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

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

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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 b

Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, Zahedan 98135-674, Iran Department of Chemistry, University of Zabol, Zabol, Iran

a r t i c l e

i n f o

Article history: Received 21 August 2017 Received in revised form 16 December 2017 Accepted 3 January 2018 Available online 5 January 2018 Keywords: Thorium Zirconium-based metal-organic framework UiO-66-OH Solid-phase extraction Water analysis Spectrophotometry

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

1. Introduction 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 environmental samples is of importance. So far, several methods such as, ion chromatography (IC) [5], inductively coupled plasma-optical emission spectrometry (ICP-OES) [6], flow injection analysis (FIA) [7], inductively coupled plasma-mass spectrometry (ICP-MS) [8], capillary zone electrophoresis (CZE) [9], fluorimetry [10], and electrochemical techniques [11] have been used for the determination of thorium. Spectrophotometry 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 disadvantages of the technique including low sensitivity and impossibility of direct determination without sample preparation [12]. ⁎ Corresponding author. E-mail address: [email protected] (M. Kaykhaii).

https://doi.org/10.1016/j.saa.2018.01.010 1386-1425/© 2018 Elsevier B.V. All rights reserved.

Nowadays, solid-phase extraction (SPE) is one of the most extensive 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 crystalline 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 conditions. 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 various 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 stability (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) \C4H3(OH)\\CO2)6 in which rigid Zr6O4(OH)4 octahedral con4(O2C\ nected together by twelve carboxylate groups from

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 synthesis of the MOF using hydrochloric acid results in missing-linker defects [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 solution, amount of Zr-based MOF, type and volume of eluting solvent, adsorption 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. Zirconium tetrachloride (ZrCl4), 2 hydroxyterephthalic acid and N,N′ diimethyl formamide (DMF) were obtained from Sigma-Aldrich (MO, USA). A stock standard solution of thorium (1000 mg·L− 1) was prepared by dissolving 2.38 g of thorium nitrate in 1000 mL of double distilled water. Working standard solutions were prepared by serial dilutions of the stock solution prior to analysis. 1 g of morin was dissolved in 1000 mL of double distilled water (1000 mg·L−1) for determination 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 spectrophotometer (UV-2100 RAYLeigh, Beijing, China) by monitoring the absorbance at maximum wavelength of 410 nm. All experiments were performed in triplicate at least and the mean values were used for optimization. A Metrohm (Switzerland) model 630 pH meter was used for pH measurements. Powder X-ray diffraction (PXRD) patterns were recorded on a Philips X'pert diffractometer (Netherlands) with

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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 Spectrum-FTIR, version 10.01.00 (USA). The morphology and chemical composition 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 experiments 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 facilitate adsorption of Th-morin complexes onto the sorbent. The MOF solid was then isolated by centrifugation (1000 rpm, 2 min). The aqueous 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

Scheme 1. Proposed structure of UiO-66-OH with missing-linker defects.

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3. Results and Discussion 3.1. Characterizations of UiO-66-OH

Fig. 1. Absorption spectra of morin, thorium-morin complex and thorium-morin complex after desorption from the sorbent.

centrifugation (1000 rpm, 2 min) and the concentration of thorium in elution was analyzed by UV–Vis spectrophotometry. The extraction recovery (ER%) was calculated using the equation:

ER% ¼

α  100 β

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 determined 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 experiments, 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.

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 to the interactions (H-bonds) between\\OH and free-carboxyl groups 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 adsorption and after desorption of the sample from its surface. As can be seen, both images look like the same which verifies that the structure of MOF 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 patterns were also recorded and showed in Fig. 2, which again validates the full stability of MOF in the strong acidic conditions. 3.2. Optimization of SPE Procedure To obtain satisfactory extraction efficiency, several important parameters such as pH of the sample solution, amount of MOF, type and volume of eluting solvent, adsorption and desorption time and concentration 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 performance [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, hydrochloride acid, and nitric acid were used. As shown in Fig. 5, nitric acid

(111)

Intensity (a.u.)

(200)

The desorbed MOF

The fresh MOF The simulated 5

10

15

20

25 30 2θ (Degree)

35

40

45

Fig. 2. PXRD patterns of the MOF; simulated (bottom), fresh (middle), and after analyte desorption (top).

50

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0

UiO-66-OH

UiO-66-OH-ThM

3850

3350

2850 2350 1850 Wavenumber (cm-1 )

1350

850

79

100 90 80 70 60 50 40 30 20 10 0

Extraction recovery (%)

Tra nsmitta nce

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350

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 solvent was also assessed in the range of 0.05 to 0.40 mol·L−1 for the extraction 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 replace 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 increased and then remained unchanged (Fig. 9(a)) which means that 30 min is enough to reach equilibrium. Desorption time was also investigated 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

Ex tra ctio n reco v ery (%)

100 95 90 85

80 75

70 65 60 0.0

0.1

0.2

0.3

Concentration of HNO3 Fig. 4. SEM images of UiO-66-OH MOF; (a) after synthesis and (b) after one cycle of extraction and desorption of thorium complex.

0.4

0.5

(mol.L −1 )

Fig. 6. Effect of eluent concentration on thorium extraction. Condition: Th+4, 2 mg·L−1, morin, 2 mg·L−1, pH = 2.

Z.S. Moghaddam et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 194 (2018) 76–82

100

120

95

100

90

Extraction recovery (%)

Extraction recovery (%)

80

85 80 75 70 65

80 60 Adsorpon me

40

Desorpon me 20 0 0

60 0.5

1.0 1.5 2.0 2.5 3.0 Volume of HNO3 0.2 mol.L-1(mL)

3.5

20

40

60

4.0 Time (min) Fig. 9. Effect of adsorption time on thorium extraction (a) and effect of desorption time on thorium extraction (b).

Fig. 7. Effect of volume of eluting solvent on thorium extraction.

carboxylate groups of the sorbent with\\OH groups of Th-Morin complex. This can be confirmed by IR spectrum (Fig. 3), which shows that 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 efficiency of extraction decreases [40]. 3.2.5. Effect of Volume of Morin Ligand Morin was used to complex thorium before its extraction. The effect of morin volume on recovery between 0 and 30 μL of it was studied. A 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 by increasing the ligand volume up to 20 μL and then decreased. In lower quantities of morin, the stoichiometry point is not reached, while at higher amounts, probably due to the competition between ligand 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. 3.2.6. Effect of Interfering Ions In order to demonstrate the selectivity of this method for the extraction of thorium, the effect of various metal ions in aqueous samples were investigated. Interference studies were performed under optimized conditions and for 2 mg·L−1 concentration of the Thorium and different concentrations of foreign ions. The not interfering limit of a foreign ion was taken as the highest amount that produced an error not exceeding 5% in the analytical signal. The results are summarized in Table 1 and showed that the normal concentrations, tested ions do not interfere on the pre-concentration and determination of Thorium. The origin of the selective enrichment of Th4+ can be considered to be in relation

100 Extraction recovery (%)

0.0

90 80 70 60 50 40 0

1

2

3

4

5

6

7

pH

Fig. 10. Effect of pH on thorium extraction.

with hydroxyl functionality on organic linkers of MOF, as coordinating and hydrogen-bonding sites via\\OH group in addition to the possibility of the non-covalent interactions between the benzene dicarboxylate linker and guest species. 3.3. Linear Range, Limit of Detection and Precision This technique was evaluated with linearity, detection limit, coefficient of determination, enrichment factor, accuracy and precision using spiked solution of aqueous samples under the optimum condition. Results were summarized in Table 2. The total thorium adsorption capacity of Zr-MOF was calculated by the equation qe = (Ci − Cf)V / w where qe is sorption capacity, Ci and Cf are the concentration of thorium

100

100 Extraction recovery (%)

Extraction recovery (%)

95 90 85 80 75 70 65 60 0

10

20 30 40 Amount of MOF (mg)

50

Fig. 8. Effect of amount of UiO-66-OH on thorium extraction.

60

90 80 70 60 50 40 0

5 10 15 20 Volume of complexing agent (µL)

25

30

35

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 Table 1 Effect of interference ions on the tolerance limits of thorium in the aqueous samples under the optimized condition. Ion

Tolerance limit (mg·L−1)

Li+, Na+, K+ Ca2+, Mg2+, Ba2+ Ag+, Zn2+, Ni2+, Co2+, Cr3+, Mn2+, Cu2+, Fe3+, Pb+2

1000 1000 10

Table 4 Determination of the thorium in water samples (n = 3). Sample

Chah nimeh # 1 Chah nimeh # 2 Chah nimeh # 3

Table 2 Analytical figure of merit for SPE extraction of thorium. Parameter

Analytical figure

Equation of calibration curve Dynamic range (μg·L−1) R2 (determination coefficient) Repeatability (RSD %, n = 7) Limit of detection (μg·L−1) Enrichment factor Capacity of sorbent (mg·g−1)

A = 0.002CTh + 0.006 10–2000 0.9976 0.84 0.35 250 47.5

81

Thorium content (μg·L−1) Added

Found

20 100 20 100 20 100

19.3 93 19.1 94 18 91.5

RSD (%)

2.4 2.9 2.7 3.5 3.1 3.1

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 missing-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 capacity toward thorium ion. This sorbent could be regenerated and reused at least 25 times without significant decrease of extraction recoveries. 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 spectrophotometric instrumentations own its merits of simplicity, cheapness, portability and so on.

(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 containing 0.02 mg of thorium at the optimum pH. Then, the solution was vigorously 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 calibration curve). The relative standard deviation (RSD %) of seven replicate 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 Thorium. 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.

Conflict of Interest The authors have declared no conflict of interest. References [1] M. Rezaee, F. Khalilian, A novel method for the determination of trace thorium by dispersive liquid-liquid microextraction based on solidification of floating organic drop, Quim Nova 39 (2016) 167–171. [2] S.R. Yousefi, S.J. Ahmadi, F. Shemirani, M.R. Jamali, M. Salavati-Niasari, Simultaneous extraction and preconcentration of uranium and thorium in aqueous samples by new modified mesoporous silica prior to inductively coupled plasma optical emission spectrometry determination, Talanta 80 (2009) 212–217. [3] A.S. Al-Kady, Optimized and validated spectrophotometric methods for the determination of trace amounts of uranium and thorium using 4-chloro-N-(2,6dimethylphenyl)-2-hydroxy-5-sulfamoylbenzamide, Sensors Actuators B Chem. 166-167 (2012) 485–491. [4] B. Kirkan, G.A. Aycik, Solid phase extraction using silica gel modified with azo-dyes derivative for preconcentration and separation of Th(IV) ions from aqueous solutions, J. Radioanal. Nucl. Chem. 308 (2015) 81–91. [5] V.V. Raut, S. Jeyakumar, M.K. Das, A. Chandane, B.S. Tomar, Separation and determination of trace thorium in uranium matrix using chelation ion chromatography, Sep. Sci. Technol. (2016) 1–7. [6] S.R. Yousefi, E. Zolfonoun, On-line solid phase extraction using ion-pair microparticles combined with ICP-OES for the simultaneous preconcentration and determination of uranium and thorium, Radiochim. Acta 104 (2016) 801–807.

3.4. Real Sample Analysis To assess the performance of this method, separation and preconcentration of thorium ion in three water samples under the optimized 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 obtained which shows the high selectivity and capability of UiO-66-OH zirconium metal-organic toward Thorium extraction. ICP-MS was used Table 3 Comparison of the proposed method with other methods for the determination of thorium. Sorbent

Detection technique

LOD (μg·L−1)

Capacity of sorbent (mg·g−1)

linear range (μg·L−1)

Enhancement factor

RSD (%)

Ref.

MCM-41 (modified mesoporous silica) Ion-pair microparticles Modified silica gel Duolite XAD761 (cross-linked phenol formaldehyde polymer) Amberlite XAD-4 resin Merrifield chloromethylated resin Amberlite XAD-2000 resin UiO-66-OH MOF

ICP-OES ICP-OES Spectrophotometry ICP-MS Spectrophotometry ICP-AES Spectrophotometry Spectrophotometry

0.3 0.21 0.43 0.0045 1.5 4.29 0.54 0.35

49 NM 37.4 NM 17.24 41.175 3.3 47.5

1–1500 2–500 1.43–103 NM 100–10,000 20–3400 200–3500 10–2000

NMa 90 20.2 NM 100 NM 100 250

2.8 3.1 2.47 b4.5 b2 1.5 3.7 0.84

[2] [6] [41] [42] [43] [44] [45] Present work

a

NM = not mentioned.

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