Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 194 (2018) 76–82

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Spectrochimica Acta Part A: Molecular and Biomolecular

Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Synthesis of UiO-66-OH zirconium metal-organic framework and its

application for selective extraction and trace determination of thorium in
water samples by spectrophotometry
Zahra Safaei Moghaddam a, Massoud Kaykhaii a,⁎, Mostafa Khajeh b, Ali Reza Oveisi b
a
Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, Zahedan 98135-674, Iran
b
Department of Chemistry, University of Zabol, Zabol, Iran

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

Article history: In this study, a zirconium-based metal-organic framework (Zr-MOF), named UiO-66-OH, was synthesized
Received 21 August 2017 by the solvo-thermal method and characterized by Fourier transform-infrared spectroscopy (FTIR), powder
Received in revised form 16 December 2017 X-ray diffraction (PXRD), and scanning electron microscopy (SEM). This Zr-MOF was then employed as a
Accepted 3 January 2018
sorbent for selective extraction and preconcentration of thorium ions after their complexation with
Available online 5 January 2018
2 (2,4 dihydroxyphenyl) 3,5,7 trihydroxychromen 4 one (morin) from environmental water samples
Keywords:
prior to its spectrophotometrical determination. The experimental parameters affecting extraction, such
Thorium as pH of sample solution, amount of Zr-MOF, type and volume of eluting solvent, adsorption and desorption
Zirconium-based metal-organic framework time, and concentration of complexing agent were evaluated and optimized. Under the optimized condi-
UiO-66-OH tions, an enrichment factor of 250 was achieved. The limit of detection was calculated to be 0.35 μg·L− 1
Solid-phase extraction with a linear range between 10 and 2000 μg·L−1of thorium. The maximum sorption capacity of MOF toward
Water analysis thorium was found to be 47.5 mg·g− 1. The proposed procedure was successfully applied to the analysis of
Spectrophotometry real water samples.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction Nowadays, solid-phase extraction (SPE) is one of the most extensive

Thorium, as one of the nuclear power sources, is found in plants,
sand, soil, rocks, and water [1]. Moreover, this radioactive element is
used in gas mantles and kerosene lamps to produce bright white light
when heated [2]. Thus, people can be exposed to thorium through air,
food and water. Studies have been shown that continuous exposure of
thorium can cause cancer in various forms [3]. According to World
Health Organization, acceptable thorium concentration in drinking
water is normally b20 μg·L−1 [4]. Thus, determination of thorium in en-
vironmental samples is of importance. So far, several methods such as,
ion chromatography (IC) [5], inductively coupled plasma-optical emis-
sion spectrometry (ICP-OES) [6], flow injection analysis (FIA) [7], induc-
tively coupled plasma-mass spectrometry (ICP-MS) [8], capillary zone
electrophoresis (CZE) [9], fluorimetry [10], and electrochemical tech-
niques [11] have been used for the determination of thorium. Spectro-
photometry represents an attractive common technique due to its
high precision and accuracy in measurement associated with its lower
cost compared to the above mentioned techniques. But there are disad-
vantages of the technique including low sensitivity and impossibility of
direct determination without sample preparation [12].
⁎ Corresponding author.
E-mail address: kaykhaii@chem.usb.ac.ir (M. Kaykhaii).
and most efficient method for the separation and pre-concentration of
trace elements in environmental samples, food and water samples,
benefiting from its high enrichment factor, high repeatability, low
need for organic solvents, saving cost and time, and ease of automation.
In SPE, solid adsorbents have been shown great potential for improving
the extraction, sensitivity, and accuracy [13–15].
Metal-organic frameworks (MOFs), are three-dimensional crystal-
line porous materials having various geometries and functional groups
within the channels/cavities, which are synthesized by mixing organic
linkers and metal salts, often under hydrothermal or solvothermal con-
ditions. Adjustable pore-sizes and controllable structural properties,
extra ordinarily large porosity, low density, and very high surface
areas are the unique characteristics of the hybrid solids. As a result,
MOFs have been considered as promising candidate materials for vari-
ous applications such as adsorption [16–18], sensing [19], catalysis
[20], separation [21], gas storage [22], luminescence [23], drug delivery
[24], conductivity [25], removal of toxic materials [26,27], nuclear waste
partitioning [28–31] and radioactive remediation [32–35]. Zirconium(-
IV)
-based metal organic frameworks show an exceptional thermal sta-
bility (up to 550 °C) and the chemical stability in water and organic
solvents. UiO-66-OH, as a Zr-based MOF, has the formula of Zr6O4(OH)
4(O2C\ \C4H3(OH)\\CO2)6 in which rigid Zr6O4(OH)4 octahedral con-
nected together by twelve carboxylate groups from

https://doi.org/10.1016/j.saa.2018.01.010
1386-1425/© 2018 Elsevier B.V. All rights reserved.
 Z.S. Moghaddam et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 194 (2018) 76–82
2 hydroxyterphthalic acid linkers (Scheme 1). The solvo-thermal syn-
thesis of the MOF using hydrochloric acid results in missing-linker de-
fects [36,37] in the framework, leading to enhanced porosity, hydroxyl
groups and zirconium open metal sites, thus, causing to increase of
the adsorption, substrate uptake, and catalytic efficiency.
These finding motivated us to prepare and apply the UiO-66-OH
MOF as sorbent for the extraction of Th(IV) ions after its chelating
with morin. The experimental parameters such as pH of sample solu-
tion, amount of Zr-based MOF, type and volume of eluting solvent, ad-
sorption and desorption time, and concentration of complexing agent
were investigated.
2. Experimental
2.1. Chemicals
Reagent grade Th(NO3)4·4H2O and nitrate or chloride salts of other
cations were obtained from Merck (Germany) and used as received. Zir-
conium tetrachloride (ZrCl4), 2 hydroxyterephthalic acid and N,N′ di-
imethyl formamide (DMF) were obtained from Sigma-Aldrich (MO,
USA). A stock standard solution of thorium (1000 mg·L− 1) was pre-
pared by dissolving 2.38 g of thorium nitrate in 1000 mL of double dis-
tilled water. Working standard solutions were prepared by serial
dilutions of the stock solution prior to analysis. 1 g of morin was dis-
solved in 1000 mL of double distilled water (1000 mg·L−1) for determi-
nation of thorium and was used as a ligand to react with Th(IV).
2.2. Instrumentation
Absorption measurements were carried out with a UV–Vis spectro-
photometer (UV-2100 RAYLeigh, Beijing, China) by monitoring the ab-
sorbance at maximum wavelength of 410 nm. All experiments were
performed in triplicate at least and the mean values were used for opti-
mization. A Metrohm (Switzerland) model 630 pH meter was used for
pH measurements. Powder X-ray diffraction (PXRD) patterns were re-
corded on a Philips X'pert diffractometer (Netherlands) with
Scheme 1. Proposed structure of UiO-66-OH with missing-linker defects.
77
monochromated Cu Kα radiation (λ = 1.5418 Å) at a range of 5° b 2θ
b 50°. Fourier transformed infrared (FTIR) spectra were recorded in
the range of 4000–500 cm−1 using KBr pellets on a Perkin Elmer Spec-
trum-FTIR, version 10.01.00 (USA). The morphology and chemical com-
position of the sample was characterized using scanning electron
microscopy (SEM, MIRA3 TESCAN, Czech Republic).
2.3. Synthesis of UiO-66-OH
The synthesis of UiO-66-OH Zr-based MOF was based on the method
suggested by Katz et al. [36]. In a 30 mL vial, ZrCl4 (125 mg, 0.54 mmol),
5 mL dimethyl formamide (DMF) and 1 mL of concentrated HCl were
loaded and sonicated for 10 min until all solids fully dissolved. Then,
2 hydroxyterephthalic acid (135 mg, 0.75 mmol) and 10 mL DMF
were added to the solution and sonicated for more 20 min. The obtained
mixture was placed in an oven and heated at 80 °C for 12 h. After cooling
down to room temperature, the resulting solid was filtered, repeatedly
washed several times with DMF and then with ethanol. Finally, it was
dried at 120 °C under vacuum to give the MOF.
2.4. SPE Procedure
For optimization of the extraction parameters, the sorption experi-
ments were performed according to a batch method: a 10 mL measuring
flask was loaded with 20 μL of the 1000 mg·L−1 standard solution of
Th(IV) (0.008 mmol) then 20 μL of morin solution (0.006 mmol) was
added. The mixture was made up to the mark with double distilled
water then was transferred to a beaker and the pH was adjusted to 2.0
by drop-wise addition of HCl 0.15 M. 10 mg of UiO-66-OH adsorbent
was added to the solutions and was shake on a shaker for 30 min to fa-
cilitate adsorption of Th-morin complexes onto the sorbent. The MOF
solid was then isolated by centrifugation (1000 rpm, 2 min). The aque-
ous phase was easily decanted by simply inverting the tube. 1 mL of
HNO3 0.2 mol·L−1 solution was added as eluent to the precipitate and
was shaken for 30 min. Finally, UiO-66-OH was separated by
78 Z.S. Moghaddam et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 194 (2018) 76–82

3. Results and Discussion

3.1. Characterizations of UiO-66-OH

The powder X-ray diffraction (PXRD) pattern of synthesized MOF is

shown in Fig. 2. It can be observed that the peaks are consistent well
with that previously reported [36,39]. The two most intensive peaks at
2θ = 7.3 and 8.5° are related to the (111) and the (200) crystal planes,
respectively.
FT-IR spectrum of MOF shows absorption bonds at 1590 and
1390 cm−1 which are assigned to the carboxylate groups (Fig. 3). The
peaks at 450–750 cm−1 are corresponded to\\OH and C\\H stretching.
After adsorption of Th-complex on the MOF, the intensity of bands
centred at about 3350 and 1610 cm−1 were increased. This can be due
Fig. 1. Absorption spectra of morin, thorium-morin complex and thorium-morin complex to the interactions (H-bonds) between\\OH and free-carboxyl groups
after desorption from the sorbent. of adsorbent and\\OH and carbonyl groups of Th-Morin complex.
Scanning electron microscopy (SEM) of the surface morphology of
UiO-66-OH MOF is presented in Fig. 4 before Thorium complex adsorp-
centrifugation (1000 rpm, 2 min) and the concentration of thorium in tion and after desorption of the sample from its surface. As can be seen,
elution was analyzed by UV–Vis spectrophotometry. both images look like the same which verifies that the structure of MOF
The extraction recovery (ER%) was calculated using the equation: is the same after the extraction and desorption process. Aggregates of
spheroidal-shaped particles in the range of about 50–200 nm are clearly
visible. In order to further confirm the stability of the sorbent, its PXRD
α
ER% ¼  100 patterns were also recorded and showed in Fig. 2, which again validates
β
the full stability of MOF in the strong acidic conditions.

where β is the absorption of standard solution and α is the absorption of
solution in eluent.
2.5. Absorption Spectra of Complex
In order to obtain the maximum wavelength of absorption for the
complex, the absorption spectra of Th(IV)-morin complex was deter-
mined in the range of 200 to 600 nm against the reagent blank, with a
maximum at 410 nm as shown in Fig. 1. During all of the following ex-
periments, the blank absorbance of all reagents was corrected.
The reaction between thorium and morin ligand is (MH) [38]:
xTh
4þ
þ yMH→Thx My þ yHþ
The stoichiometric ratio of Th to ligand is 1:1.
3.2. Optimization of SPE Procedure
To obtain satisfactory extraction efficiency, several important pa-
rameters such as pH of the sample solution, amount of MOF, type and
volume of eluting solvent, adsorption and desorption time and concen-
tration of complexing agent were investigated and optimized which are
discussed below. For all these experiments, a standard solution of
1000 mg·L−1 of Th(IV) was used.
3.2.1. Effect of Type, Concentration and Volume of the Eluent
It is very important to choose eluting solvent which can effectively
elute Th(IV) from MOF. This will greatly influence the elution perfor-
mance [15]. The choice of solvent was appraised for the extraction of
10 mL of a standard Th(IV) solution containing 2 mg·L−1 of the analyte
in deionised water. In order to choose a proper eluent, various usual
SPE eluting solvents such as methanol, ethanol, toluene, acetonitrile, hy-
drochloride acid, and nitric acid were used. As shown in Fig. 5, nitric acid

(111)

(200)
Intensity (a.u.)

The desorbed MOF

The fresh MOF

The simulated

5 10 15 20 25 30 35 40 45 50
2θ (Degree)

Fig. 2. PXRD patterns of the MOF; simulated (bottom), fresh (middle), and after analyte desorption (top).
 Z.S. Moghaddam et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 194 (2018) 76–82 79

0.9 100

Extraction recovery (%)

0.8 90
Tra nsmitta nce

0.7 80
0.6 70
0.5 60
UiO-66-OH
0.4 50
0.3 40
0.2 30
0.1 20
0.0
UiO-66-OH-ThM 10
0
3850 3350 2850 2350 1850 1350 850 350
Wavenumber (cm-1 )

Fig. 3. FT-IR spectrum of UiO-66-OH before and after thorium complex sorption.

affording the highest extraction recovery and hence was chosen as the
best elution solvent. The influence of concentration of desorption sol-
vent was also assessed in the range of 0.05 to 0.40 mol·L−1 for the ex-
traction of the same standard solution. Results which are presented in
Fig. 6 show that nitric acid at a concentration of 0.2 mol·L−1 has the
highest elution power; presumably because its protons can be easily re-
place Th-complex in the structure of the MOF (this concentration of acid
Eluent type
Fig. 5. Effect of eluent type on thorium extraction. Condition: Th+4, 2 mg·L−1, morin,
2 mg·L−1, pH = 2.
has a pH of 0.7). The effect of the volume of eluting solvent was studied
in the range of 0.2 to 4.0 mL (Fig. 7). The maximum extraction recovery
of the analyte was obtained when the volume of the elution solvent was
1.0 mL. In higher volumes a diverse effect is observed, probably due to
the dilution of the preconcentrated thorium.

3.2.2. Influence of the Amount of Adsorbent

Next, the amount of UiO-66-OH MOF was varied within the range of
5.0–50.0 mg while all other parameters were constant. As can be seen in
Fig. 8, the maximum extraction recovery was obtained when the
amount of the sorbent was 10.0 mg. That's mainly because at higher
amounts, the retained thorium could not be completely eluted by
1 mL of 0.2 mol·L− 1 HNO3. It is not also possible to further increase
the volume of the acid, because it needs a longer settling down times,
so, 10.0 mg of MOF was employed in the following experiments.

3.2.3. Effect of the Adsorption and Desorption Times

Solid phase extraction is an equilibrium distribution process. To find
the best equilibrium time, absorption was tested from 5 to 50 min. It
was observed that up to 30 min, the extraction recovery of analyte in-
creased and then remained unchanged (Fig. 9(a)) which means that
30 min is enough to reach equilibrium. Desorption time was also inves-
tigated up to 50 min and the results are shown in Fig. 9(b). The recovery
increases by increasing contact time of eluting solvent and MOF, and at
30 min, Th(IV) is almost completely eluted.

3.2.4. Effect of pH
The effect of pH of the sample on the Thorium extraction using the
MOF adsorbent was investigated and shown in Fig. 10. HCl 0.15 M was
used for pH adjustments. The best adsorption efficiency was obtained
at pH 2.0. In this pH, H-bond interactions occur between \\OH and

100
95
Ex tra ctio n reco v ery (%)

90
85
80
75
70
65
60
0.0 0.1 0.2 0.3 0.4 0.5
Concentration of HNO3 (mol.L −1 )

Fig. 4. SEM images of UiO-66-OH MOF; (a) after synthesis and (b) after one cycle of Fig. 6. Effect of eluent concentration on thorium extraction. Condition: Th+4, 2 mg·L−1,
extraction and desorption of thorium complex. morin, 2 mg·L−1, pH = 2.
80 Z.S. Moghaddam et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 194 (2018) 76–82

100 120

95 100
Extraction recovery (%)

90

Extraction recovery (%)

80
85
60
80
Adsorpon me
75 40
Desorpon me
70 20
65
0
60 0 20 40 60
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Volume of HNO3 0.2 mol.L-1(mL) Time (min)

Fig. 7. Effect of volume of eluting solvent on thorium extraction. Fig. 9. Effect of adsorption time on thorium extraction (a) and effect of desorption time on
thorium extraction (b).

carboxylate groups of the sorbent with\\OH groups of Th-Morin com-

plex. This can be confirmed by IR spectrum (Fig. 3), which shows that
100
the intensity of \\OH bond is reduced due to this interaction. When
pH is higher than 2, Th-Morin complex is not stable, therefore, the effi- 90

Extraction recovery (%)

ciency of extraction decreases [40].
80

70
3.2.5. Effect of Volume of Morin Ligand
Morin was used to complex thorium before its extraction. The effect 60
of morin volume on recovery between 0 and 30 μL of it was studied. A
50
concentration of 1000 mg·L− 1 of the ligand was used. Results are
showed in Fig. 11. As can be seen, extraction recovery was enhanced 40
by increasing the ligand volume up to 20 μL and then decreased. In 0 1 2 3 4 5 6 7
pH
lower quantities of morin, the stoichiometry point is not reached,
while at higher amounts, probably due to the competition between li-
Fig. 10. Effect of pH on thorium extraction.
gand itself and Th-morin complex to absorb to the MOF, a decrease in
recovery observes Thus, a volume of 20 μL of morin was chosen for
the subsequent experiments.
with hydroxyl functionality on organic linkers of MOF, as coordinating
and hydrogen-bonding sites via\\OH group in addition to the possibil-
3.2.6. Effect of Interfering Ions
ity of the non-covalent interactions between the benzene dicarboxylate
In order to demonstrate the selectivity of this method for the extrac-
linker and guest species.
tion of thorium, the effect of various metal ions in aqueous samples
were investigated. Interference studies were performed under opti-
3.3. Linear Range, Limit of Detection and Precision
mized conditions and for 2 mg·L−1 concentration of the Thorium and
different concentrations of foreign ions. The not interfering limit of a for-
This technique was evaluated with linearity, detection limit, coeffi-
eign ion was taken as the highest amount that produced an error not ex-
cient of determination, enrichment factor, accuracy and precision
ceeding 5% in the analytical signal. The results are summarized in Table
using spiked solution of aqueous samples under the optimum condi-
1 and showed that the normal concentrations, tested ions do not inter-
tion. Results were summarized in Table 2. The total thorium adsorption
fere on the pre-concentration and determination of Thorium. The origin
capacity of Zr-MOF was calculated by the equation qe = (Ci − Cf)V / w
of the selective enrichment of Th4+ can be considered to be in relation
where qe is sorption capacity, Ci and Cf are the concentration of thorium

100
100
95
90
Extraction recovery (%)

Extraction recovery (%)

90

85 80

80 70
75
60
70

65 50

60 40
0 10 20 30 40 50 60 0 5 10 15 20 25 30 35
Amount of MOF (mg) Volume of complexing agent (µL)

Fig. 8. Effect of amount of UiO-66-OH on thorium extraction. Fig. 11. Effect of concentration of complexing agent (morin) on thorium extraction.
 Z.S. Moghaddam et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 194 (2018) 76–82 81

Table 1 Table 4
Effect of interference ions on the tolerance limits of thorium in the aqueous samples under Determination of the thorium in water samples (n = 3).
the optimized condition.
Sample Thorium content (μg·L−1) RSD (%)
Ion Tolerance limit (mg·L−1)
Added Found
Li+, Na+, K+ 1000
Chah nimeh # 1 20 19.3 2.4
Ca2+, Mg2+, Ba2+ 1000
100 93 2.9
Ag+, Zn2+, Ni2+, Co2+, Cr3+, Mn2+, Cu2+, Fe3+, Pb+2 10
Chah nimeh # 2 20 19.1 2.7
100 94 3.5
Chah nimeh # 3 20 18 3.1
Table 2 100 91.5 3.1
Analytical figure of merit for SPE extraction of thorium.

Parameter Analytical figure

Equation of calibration curve A = 0.002CTh + 0.006

Dynamic range (μg·L−1) 10–2000
R2 (determination coefficient) 0.9976
Repeatability (RSD %, n = 7) 0.84
Limit of detection (μg·L−1) 0.35
Enrichment factor 250
Capacity of sorbent (mg·g−1) 47.5
(mg·L−1) before and after the adsorption procedure, V is the volume of
the sample solution (mL) and w is the amount of sorbent (g). A sorbent
amount of 10 mg was added to the 250 mL of aqueous solution contain-
ing 0.02 mg of thorium at the optimum pH. Then, the solution was vig-
orously shaken for 30 min. After centrifugation, the remaining thorium
in the supernatant solution was determined spectrophotometrically.
The results indicated a large adsorption capacity of 47.5 mg·g− 1 for
the Zr-MOF. Linearity of the method was obtained in the concentration
range of 10–2000 μg·L−1 with the coefficient of determination (R2) of
0.998. The limit of detection (LOD) was calculated 0.35 μg·L−1 based
on the equation CLOD = 3(Sd)blank / m (Sd is the standard deviation of
ten consecutive measurements of the blank and m is the slope of cali-
bration curve). The relative standard deviation (RSD %) of seven repli-
cate determinations was b 0.84% (C = 2 mg·L−1). This indicated that
the method has good precision for the analysis of trace amounts of Tho-
rium. A comparison between the figures of merit of this method with
other SPE methods used for preconcentration and analysis of thorium
are summarized in Table 3. As can be seen, the MOF sorbent has high
sorption capacity for thorium and LOD is better than the listed methods.
3.4. Real Sample Analysis
To assess the performance of this method, separation and
preconcentration of thorium ion in three water samples under the opti-
mized condition was tested. Water samples were collected from three
surface water reservoirs (Chah-Nimeh, Zabol, Iran) and were analyzed
without filtration. Since in the real samples no thorium was detected,
they were spiked with two levels of concentrations of Th(IV) (Table
4). It can be seen that can see that good recoveries and RSDs were ob-
tained which shows the high selectivity and capability of UiO-66-OH
zirconium metal-organic toward Thorium extraction. ICP-MS was used
for the comparison with the spectrophotometric determination of the
real samples for further validation.
4. Conclusion
In the present study, a porous Zr-based MOF, UiO-66-OH, with miss-
ing-linker defects was prepared and successfully applied as a selective
sorbent for solid phase extraction of thorium ions in batch mode by
spectrophotometry. The prepared sorbent has high stability, reusability
and low toxicity. It was exhibited high extraction efficiency and high ca-
pacity toward thorium ion. This sorbent could be regenerated and
reused at least 25 times without significant decrease of extraction re-
coveries. The proposed analytical method based on this sorbent showed
adequate accuracy, very low detection limits, and good RSD. The
method compares favourably with a reference ICP method, while spec-
trophotometric instrumentations own its merits of simplicity, cheap-
ness, portability and so on.
Conflict of Interest
The authors have declared no conflict of interest.
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