then the precipitate was
measured with a Carry 5030 spectrophotometer from Varian Co. washed with CHCl3. Afterwards the NbTPP–GO was washed with
A Corning ion analyzer 250 pH/mV meter was used for potential a small quantity of water to remove triethylamine, and finally
measurements at 25.070.1 1C. dried under vacuum.

2.3. Ionophore preparation

Synthesis of Nb-TPP covalently bonded to graphene oxide 2.4. Fabrication of the CWE
molecules via an amide bond (NbTPP–GO, Fig. 1) was carried
out in two stages: Membrane solution were prepared by thoroughly dissolving
27 mg powdered PVC, 15 mg ionophore NbTPP–GO, 4 mg NaTPB
2.3.1. Preparation of graphene oxide and 54 mg plasticizer NPOE in 5 mL of THF. The resulting mixture
GO was synthesized with the Hummers method [59]. Nature was transferred into a glass dish of 2 cm diameter. Coating
flake graphite was added to a flask with 50 mL of 98% H2SO4 in an process of CWEs was performed by dipping each platinum wire
ice bath, followed by slow addition of KMnO4 and NaNO3 under five times into this mixture. After each coating the membrane was
stirring. Then, deionized water was added and the temperature air-dried for 12 h until a thin film was formed. The electrode was
was raised to 98 1C. H2O2 was subsequently added into the flask. finally conditioned for 1 h in a 10  2 M of NaF solution.
After cooling of the resultant mixture to room temperature, the
mixture was filtrated and the filtered product was dried overnight
at 60 1C. The product was suspended in water to yield a brown 2.5. Emf measurement
dispersion and subjected to dialysis to remove residual metal ions
and acids. The purified dispersion was sonicated for 1.5 h at All measurements of emf were made at 2570.1 1C by use of
300 W to exfoliate the GO, and unexfoliated GO was removed the following assembly:
by centrifugation (4000 rpm, 5 min). At last, the GO sheets were Pt wire/membrane/sample solution/Hg–Hg2Cl2, KCl (satd.)
obtained. A Corning ion analyzer 250 pH/mV meter was used for
potential measurements. The emf observations were made rela-
2.3.2. Synthesis of NbTPP–GO tive to a double-junction saturated calomel electrode (SCE,
According to the Xu et al. method [60] under argon atmo- Philips) with the chamber filled with an ammonium nitrate
sphere, graphene oxide was refluxed in SOCl2 in the presence solution. The performance of the electrodes was investigated by
of DMF at 70 1C for 24 h. At the end of the reaction, excess SOCl2 measuring the emfs of sodium fluoride solutions prepared with
and solvent were removed by distillation. In the presence of tri- concentration range 10  1–10  8 mol L  1 serial dilution. Each
ethylamine and under argon atmosphere, the above product solution was stirred and the potential reading was recorded when
was allowed to react with NbTPP in DMF at 130 1C for 72 h. it became stable (change within 1–2 mV), and then plotted as
To precipitate the product, the solution was cooled to room logarithmic function of F  activity. Activities were calculated
temperature and poured into ether. The product was isolated by according to the Debye–Huckel procedure [61].
130 T. Poursaberi et al. / Talanta 101 (2012) 128–134

3. Results and discussion stretching band of the amide group. The stretching band of the
amide C–N peak also appeared at 1260 cm  1. These results
3.1. Structural characterization clearly proves that the Nb (V)-porphyrin complex has covalently
attached to the carboxylic groups of GO through the formation of
The X-ray diffraction (XRD) patterns of graphite and GO are a stable amide bond.
shown in Fig. 2. The pattern of pure graphite shows a peak at The thermal property and the composition of the GO and
26.61 corresponding to a basal spacing d002 ¼3.34 Å. In compar- NbTPP–GO were characterized by TG analysis (Fig. 4). As shown in
ison to the natural graphite, a wide peak is observed for GO at Fig. 4.a, there are three steps for mass losing upon temperature
12.01 corresponding to a basal spacing of d001 ¼7.33 Å. [62,63] increments. The mass loss at around 100 1C could be ascribed to
because of the presence of intercalated H2O molecules and the removal of adsorbed water. The mass loss at around 200 1C
various oxide groups (Fig. 2) [64] which clearly indicates the was attributed to the decomposition of labile oxygen functional
damage of the regular crystalline pattern of graphite during the groups [66]. The mass loss at around 500 1C was ascribed to the
oxidation [65]. carbon combustion [63]. The weight-loss stage in the region of
In order to understand the interaction between NbTPP and GO, 330–380 1C of NbTPP–GO TGA curve may result from the decom-
FTIR spectrum was recorded (Fig. 3). It is seen that the GO sheets position of metalloporphyrins [67–69]. These data showed that
carried adsorbed water molecules and structural OH groups modification of GO nanoparticles with metalloporphyrin has been
(a strong absorption band at 3410 cm  1 due to O–H stretching performed and they have been bonded to each other chemically.
vibrations), CQO (the CQO stretching vibrations from carbonyl
and carboxylic groups at 1734 cm  1), and C–O (C–OH stretching
vibrations at 1200 cm  1 or O–C–O stretching vibrations at 3.2. Stability constants of different anion-NbTPP complexes
1050 cm  1) groups, indicated the attachment of oxo-groups on
GO sheets after the chemical oxidation of the flake graphite. The Previous studies showed that the metalloporphyrin complexes
spectrum also showed a band around 1520 cm  1 corresponding containing different central metal exhibit different anion selec-
to the CQC stretching vibrations of carbon–carbon bonds in the tivity [30–38]. Thus, at first we carried out some spectrometric
aromatic ring. In the spectrum of NbTPP–GO, the peak at measurements in acetonitrile–water (1:1, v/v) solution in order to
1734 cm  1 almost disappeared, and a new band emerged at obtain quantitative information about the anion–NbTPP interac-
1640 cm  1, which corresponds to the CQO characteristic tions. The NbTPP spectrum (Fig. 5) exhibited a strong Soret
absorption at 420 nm, and weak Q-bands between 500 and

Fig. 2. XRD patterns of graphite (a) and GO (b). Fig. 4. TGA curves of GO (a) and NbTPP–GO (b).

Fig. 3. FT-IR spectra of GO (a) and NbTPP–GO (b).

 T. Poursaberi et al. / Talanta 101 (2012) 128–134 131

700 nm, which were consistent with that of TPP-NH2 analogues content until a value of 15% (M1–M3) the sensitivity of electrode
[70]. The addition of fluoride ion to a NbTPP solution resulted in a response has increased. However, further addition of ionophore,
increase in Soret absorption and the formation of a stable 1:1 resulted in the diminished response of the electrode (M4), most
fluoride-NbTPP complex in solution. The formation constants probably due to some inhomogeneities and possible saturation of
(log Kf) of the NbTPP and some anions are summarized in the membrane. The potentiometric response of the membrane
Table 1. As it is seen; there was a strong interaction between ion-selective electrodes was greatly influenced by the polarity of
fluoride and NbTPP. This could be mainly due to the selective the membrane medium, which is defined by the dielectric con-
bonding of fluoride to the metal center which is thought to be the stants of the major membrane components [71–73]. The influence
origin of the selectivity of NbTPP-based electrode for fluoride over of the nature of plasticizer on the F  response was studied on
other anions. electrodes. Three types of plasticizers having different dielectric
constants, namely, DES, DBP, and NPOE were studied. As shown in
3.3. Effect of membrane composition Table 2 (M3, M5, M6), NPOE with the highest dielectric constant in
the series resulted in the best sensitivity of the potential
Different aspects of membrane preparation based on the responses. The response properties of anion-selective electrodes
NbTPP–GO for F  ion were optimized and the results are based on ion carriers were strongly influenced by the lipophilic
summarized in Table 2. As seen with increasing NbTPP–GO ionic sites [74]. The response of ISE membrane in the presence of
various ionic sites was used to determine whether the carrier has
acted as electrically charged or uncharged. In cases in which a
charged carrier mechanism (the ionophore is initially positively
charged and becomes neutral upon subsequent ligation of an
anion) was prevalent, anionic (typically tetraphenylborate deri-
vates) sites were added to the polymer membrane. In this way a
Nernstian response, diminution of the membrane resistance,
lessening of the co-anion interferences, improvement of the
detection limit and optimization of the selectivity could be
obtained. However, when a neutral carrier mechanism (when
the ionophore is initially neutral and becomes negatively charged
when bound to a sample ion) was dominant, cationic (typically
quaternary ammonium salts) sites were introduced. So, the
possible response mechanism and the effect of additives on the
potentiometric response of NbTPP-based ISE, was investigated by
varying the nature and amount of ionic additives (M3, M7, M8).
Results in Table 2 showed that the addition of HTAB as a cationic
additive had no significant effect on the slope and dynamic range
of the calibration graph (compare M3 and M8). On the other hand,
Fig. 5. Absorbance spectrum of NbTPP. addition of NaTPB to the membrane (M7) caused an increase in
the slope of the calibration graph, which approached the Nerns-
tian behavior (58.3 mv/decade). These results revealed that
NbTPP in the membrane has acted as a positively charged carrier.
Table 1
Stability constants of anion-NbTPP complexes.
In anion-selective electrodes based on positively charged carriers,
ionic sites with the same charge sign as the primary ion was
Aniona log Kf required to optimize selectivity. As is shown in selectivity studies,
the selectivity of the membrane has improved upon addition of
F 5.40 70.03
NaTPB and worsened in the presence of HTAB which was another
SCN  4.85 70.03
ClO4 4.72 70.04 evidence for the electrode functioning based on charged carrier
Cl  4.42 70.02 mechanism. It should be also noted that when the plasticizer/PVC
Br  4.19 70.05 ratio was twice the best slope and linear dynamic range was
NO3 3.93 70.04 obtained. Thus, the membrane M7 with the optimized composi-
I 3.58 70.02
SO24  3.25 70.03
tion of NPOE:PVC:NbTPP–GO:NaTPB ratio of 54:27:15:4 was
selected for the preparation of CWE for fluoride ion.

Table 2
Effect of different membrane composition on fluoride selective electrode response, the membrane code M7 that indicated with box is the optimum membrane
composition.

Membrane code Composition (%) Working range (M) Slope (mVdecade  1)

PVC Plasticizer Ionic site Nb–TPP–GO

M1 30 65,NPOE – 5 1.0  10  3–5.0  10  5  35.2

M2 30 60,NPOE – 10 5.0  10  2–1.0  10  5  45.3
M3 30 55,NPOE – 15 5.0  10  1–1.0  10  5  53.5
M4 30 50,NPOE – 20 1.0  10  2–1.0  10  6  46.5
M5 30 55,DES – 15 5.0  10  1–5.0  10  6  45.4
M6 30 55,DBP – 15 1.0  10  2–1.0  10  5  42.2
M7 27 54,NPOE 4 NaTPB 15 5.0  10  1–5.0  10  7  58.3
M8 27 54,NPOE 4 HTAB 15 1.0  10  2–5.0  10  5  45.7
132 T. Poursaberi et al. / Talanta 101 (2012) 128–134

3.4. Calibration curve protonated form, therefore the concentration used to plot cali-
bration curve represent the free fluoride anion concentration, not
The EMF response of the proposed F  sensor based on NbTPP– the total fluoride added to the sample solution.
GO, prepared under optimal membrane ingredients, indicated a
linear range from 5.0  10  1–5.0  10  7 mol L  1 (Fig. 6). The 3.6. Response time
slope of calibration curve was  58.370.5 mV per decade. The
limit of detection, as determined from the intersection of the two Dynamic response time is an important factor for any ion-
extrapolated segments of the calibration graph, was 8.0  10  8 M. selective electrode. In this study, the practical response time of
the F  -selective electrode was recorded by using solutions with
3.5. Effect of pH different F  concentrations. The measurements sequence was
from the lower (1.0  10  7 M) to the higher (1.0  10  2 M)
The influence of pH of the test solution (1.0  10  3 mol L  1 concentrations. The actual potential versus time traces is shown
fluoride) on the potential response of the membrane sensor was in Fig. 8. As it is seen, the response time for the electrode was
tested in the pH range of 2.0 to12.0 adjusted with either H2SO4 or about 20 s for dilute fluoride solutions ( o10  3 M) and at higher
KOH. The results, shown in Fig. 7, implied that the metal center of concentrations ( 410  3 M), response time was shorter (  10 s).
the complex was mainly responsible for the pH response of the
membrane. In fact, OH  and F  ions coordinated competitively 3.7. Life time
with the metal center of the ionophore. However the response of
the electrode was hardly affected by pH changes in the range of Lifetime study is based on monitoring the change in electrode
3.0–7.0. As the pH of solution increased, OH  became the primary slope and linear dynamic range with time. After 12 weeks a very
ion and consequently, the potentiometric response of the elec- slight gradual decrease in slope was observed (i.e.,  57.9 mV per
trode for F  ion deviated from linearity. Therefore, at low F  decade). The reproducibility of the sensor was tested. The stan-
concentrations, it was necessary to work at the more acidic region dard deviation of potential measurements for 10 different solu-
of the pH-potential response curve. To avoid the nearly complete tions at 1.0  10  4 mol L  1 fluoride was 71.4 mV.
protonation of F  in sample solutions with lower pH (The pKa of
Hf acid is 3.15 so the concentration ratio of F  /HF at pH 3.5 is 2.0) 3.8. Selectivity
[75] and the interference of OH  at higher pHs, pH 3.5 (Gly/HCl
buffer) was chosen for further experiments. It should be noted The influence of interfering ion on the response behavior of
that, since in this pH half of the fluoride anions were in ion-selective membrane electrode is usually described in terms of
selectivity coefficients. Potentiometric selectivity coefficient
values for the present sensor were determined by the match
potential method (MPM) which is recommended by IUPAC
[76,77]. According to this method, the specified activity (concen-
tration) of the primary ion (A) is added to a reference solution,
and the potential is measured. In a separate experiment, the
interfering ion (B) is successively added to an identical reference
solution until the measured potential matched that obtained
before by adding the primary ions. The matched potential
selectivity coefficients, is then given by the resulting primary
ion to interfering ion activity (concentration) ratio. The experi-
mental conditions employed and the resulting values are given in
Fig. 9.
As it can be seen from Fig. 9, the electrode is very selective to
fluoride ion and the observed selectivity pattern significantly
differs from the so-called Hofmeister selectivity sequence. The
order of anion selectivity of the electrode shown in Fig. 9

Fig. 6. Potential responses of F  -selective electrode based on NbTPP–GO.

Fig. 8. Dynamic response of fluoride membrane electrode for step changes in

Fig. 7. Effect of pH of the test solution (1.0  10  3 mol L  1of F  ) on the potential concentration of F  (A) 1.0  10  7, (B) 1.0  10  6, (C) 1.0  10  5, (D) 1.0  10  4,
response of the F  selective electrode. (E) 1.0  10  3 and (F) 1.0  10  2 M.
 T. Poursaberi et al. / Talanta 101 (2012) 128–134 133

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