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Preparation of polyvinylpyrrolidone modified nanomagnetite for degradation of nicotine by heterogeneous Fenton process
Journal of Environmental Chemical Engineering 7 (2019) 102988
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Preparation of polyvinylpyrrolidone modified nanomagnetite for degradation of nicotine by heterogeneous Fenton process Roman Buláneka, Radim Hrdinab, Asaad F. Hassana,c,
T
⁎
a
Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice, Czechia Institute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of Pardubice, Czechia c Department of Chemistry, Faculty of Science, University of Damanhour, Damanhour, Egypt b
A R T I C LE I N FO
A B S T R A C T
Keywords: Nanomagnetite Composite Characterization Nicotine Fenton
Nanomagnetite (Ng), polyvinylpyrrolidone modified nanomagnetite (NgM), and polyvinylpyrrolidone/nanomagnetite composite (NgC) were prepared in presence of nitrogen gas. Thermogravimetric analysis showed that NgC contains higher polyvinylpyrrolidone/nanomagnetite (PVP/Ng) ratio. Assessments of nitrogen adsorption, SEM, TEM, and EDX data indicate that specific surface area of investigated materials is in order Ng ≈ ≈ NgM > NgC, materials form nano spheres with particle size around 9.0 nm according to TEM and Debye–Scherrer diffraction formula and content of magnetite in the prepared catalysts were 98.04, 76.88, and 56.95% in case of Ng, NgM and NgC, respectively. XRD confirms the cubic structure of nanocatalysts. FTIR spectra confirm the presence of stretching vibration of Fe-O bonds and magnetite fingerprint of skeletal vibrations. Degradation of nicotine by Fenton process catalyzed by nanomagnetite-based heterogeneous catalysts was studied under different conditions. Optimal reaction conditions for nicotine decomposition were found to be: equilibrium degradation time = 100 min, nanocatalyst dosage = 2.5 g L−1, pH = 2.5, hydrogen peroxide initial nicotine concentration = 100 mg L−1 and degradation concentration = 14 mmol L−1, temperature = 35 °C. Kinetic studies showed that the Fenton degradation of nicotine in the presence of polyvinylpyrrolidone modified nanomagnetite catalysts follows the pseudo-first order kinetic model. Catalyst reusability proved that NgM is efficient, reusable nanocatalyst materials for degradation of nicotine by Fenton process compared with the other two catalysts.
1. Introduction Alkaloid is a type of naturally occurring nitrogenous organic containing bases having a different physiological effects on animals and human. The well-known alkaloids include ephedrine, strychnine, quinine, morphine and nicotine. Some alkaloids, such as nicotine, are illicit and poison drugs obtained from Nicotiana tabacum (tobacco plant). For adult human beings forty to sixty milligrams of nicotine can be a lethal dosage [1]. Nicotine (3- substituted pyridine, C10H14N2) may cause many health problems to the eyes, digestive system, brain, heart and even genetic damage [2]. There are many reasons standing behind environmental pollution with aqueous nicotine such as: nicotine emission in the side stream and exhaled mainstream smoke of cigarettes. Nicotine is transferred to aqueous medium with a large amount during tobacco manufacturing and processing. Tobacco dust, as a by-product during manufacture of cigarette, with high amounts of nicotine accumulates in the environment of cigarettes manufacture and cannot be
⁎
recovered. It can be easily extracted from the tobacco dust and transported into ground-water [3,4]. Production of some pharmaceutical products (such as Habitrol, Nicoderm, Nicorette, Nicotrol, and Tetrahydronicotyrine) requires nicotine as the main ingredient material, which is responsible for other environmental nicotine pollution [5]. Removal of nicotine from aqueous medium has been studied through adsorption [6–9], photocatalysis [10] and extraction using organic eluents, such as, cyclohexane, toluene, hexane, kerosene or 1-butanole [3]. Biodegradation using microorganisms is still the main procedure for nicotine contamination treatment [11,12], but biological treatment of organic pollutants is time-consuming and not always recommended, as it removes only some of the wide range of pollutants [13,14]. Another alternative, how to remove organic pollutants frequently used in environment and pollution control is application of Fenton process. H.J.H. Fenton in 1894 described a new method for H2O2 decomposition by Fe+2 salts in the oxidation of tartaric acid [15]. Ferrous ions generate hydroxyl radicals [16] by the following reactions:
Corresponding author at: Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice, Czechia. E-mail address: [email protected] (A.F. Hassan).
https://doi.org/10.1016/j.jece.2019.102988 Received 5 September 2018; Received in revised form 21 February 2019; Accepted 25 February 2019 Available online 25 February 2019 2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
Journal of Environmental Chemical Engineering 7 (2019) 102988
R. Bulánek, et al.
Fe+2 +H2O2 → Fe+3 + HO + HO% (k = 63e76 M−1 s−1) Fe
+3
+ H2O2→ Fe
+2
%
+
+ HOO + H (k = 10
−3
e10 M s ) -2
-1
-1
2.3. Characterization
(1) (2)
Thermal gravimetric analysis (TGA) was investigated to gain knowledge on the thermal behavior of the prepared solid catalyst samples (Ng, NgM and NgC) using a differential thermal analyzer (Shimadzu DTA-50, Japan). Surface area (SBET, m2 g−1), total pore volume (VP, cm3 g−1) and pore size (nm) of samples were determined using ASAP 2020 gas sorption analyzer (Micromeritics). Nitrogen adsorption/desorption isotherms were determined at its boiling point. The samples were activated under vacuum at 350 °C for 4 h prior to measurement. The diffraction patterns (Cu Kα, λ = 1.5418 Å) were recorded on powdered samples using a D8 advance diffractometer (Bruker AXS, Germany) with Bragg-Brentano θ-θ goniometer (radius 217.5 mm) equipped with a secondary beam curved graphite monochromator and NaI scintillation detector. The scan was performed at room temperature from 10 to 70° (2 θ) in 0.02° step with a counting time of 10 s per step. Raman spectra were collected by Nicolet DXR2 Raman microscope (Thermo Scientific, USA) equipped by Smart excitation laser with wavelength of 785 nm. Spectra were recorded by accumulation of 100 scans (scan time was 10 s, resolution of 2 cm−1, laser power was 2 mW). The SEM of prepared particles was carried out on scanning electron microscope JEOL JSM-7500 F apparatus. In order to increase its conductivity, the sample was coated with an Au layer (0.2 nm) with the help of dust sprinkling equipment "Bio-Rad Polaron". HRTEM (High-resolution transmission electron microscopy) with EDX (energy dispersive X-ray) spectroscopy (JEOL-2100 F TEM) was utilized to get high magnification micrographs of the prepared samples and their chemical analysis. The instrument was operated at an accelerating voltage of 200 kV. The samples were subjected to ultrasonic in ethanol for 30 min and then dropped on a carbon-coated Cu TEM grid. Fourier transform infrared spectroscopy (FTIR) using a Mattson 5000 FTIR spectrometer in the range between 400 and 4000 cm−1. Discs were prepared by mixing 0.001 g of dried nanocatalyst sample with 0.4 g of KBr (spectroscopic purity, Merck) in an agate mortar, followed by pressing the mixture at 5 ton cm-3 for 3 min and 10 ton cm-3 for 5 min under vacuum.
By applying Photo-Fenton, the presence of UV–Vis illumination can accelerate the reduction process according to the following equations [17]: Fe+2 +H2O2 → Fe+3 + HO + HO%
(3)
Fe+3 +H2O + hυ → Fe+2 + HO%+ H+
(4)
Fe+3 + H2O2→ Fe+2 +HOO+ H+
(5)
Fenton process has been studied for removal of various pollutants from the waste waters. Homogeneous and heterogeneous applications of Fenton reaction are possible, but heterogeneous Fenton has great advantages in reducing iron loss, raising the efficiency of H2O2, and reducing iron sludge generation compared with homogeneous Fenton. The use of polyvinylpyrrolidone as polar organic additive during synthesis of nanomagnetite particle has been proposed to control the shape of the magnetic nanoparticle and show a plausible size distribution [18]. To the best of our knowledge, application of Fenton process for nicotine removal was not studied up to now. The goal of the present work was to prepare both nanomagnetite particles (Ng) and nanomagnetite particles modified by polyvinylpyrrolidone. Prepared materials were characterized by various physico-chemical techniques (thermal gravimetric analysis, N2 physisorption, XRD, FTIR, and SEM/ TEM) and tested in catalytic decomposition of nicotine as a toxic alkaloid at different reaction conditions, such as catalyst dosage, pH of nicotine solution, initial nicotine concentration, concentration of H2O2 and temperature. These are important experimental factors to choose the optimum conditions for nicotine degradation. 2. Materials and methods 2.1. Materials Polyvinylpyrrolidone (k 90, powder, average MW 360000, CAS 9003-39-8) and nicotine (> 99%) were obtained from Fluka Co. Ferric chloride, and ferrous chloride were obtained from Alfa-Aesar Co. Ltd. Other reagents were obtained from El-Nasr for pharmaceutical and chemical industrial Co., Egypt. All reagents were used without further purification.
2.4. Catalyst activity measurement The experiments were carried out in 250 mL stoppered Erlenmeyer flasks with an agitation of 120 rpm for about 160 min. Experiments were performed by taking the desired amount of stock nicotine solution (500 mg L−1) diluted to 200 mL with distilled water and followed by addition of the required amount of solid nanocatalyst. Initial pH of the solution was adjusted using 0.01 M H2SO4 or 0.01 M NaOH solution. Finally, the predetermined amount of hydrogen peroxide was added to start the reaction. Thereafter, 2 mL of samples were removed periodically from the solution reaction and analyzed for residual nicotine at λmax 260 nm [1] using UV–vis spectrophotometer Unicam UV/VIS 5625. The systematic errors in measurements of nicotine concentration by UV–vis spectrophotometer were ∓ 0.01. The used average concentration values were calculated after repetition of three times experimental measurements. The error bars were calculated and showed in different figures. Removal efficiency (%) for each experiment was calculated by:
2.2. Preparation of nanocatalyst particles Nanomagnetite particles were prepared by dissolving 2.21 g of tetrahydrated ferrous chloride salt and 5.82 g of hexahydrated ferric chloride salt (with molar ratio1:2) in 175 mL deionized water in the presence of nitrogen gas. The last mixture was heated at 80 °C under mechanical stirring followed by addition of 15 mL of concentrated ammonia as one dose. The resulting black colored solution was heated for another 10 min with stirring, stop heating and filtration in strong magnetic field (magnetic filtration). The black particles were washed with deionized water and dried at 80 °C (Ng). Polyvinylpyrrolidone modified nanomagnetite particles (NgM) were prepared as Ng but in the presence of 0.20 g of polyvinylpyrrolidone as modifying agent. Polyvinylpyrrolidone nanomagnetite composite (NgC) was prepared by dissolving 1.0 g of polyvinylpyrrolidone, 2.21 g of FeCl2.4H2O and 5.82 g of FeCl3.6H2O (with molar ratio1:2) in 175 mL deionized water in the presence of nitrogen gas. The resulting mixture was heated at 80 °C under vigorous mechanical stirring for 10 min. Then, 15 mL of ammonia was added rapidly to the solution and kept under stirring at the same temperature for another 10 min and then the solution was heated to 80 °C until all the solvent had evaporated. Finally, the material was dried at 80 °C.
Removal %=
Ci − C × 100 Ci
(6)
where Ci and C are the initial and final concentrations of nicotine solution, respectively. The activity of solid nanocatalysts was also investigated at different parameters, such as nanocatalyst dosage (0.5e3.0 g L−1), pH of nicotine solution (1.0e5.0), temperature (15e50 °C), initial concentration of nicotine (20e120 mg L−1) and H2O2 concentration −1 (2e20 mmol L ). During studying the effect of certain parameter, the 2
Journal of Environmental Chemical Engineering 7 (2019) 102988
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Table 1 Textural characterization of Ng, NgM and NgC. Sample
SBET(m2 g−1)
VP(cm3 g−1)
Vμ (cm3 g−1)
BJH pore size(nm)
Ng NgM NgC
77.4 80.4 3.1
0.177 0.180 0.010
0.0 0.0 0.0
8 10 11
desorption isotherms for Ng, NgM and NgC. Adsorption isotherms follow type IV, according to IUPAC classification [20]. Table 1 summarizes the textural data for the three nanocatalysts. Upon analysis of the data we can conclude that surface area of Ng and NgM is approximately the same (77.4 and 80.4 m2 g−1), indicating that PVP does not affect the textural properties of catalyst, whereas surface area of NgC sharply decreases compared with Ng and NgM to only 3.1 m2 g−1, which may be related to coagulation of Ng particles by the effect of PVP and pore blocking of Ng through occlusion of PVP molecules, hysteresis loop for all the investigated samples resemble of type H2 which belongs to many porous inorganic oxides that they were related to the pore connectivity effects [21,22]. Pore size distribution was calculated from the isotherms by BJH methodology [23] (see the insets in Fig. 2). Peaks in pore size distribution (PSD) plots were located at 8.0, 10.0 and 11.0 nm for Ng, NgM and NgC materials, respectively. These values correspond well with the size of particles determined by SEM/TEM (cf. Figs. 4 and 5) and size of magnetite crystallites determined by Debye–Scherrer equation (see Eq. 7 below). It means that observed condensation steps and hysteresis loops are caused by condensation of nitrogen in interparticle void space and not in internal free volume of mesopores. Low surface area of NgC material is probably caused by sintering/sticking of the nanoparticles by surplus of the PVP. Total pore volume were found to be related directly to surface area where, VP for NgM > Ng > NgC (0.180, 0.177, and 0.01 cm3 g-1, respectively) and that is also can be related to pore blocking and sintering/sticking effects. XRD patterns and Raman spectra of Ng, NgM and NgC are presented in Fig. 3A and B. Fig. 3A shows that seven peaks were located at 2θ angle of 18.2, 30.1, 35.5, 43.4, 53.5, 57.2, and 62.7, which are fitted with (111), (220), (311), (400), (422), (511), and (440), respectively, and ascribed to the cubic structure of magnetite (ICDD card no. 731964) with an inverse spinal structure [24–27]. PVP does not affect the crystalline structure of Ng, but there are observable decreases in peaks intensities. The same observation was reported for poly(styrene–glucidylmethacrylate) composite with nanomagnetite [28]. The average crystalline sizes for nanocatalysts were calculated using Debye–Scherrer diffraction formula [29]:
Fig. 1. TGA curves of PVP (a), Ng (b), NgM (c) and NgC (d).
other parameters were unchanged. Kinetic studies were performed by mixing 0.5 g of the nanocatalyst (Ng, NgC, or NgM) with 200 mL of 100 mg L−1 nicotine solution at pH = 3 in the presence of 15 mmol L−1 H2O2 at 25 °C with an agitation rate of 120 rpm. After different time intervals up to 100 min., 1 mL of the solution was removed to determine the residual nicotine concentration. Catalysts reusability was tested by three reaction cycles where, 2.5 g L−1 as adsorbent dosage, pH = 3, 100 mg L−1 as initial nicotine concentration, 25 °C, 180 min, and 15 mmol L−1 hydrogen peroxide concentration were used as experimental conditions. The nanocatalyst was washed with distilled water and dried at 80 °C after every cycle. 3. Results and discussion 3.1. Characterization of nanocatalysts Thermal analysis was used to quantify the proportion of organic and inorganic contents in the resulting catalysts. Fig. 1 shows the TG curves for Ng, PVP, NgM and NgC from room temperature up to 700 °C. Pure PVP powder exhibited a weight loss about 8% at 110 °C related to moisture loss and start combustion at 420 °C leaving a residue about 9% at 500 °C [19]. Thermal degradation of solid Ng presents a tiny mass loss indicating its thermal stability, where loss at 500 °C is less than 7%. Polyvinylpyrrolidone modified nanomagnetite showed a slightly higher mass loss (12%) than nanomagnetite, which can be related to the PVP content in the material. The PVP content in NgM also raise the polarity of particles which was confirmed by the increase in moisture content related to mass loss at 110 °C (2.4 and 4% in case of Ng and NgM, resp.). NgC composite TG curve exhibited a 22% and 35% weight loss at 420 and 600 °C evidencing higher content of PVP in NgC compared with NgM. We concluded from TGA that PVP content in case of NgM is very low compared with that in NgC. Activity of solid materials depends mainly on its surface area, pore structure and total pore volume. Fig. 2 shows nitrogen adsorption/
Ps (nm) =
λk β cosθ
(7)
Where, λ = 0.15418 nm is the X-ray wavelength, k = 0.9, and β is the
Fig. 2. Nitrogen adsorption/desorption isotherms and BJH pore size distribution curve (inserted) for Ng (A), NgM (B), and NgC (C). 3
Journal of Environmental Chemical Engineering 7 (2019) 102988
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Fig. 3. XRD patterns (A) and Raman spectra (B) of Ng (a), NgM (b), and NgC (c).
exhibits slightly broader distribution; 40% of the particles lie in the 5–10 nm range and another 40% are between 10–15 nm. NgC sample shows shift of particle size to higher values (38% in the range of 10–15 and 25% in the range of 15–20 nm). We concluded that using PVP as a composite forming agent raise particle size of NgC more than the increase in particle size of NgM when it is used as modifying agent. Fig. 5g, h and i show EDX analysis of the three solid samples, indicating that the weight % of magnetite content decreases in the following order: Ng (98.04%) > NgM (76.88%) > NgC (56.95%), and there is no any observable amount of carbon in case of Ng, while in NgM and NgC it was 4.91 and 13.66%, respectively. FTIR spectroscopy analysis is essential technique to investigate the surface chemistry of solid catalysts. Fig. 6 shows FTIR of the prepared nanocatalysts, where strong absorption peak at 564 cm−1 is related to stretching vibration of Fe-O [32,33]. The broad band at 3395 cm-1 was attributed to stretching vibrations of eOH groups, while peak located at 1619 cm−1 was attributed to the bending vibrations of HeOeH arising from physisorbed water molecules on the surface [31,34].
full width at 0.5 height. It was found to be 8.0, 8.2, 9.3 nm for Ng, NgM and NgC, respectively. Fig. 3B shows Raman spectra of Ng, NgM, and NgC. NgC material exhibits Raman spectrum of magnetite with characteristic band at ca 670 cm−1 accompanied by weak peaks at 510 and 310 cm−1. NgM and Ng exhibit Raman bands corresponding to product of magnetite oxidation: (i) maghemite with characteristic bands at ca 360, 500 and broad band between 620 and 710 cm−1 and (ii) hematite with the bands at 221 and 283 cm−1 while, nanomagnetite contents in NgC may be completely protected from oxidation by the effect of higher percentage of PVP. The presence of magnetite in case of Ng and NgM was confirmed by XRD and not indicated by Raman microscope due to different time spent on the air between XRD and Raman measurement, Raman spectroscopy brings information from surface and XRD from bulk of the particle. Morphology of the nanocatalysts was investigated by SEM (Fig. 4). It appears as agglomerated spherical globules in case of Ng and NgM. Nanomagnetite/PVP nanocomposite morphology shows a larger particle size and more agglomerations for the composite particles due to uniform incorporation of nanomagnetite spheres into the blend of PVP. Similar result was observed by Vunain et al. for ethylene-vinyl acetate (EVA)/polycaprolactone (PCL)–Fe3O4 composites [30]. TEM micrographs of Ng, NgM, and NgC are shown in Fig. 5 a, b, and c, respectively. It is obvious that most of the particles had an almost spherical shape with an average diameter 8.4, 9.5 and 10.8 nm for Ng, NgM and NgC, respectively. Two different regions of electron densities, especially for NgC sample, can be observed: the dense region is related to presumably magnetic nanoparticle core, and the less dense and more translucent region due to PVP shell [31]. Fig. 5 d, e and f show the histograms of nanocatalyst sizes as calculated, based on analysis of 100 particles in different regions of the micrographs. Ng shows that about 57% of the particles in the range between 5–10 nm. NgM sample
3.2. Degradation of nicotine by the heterogeneous Fenton process 3.2.1. Effect of catalyst dosage The effect of nanocatalysts dosage on nicotine degradation against time is illustrated in Fig.7. For all of the three nanocatalysts raising the catalyst dosage from 0.5 to 2.5 g L−1, there are increases in the catalyst efficiency for degradation of nicotine, and further increase in the catalyst dosage (3.0 g L−1) is accompanied by a decrease in degradation efficiency (Table 2). The last observation can be explained on the basis of increasing amount of the active sites with increasing the nanocatalysts dosage (0.5–2.5 g L−1) and more H2O2 molecules decomposed to % OH [35,36]. Further increase in nanocatalyst dosage (> 2.5 g L−1) leads to a decrease in nicotine degradation, which can be related to the
Fig. 4. SEM micrographs of Ng (a), NgM (b), and NgC (c). 4
Journal of Environmental Chemical Engineering 7 (2019) 102988
R. Bulánek, et al.
Fig. 5. TEM micrographs (a, b, c), histograms (d, e, f) and EDX spectra (g, h, i) of Ng, NgM, and NgC, respectively.
Fig. 6. FTIR spectra of Ng (a), NgM (b) and NgC (c).
scavenging effect of Fe+2 on ∙OH, as shown in Eq. 8 [37,38]. Fe+2 + %OH → Fe+3+ OH−
Fig. 7. Effect of initial catalyst dosage on the degradation of nicotine by Ng (a), NgM (b), and NgC (c). Reaction conditions: initial nicotine concentration = 100 mg L−1, temp. = 25 °C, [H2O2] = 15 mmol L−1, and pH = 3.
(8)
From Fig. 7 and Table 2 data, we concluded that: (i) the maximum nanocatalyst efficiency reached at time about 100 min, which can be explained by the low reduction rate of Fe+3 into Fe+2 (Eq. (2)) [39]. (ii) NgC shows a lower degradation efficiency compared with the other two nanocatalysts due to its lower iron content (56.95%) and lower surface area (3.1 m2 g−1). (iii) NgM nanocatalyst exhibited the most
nicotine degradation efficiency, which can be related to the more polarity of NgM, due to PVP addition which reduce the escape of H2O2 and ∙OH from the nanocatalyst surface, beside its higher surface area and higher iron contents. As a result, 100 min and 2.5 g L−1 5
Journal of Environmental Chemical Engineering 7 (2019) 102988
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Table 2 Degradation % of nicotine by Ng, NgM, and NgC at 100 min using different nanocatalysts dosage. Sample
0.5 g L−1
1.0 g L−1
2.5 g L−1
3.0 g L−1
Ng NgM NgC
45.0% 73.0% 15.2%
53.0% 78.0% 17.5%
61.5% 89.0% 24.0%
60.0% 82.0% 20.5%
Fig. 9. Effect of initial nicotine concentration on degradation efficency by Ng (a), NgM (b), and NgC (c). Reaction conditions: pH = 2.5, temp. = 25 °C, [H2O2] = 15 mmol L−1, time = 100 min, and catalyst dosage = 2.5 g L−1.
reason we use nicotine concentration of 100 mg L−1 as the optimum value in the other experiments. 3.2.4. Effect of H2O2 concentrations Hydrogen peroxide concentration is the main factor in Fenton reaction, where it is the source of free oxidizing radical in degradation of organic pollutant for that Fig. 10 shows the effect of H2O2 concentration (varying in the range 2–20 mmol L−1) on the conversion of nicotine. As the concentration of H2O2 increases, there is observable increase in the degradation efficiency of nicotine, especially at the beginning, and that increase slows down at higher concentrations. For NgM removal % of nicotine at [H2O2] = 2 mmol L−1 was 25% and reached the maximum removal efficiency at 14 mmol L−1 (removal = 93%) but started to decrease after that value to reach 80% at 20 mmol L−1, and the same trend was observed for all the other two nanocatalysts (Ng, NgC). At certain catalyst dosage and low concentration of H2O2, the produced ∙OH is not sufficient to achieve higher degradation efficiency, and with increasing H2O2 concentration, the released oxidizing radical concentration increases (∙OH), which is accompanied with a sharp increase in nanocatalysts efficiencies. At higher concentrations of H2O2 > 14 mmol L−1, the decrease in efficiency was related to ∙OH scavenging, due to the deviation from the original mechanism of Fenton oxidation process and formation of less active oxidizing agent (O2), as described by Eqs. 11, 12 [40,49,50].
Fig. 8. Effect of pH on nicotine degradation by Ng (a), NgM (b), and NgC (c). Reaction conditions: initial nicotine concentration = 100 mg L−1, temp. = 25 °C, [H2O2] = 15 mmol L−1, time = 100 min, and catalyst dosage = 2.5 g L−1.
nanocatalyst dosage are the optimum conditions for the other experiments. 3.2.2. Effect of pH The effect of initial nicotine solution acidity was investigated in the pH range of 1.0–5.0 (Fig. 8). Removal % of nicotine increased in the range of pH from 1.0 to 2.5 when reached maximum efficiency. Further increase in pH value (> 3.0) is accompanied with a decrease in the degradation efficiency of nicotine. These observations are consistent with previously published results [40–43]. At pH values < 2, the degradation of nicotine is lower because H2O2 is probably stable, due to protonation with H+ forming oxonium ion (H3O2+), and that ion makes H2O2 electrophilic to raise the stability and probably reduce the reactivity with Fe+2 [43,44]. In addition, ∙OH will be converted into H2O (Eq. (10)) at lower pH values [45,46]. At higher pH values (> 3.0), the observable decrease in nicotine degradation efficiency can be related to the decomposition of H2O2 into O2 and H2O [47] and the more iron tendency to form iron hydroxide rather than incorporation in the formation of ∙OH [43]. H2O2 +H+ → H3O2+ %
+
OH + H
+ e → H2O
(9) (10)
3.2.3. Effect of initial nicotine concentration Fig. 9 shows the effect of initial nicotine concentration (20–120 mg L−1). It is observed that as the initial concentration of nicotine increases the degradation efficiency of nicotine by Fenton oxidation process increases. This can be explained by the increase in number of nicotine molecules which raises the probability of collision between nicotine molecules and unstable oxidizing species (responsible for degradation) [48]. At nicotine concentration > 80 mg L−1, the increase in degradation of nicotine is slow down due to the lack of oxidizing species. That confirms the dependence of degradation rate on concentration of organic molecules (nicotine) and oxidizing species and for this
Fig. 10. Effect of hydrogen peroxide concentration on nicotine degradation by Ng (a), NgM (b), and NgC (c). Reaction conditions: initial nicotine concentration = 100 mg L−1, pH = 2.5, temp. = 25 °C, Time = 100 min, and catalyst dosage = 2.5 g L−1. 6
Journal of Environmental Chemical Engineering 7 (2019) 102988
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H2O2 + %OH → H2O +%OOH %
rising the temperature from 15 to 25 °C, there is sharp increase in degradation of nicotine, which is observed in case of NgM and Ng (4 and 3 times), while the maximum degradation was observed at 35 °C. This is related to the increase in reaction rate between H2O2 and nanocatalysts, which is accompanied by increasing in %OH and Fe+3 concentrations [43]. At temperature > 35 °C, the removal% of nicotine starts to decrease, which may be related to the instability of H2O2 and oxidizing species. Heretofore reported results indicated that 35 °C is the optimum temperature in degradation of nicotine with magnetite nanocatalysts. The activation energies for degradation of nicotine using Ng, NgC and NgM were determined by the application of the following Arrhenius equation [54].
(11)
%
OOH + OH → H2O+O2 (radical- radical recombination)
(12)
Rodriguez et al. [51] proved that complete and safe mineralization of nicotine with Fenton oxidation was applied at higher oxidation–reduction potential (ORP) which could be confirmed by using the amount of H2O2 more than two times the theoretically required for complete mineralization according to the following equation: C10H14N2 + 32H2O2 → 10CO2 + 38H2O + 2HNO3
(13)
In the present work higher [H2O2]: [nicotine] ratio than the theoretical (≈ 13 times) ratio is used to convert all nicotine into CO2, H2O and NO2 gases.
lnkapp = ln A‒
3.2.5. Degradation kinetics Kinetics of nicotine degradation by heterogeneous Fenton process was described according to the following pseudo-first order (PFO) equation [52]:
−
dc = kapp C dt
Where A is the frequency factor (min ), kapp is the calculated rate constant, T is the thermodynamic temperature of the solution (K), Ea is the activation energy (kJ mol−1) and R is the ideal gas constant (0.0083 kJ mol−1 K−1). Figures S1 A, B and C show the residual fraction of nicotine against degradation time while Figures S1 D, E and F show the linear PFO kinetic models (Eq. 15) in the presence of Ng, NgC, and NgM catalysts, respectively at 15, 25 and 35 °C. The obtained kapp values were used in the application of Eq. 16. Fig. 12 B displays the linearized plot of Arrhenius equation. The calculated Ea from the slope of Arrhenius equation plots were found to be 19.3, 29.1 and 9.3 kJ mol−1 while A as calculated from the intercepts equals 0.01811, 0.00910 and 0.0352 L g−1 min−1 for Ng, NgM and NgC, respectively. Activation energy required for oxidation of nicotine in the absence of any catalyst was calculated in previous work as 56.0 ± 7 kJ mol-1 [55] and it is observed that the presence of solid-liquid interfaces as heterogeneous catalysis reduce the required activation energy for nicotine decomposition to a lower values [56].
(14)
Where, C is the concentration of nicotine (mg L ) and kapp is a combined constant rate term (min−1). Integration of Eq. 14 gives the linear pseudo-first order equation
Co = kapp t Ct
(16) −1
−1
ln
Ea RT
(15)
Where, Co is the initial nicotine concentration and Ct is the concentraC tion at time t. Plotting ln Co against t we can obtain kapp. We applied the t first time range for pseudo-first order kinetic models (PFO) application to avoid the deviation at higher time [53]. Fig. 11 A shows the residual fraction of nicotine against degradation time in the presence of Ng, NgC, and NgM catalysts while, Fig. 11 B shows the linear PFO kinetic models. The calculated kapp for NgM > Ng > NgC (0.03325, 0.01861 and 0.00943 min−1, respectively) indicating the higher catalytic activity of NgM compared with the other two solid nanocatalysts. The higher correlation coefficient values (0.98092, 0.98819, and 0.97004) related to NgM, Ng, and NgC, respectively prove the applicability of PFO kinetic models.
3.2.7. Catalyst reusability Catalysts reusability was investigated by catalytic experiments after three cycles of applications of recovered catalyst. Reusability results are shown in Fig. 13. Catalyst efficiency slightly decreases with catalyst reusing where after three cycles of applications Ng, NgM and NgC efficiency decreased by about 11.1, 2.2, and 6.9%, which may be related to the coagulation of nanoparticles and decrease in surface area [57]. NgM exhibited the most stability and reusability catalyst among the others. Nicotine oxidation has been studied on wide set of catalysts such as Feᴼ/H2O2, FeSO4/H2O2, permanganate ion in acid perchlorate, goethite particles, and zeolite-supported platinum [3,51,58–60]. This study deals with Fenton oxidation of nicotine using polyvinylpyrrolidone
3.2.6. Effect of temperature Fig. 12 A shows the effect of temperature on degradation of nicotine by Fenton oxidation process at pH 3, 2.5 g L−1 as nanocatalyst dosage, an initial nicotine concentration of 100 mg L-1 and an initial hydrogen peroxide concentration of 14 mmol L−1. The degradation of nicotine was carried out at 15, 25, 35, 45, and 50 °C for all the nanocatalysts. By
Fig. 11. Effect of time on nicotine degradation (A) and pseudo-first-order plot (B) by Ng (a), NgM (b), and NgC (c). Reaction conditions: initial nicotine concentration = 100 mgL−1, pH = 3, temp. = 25 °C, time = 100 min, weight of catalyst = 0. 5 g, volume of solution = 200 mL. 7
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Fig. 12. Effect of temperature (A) and Linear Arrhenius plot (B) on nicotine degradation by Fenton oxidation process in the presence of Ng (a), NgM (b), and NgC (c).
nicotine concentration of 100 mg L−1, pH 2.5, 14 mmol L−1 H2O2, and 2.5 g L−1 as nanocatalyst dosage. Catalyst reusability showed the well applicability of NgM as a catalyst after a different application cycle in heterogeneous Fenton oxidation process. The presence of NgM nanocataly st reduces the energy barriers for nicotine degradation reaction from 56.0 ± 7 to 29.1 kJ mol-1 and proved the higher efficiency of the used nanocatalyst. Acknowledgments This research was financed by the Research Sector of Damanhour University, Egypt and partially supported by the Czech Science Foundation Grant No. P106/12/G015 (Centre of Excellence). Appendix A. Supplementary data Fig. 13. Catalyst reusability results after three cycles of applications for nicotine degradation by Ng (a), NgM (b), and NgC(c).
Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.jece.2019.102988.
Table 3 Comparison of the maximum removal percentage for nicotine onto NgM with other catalysts reported in previous researches. Catalysts
R%
References
Feᴼ/H2O2 FeSO4/H2O2 Permanganate ion in acid perchlorate Goethite particles Zeolite-supported platinum NgM
81.3 80.0 36.5 36.1 47.2 89
[3] [51] [58] [59] [60] This study
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modified nanomagnetite graphitic materials (NgM) as a solid catalyst. Upon inspection of data in Table 3 we can conclude that NgM reported here shows higher catalytic activity (R = 89%) compared with the other oxidation process.
4. Conclusion Polyvinylpyrrolidone modified nanomagnetite is efficient in removal of nicotine from aqueous medium by heterogeneous Fenton oxidation mechanism, where modification of nanomagnetite particles with PVP does not affect its textural structure, but raises the ability of particles to collect H2O2 and raises the production of ∙OH. Kinetic studies indicate that Fenton degradation of nicotine over polyvinylpyrrolidone modified nanomagnetite reaction obey pseudo-first order kinetic model. Nicotine degradation efficiency by Ng, NgM, and NgC was 61.5, 89 and 24%, respectively at 100 min, 25 °C, initial 8
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Preparation of polyvinylpyrrolidone modified nanomagnetite for degradation of nicotine by heterogeneous Fenton process Roman Buláneka, Radim Hrdinab, Asaad F. Hassana,c,
T
⁎
a
Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice, Czechia Institute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of Pardubice, Czechia c Department of Chemistry, Faculty of Science, University of Damanhour, Damanhour, Egypt b
A R T I C LE I N FO
A B S T R A C T
Keywords: Nanomagnetite Composite Characterization Nicotine Fenton
Nanomagnetite (Ng), polyvinylpyrrolidone modified nanomagnetite (NgM), and polyvinylpyrrolidone/nanomagnetite composite (NgC) were prepared in presence of nitrogen gas. Thermogravimetric analysis showed that NgC contains higher polyvinylpyrrolidone/nanomagnetite (PVP/Ng) ratio. Assessments of nitrogen adsorption, SEM, TEM, and EDX data indicate that specific surface area of investigated materials is in order Ng ≈ ≈ NgM > NgC, materials form nano spheres with particle size around 9.0 nm according to TEM and Debye–Scherrer diffraction formula and content of magnetite in the prepared catalysts were 98.04, 76.88, and 56.95% in case of Ng, NgM and NgC, respectively. XRD confirms the cubic structure of nanocatalysts. FTIR spectra confirm the presence of stretching vibration of Fe-O bonds and magnetite fingerprint of skeletal vibrations. Degradation of nicotine by Fenton process catalyzed by nanomagnetite-based heterogeneous catalysts was studied under different conditions. Optimal reaction conditions for nicotine decomposition were found to be: equilibrium degradation time = 100 min, nanocatalyst dosage = 2.5 g L−1, pH = 2.5, hydrogen peroxide initial nicotine concentration = 100 mg L−1 and degradation concentration = 14 mmol L−1, temperature = 35 °C. Kinetic studies showed that the Fenton degradation of nicotine in the presence of polyvinylpyrrolidone modified nanomagnetite catalysts follows the pseudo-first order kinetic model. Catalyst reusability proved that NgM is efficient, reusable nanocatalyst materials for degradation of nicotine by Fenton process compared with the other two catalysts.
1. Introduction Alkaloid is a type of naturally occurring nitrogenous organic containing bases having a different physiological effects on animals and human. The well-known alkaloids include ephedrine, strychnine, quinine, morphine and nicotine. Some alkaloids, such as nicotine, are illicit and poison drugs obtained from Nicotiana tabacum (tobacco plant). For adult human beings forty to sixty milligrams of nicotine can be a lethal dosage [1]. Nicotine (3- substituted pyridine, C10H14N2) may cause many health problems to the eyes, digestive system, brain, heart and even genetic damage [2]. There are many reasons standing behind environmental pollution with aqueous nicotine such as: nicotine emission in the side stream and exhaled mainstream smoke of cigarettes. Nicotine is transferred to aqueous medium with a large amount during tobacco manufacturing and processing. Tobacco dust, as a by-product during manufacture of cigarette, with high amounts of nicotine accumulates in the environment of cigarettes manufacture and cannot be
⁎
recovered. It can be easily extracted from the tobacco dust and transported into ground-water [3,4]. Production of some pharmaceutical products (such as Habitrol, Nicoderm, Nicorette, Nicotrol, and Tetrahydronicotyrine) requires nicotine as the main ingredient material, which is responsible for other environmental nicotine pollution [5]. Removal of nicotine from aqueous medium has been studied through adsorption [6–9], photocatalysis [10] and extraction using organic eluents, such as, cyclohexane, toluene, hexane, kerosene or 1-butanole [3]. Biodegradation using microorganisms is still the main procedure for nicotine contamination treatment [11,12], but biological treatment of organic pollutants is time-consuming and not always recommended, as it removes only some of the wide range of pollutants [13,14]. Another alternative, how to remove organic pollutants frequently used in environment and pollution control is application of Fenton process. H.J.H. Fenton in 1894 described a new method for H2O2 decomposition by Fe+2 salts in the oxidation of tartaric acid [15]. Ferrous ions generate hydroxyl radicals [16] by the following reactions:
Corresponding author at: Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice, Czechia. E-mail address: [email protected] (A.F. Hassan).
https://doi.org/10.1016/j.jece.2019.102988 Received 5 September 2018; Received in revised form 21 February 2019; Accepted 25 February 2019 Available online 25 February 2019 2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
Journal of Environmental Chemical Engineering 7 (2019) 102988
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Fe+2 +H2O2 → Fe+3 + HO + HO% (k = 63e76 M−1 s−1) Fe
+3
+ H2O2→ Fe
+2
%
+
+ HOO + H (k = 10
−3
e10 M s ) -2
-1
-1
2.3. Characterization
(1) (2)
Thermal gravimetric analysis (TGA) was investigated to gain knowledge on the thermal behavior of the prepared solid catalyst samples (Ng, NgM and NgC) using a differential thermal analyzer (Shimadzu DTA-50, Japan). Surface area (SBET, m2 g−1), total pore volume (VP, cm3 g−1) and pore size (nm) of samples were determined using ASAP 2020 gas sorption analyzer (Micromeritics). Nitrogen adsorption/desorption isotherms were determined at its boiling point. The samples were activated under vacuum at 350 °C for 4 h prior to measurement. The diffraction patterns (Cu Kα, λ = 1.5418 Å) were recorded on powdered samples using a D8 advance diffractometer (Bruker AXS, Germany) with Bragg-Brentano θ-θ goniometer (radius 217.5 mm) equipped with a secondary beam curved graphite monochromator and NaI scintillation detector. The scan was performed at room temperature from 10 to 70° (2 θ) in 0.02° step with a counting time of 10 s per step. Raman spectra were collected by Nicolet DXR2 Raman microscope (Thermo Scientific, USA) equipped by Smart excitation laser with wavelength of 785 nm. Spectra were recorded by accumulation of 100 scans (scan time was 10 s, resolution of 2 cm−1, laser power was 2 mW). The SEM of prepared particles was carried out on scanning electron microscope JEOL JSM-7500 F apparatus. In order to increase its conductivity, the sample was coated with an Au layer (0.2 nm) with the help of dust sprinkling equipment "Bio-Rad Polaron". HRTEM (High-resolution transmission electron microscopy) with EDX (energy dispersive X-ray) spectroscopy (JEOL-2100 F TEM) was utilized to get high magnification micrographs of the prepared samples and their chemical analysis. The instrument was operated at an accelerating voltage of 200 kV. The samples were subjected to ultrasonic in ethanol for 30 min and then dropped on a carbon-coated Cu TEM grid. Fourier transform infrared spectroscopy (FTIR) using a Mattson 5000 FTIR spectrometer in the range between 400 and 4000 cm−1. Discs were prepared by mixing 0.001 g of dried nanocatalyst sample with 0.4 g of KBr (spectroscopic purity, Merck) in an agate mortar, followed by pressing the mixture at 5 ton cm-3 for 3 min and 10 ton cm-3 for 5 min under vacuum.
By applying Photo-Fenton, the presence of UV–Vis illumination can accelerate the reduction process according to the following equations [17]: Fe+2 +H2O2 → Fe+3 + HO + HO%
(3)
Fe+3 +H2O + hυ → Fe+2 + HO%+ H+
(4)
Fe+3 + H2O2→ Fe+2 +HOO+ H+
(5)
Fenton process has been studied for removal of various pollutants from the waste waters. Homogeneous and heterogeneous applications of Fenton reaction are possible, but heterogeneous Fenton has great advantages in reducing iron loss, raising the efficiency of H2O2, and reducing iron sludge generation compared with homogeneous Fenton. The use of polyvinylpyrrolidone as polar organic additive during synthesis of nanomagnetite particle has been proposed to control the shape of the magnetic nanoparticle and show a plausible size distribution [18]. To the best of our knowledge, application of Fenton process for nicotine removal was not studied up to now. The goal of the present work was to prepare both nanomagnetite particles (Ng) and nanomagnetite particles modified by polyvinylpyrrolidone. Prepared materials were characterized by various physico-chemical techniques (thermal gravimetric analysis, N2 physisorption, XRD, FTIR, and SEM/ TEM) and tested in catalytic decomposition of nicotine as a toxic alkaloid at different reaction conditions, such as catalyst dosage, pH of nicotine solution, initial nicotine concentration, concentration of H2O2 and temperature. These are important experimental factors to choose the optimum conditions for nicotine degradation. 2. Materials and methods 2.1. Materials Polyvinylpyrrolidone (k 90, powder, average MW 360000, CAS 9003-39-8) and nicotine (> 99%) were obtained from Fluka Co. Ferric chloride, and ferrous chloride were obtained from Alfa-Aesar Co. Ltd. Other reagents were obtained from El-Nasr for pharmaceutical and chemical industrial Co., Egypt. All reagents were used without further purification.
2.4. Catalyst activity measurement The experiments were carried out in 250 mL stoppered Erlenmeyer flasks with an agitation of 120 rpm for about 160 min. Experiments were performed by taking the desired amount of stock nicotine solution (500 mg L−1) diluted to 200 mL with distilled water and followed by addition of the required amount of solid nanocatalyst. Initial pH of the solution was adjusted using 0.01 M H2SO4 or 0.01 M NaOH solution. Finally, the predetermined amount of hydrogen peroxide was added to start the reaction. Thereafter, 2 mL of samples were removed periodically from the solution reaction and analyzed for residual nicotine at λmax 260 nm [1] using UV–vis spectrophotometer Unicam UV/VIS 5625. The systematic errors in measurements of nicotine concentration by UV–vis spectrophotometer were ∓ 0.01. The used average concentration values were calculated after repetition of three times experimental measurements. The error bars were calculated and showed in different figures. Removal efficiency (%) for each experiment was calculated by:
2.2. Preparation of nanocatalyst particles Nanomagnetite particles were prepared by dissolving 2.21 g of tetrahydrated ferrous chloride salt and 5.82 g of hexahydrated ferric chloride salt (with molar ratio1:2) in 175 mL deionized water in the presence of nitrogen gas. The last mixture was heated at 80 °C under mechanical stirring followed by addition of 15 mL of concentrated ammonia as one dose. The resulting black colored solution was heated for another 10 min with stirring, stop heating and filtration in strong magnetic field (magnetic filtration). The black particles were washed with deionized water and dried at 80 °C (Ng). Polyvinylpyrrolidone modified nanomagnetite particles (NgM) were prepared as Ng but in the presence of 0.20 g of polyvinylpyrrolidone as modifying agent. Polyvinylpyrrolidone nanomagnetite composite (NgC) was prepared by dissolving 1.0 g of polyvinylpyrrolidone, 2.21 g of FeCl2.4H2O and 5.82 g of FeCl3.6H2O (with molar ratio1:2) in 175 mL deionized water in the presence of nitrogen gas. The resulting mixture was heated at 80 °C under vigorous mechanical stirring for 10 min. Then, 15 mL of ammonia was added rapidly to the solution and kept under stirring at the same temperature for another 10 min and then the solution was heated to 80 °C until all the solvent had evaporated. Finally, the material was dried at 80 °C.
Removal %=
Ci − C × 100 Ci
(6)
where Ci and C are the initial and final concentrations of nicotine solution, respectively. The activity of solid nanocatalysts was also investigated at different parameters, such as nanocatalyst dosage (0.5e3.0 g L−1), pH of nicotine solution (1.0e5.0), temperature (15e50 °C), initial concentration of nicotine (20e120 mg L−1) and H2O2 concentration −1 (2e20 mmol L ). During studying the effect of certain parameter, the 2
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Table 1 Textural characterization of Ng, NgM and NgC. Sample
SBET(m2 g−1)
VP(cm3 g−1)
Vμ (cm3 g−1)
BJH pore size(nm)
Ng NgM NgC
77.4 80.4 3.1
0.177 0.180 0.010
0.0 0.0 0.0
8 10 11
desorption isotherms for Ng, NgM and NgC. Adsorption isotherms follow type IV, according to IUPAC classification [20]. Table 1 summarizes the textural data for the three nanocatalysts. Upon analysis of the data we can conclude that surface area of Ng and NgM is approximately the same (77.4 and 80.4 m2 g−1), indicating that PVP does not affect the textural properties of catalyst, whereas surface area of NgC sharply decreases compared with Ng and NgM to only 3.1 m2 g−1, which may be related to coagulation of Ng particles by the effect of PVP and pore blocking of Ng through occlusion of PVP molecules, hysteresis loop for all the investigated samples resemble of type H2 which belongs to many porous inorganic oxides that they were related to the pore connectivity effects [21,22]. Pore size distribution was calculated from the isotherms by BJH methodology [23] (see the insets in Fig. 2). Peaks in pore size distribution (PSD) plots were located at 8.0, 10.0 and 11.0 nm for Ng, NgM and NgC materials, respectively. These values correspond well with the size of particles determined by SEM/TEM (cf. Figs. 4 and 5) and size of magnetite crystallites determined by Debye–Scherrer equation (see Eq. 7 below). It means that observed condensation steps and hysteresis loops are caused by condensation of nitrogen in interparticle void space and not in internal free volume of mesopores. Low surface area of NgC material is probably caused by sintering/sticking of the nanoparticles by surplus of the PVP. Total pore volume were found to be related directly to surface area where, VP for NgM > Ng > NgC (0.180, 0.177, and 0.01 cm3 g-1, respectively) and that is also can be related to pore blocking and sintering/sticking effects. XRD patterns and Raman spectra of Ng, NgM and NgC are presented in Fig. 3A and B. Fig. 3A shows that seven peaks were located at 2θ angle of 18.2, 30.1, 35.5, 43.4, 53.5, 57.2, and 62.7, which are fitted with (111), (220), (311), (400), (422), (511), and (440), respectively, and ascribed to the cubic structure of magnetite (ICDD card no. 731964) with an inverse spinal structure [24–27]. PVP does not affect the crystalline structure of Ng, but there are observable decreases in peaks intensities. The same observation was reported for poly(styrene–glucidylmethacrylate) composite with nanomagnetite [28]. The average crystalline sizes for nanocatalysts were calculated using Debye–Scherrer diffraction formula [29]:
Fig. 1. TGA curves of PVP (a), Ng (b), NgM (c) and NgC (d).
other parameters were unchanged. Kinetic studies were performed by mixing 0.5 g of the nanocatalyst (Ng, NgC, or NgM) with 200 mL of 100 mg L−1 nicotine solution at pH = 3 in the presence of 15 mmol L−1 H2O2 at 25 °C with an agitation rate of 120 rpm. After different time intervals up to 100 min., 1 mL of the solution was removed to determine the residual nicotine concentration. Catalysts reusability was tested by three reaction cycles where, 2.5 g L−1 as adsorbent dosage, pH = 3, 100 mg L−1 as initial nicotine concentration, 25 °C, 180 min, and 15 mmol L−1 hydrogen peroxide concentration were used as experimental conditions. The nanocatalyst was washed with distilled water and dried at 80 °C after every cycle. 3. Results and discussion 3.1. Characterization of nanocatalysts Thermal analysis was used to quantify the proportion of organic and inorganic contents in the resulting catalysts. Fig. 1 shows the TG curves for Ng, PVP, NgM and NgC from room temperature up to 700 °C. Pure PVP powder exhibited a weight loss about 8% at 110 °C related to moisture loss and start combustion at 420 °C leaving a residue about 9% at 500 °C [19]. Thermal degradation of solid Ng presents a tiny mass loss indicating its thermal stability, where loss at 500 °C is less than 7%. Polyvinylpyrrolidone modified nanomagnetite showed a slightly higher mass loss (12%) than nanomagnetite, which can be related to the PVP content in the material. The PVP content in NgM also raise the polarity of particles which was confirmed by the increase in moisture content related to mass loss at 110 °C (2.4 and 4% in case of Ng and NgM, resp.). NgC composite TG curve exhibited a 22% and 35% weight loss at 420 and 600 °C evidencing higher content of PVP in NgC compared with NgM. We concluded from TGA that PVP content in case of NgM is very low compared with that in NgC. Activity of solid materials depends mainly on its surface area, pore structure and total pore volume. Fig. 2 shows nitrogen adsorption/
Ps (nm) =
λk β cosθ
(7)
Where, λ = 0.15418 nm is the X-ray wavelength, k = 0.9, and β is the
Fig. 2. Nitrogen adsorption/desorption isotherms and BJH pore size distribution curve (inserted) for Ng (A), NgM (B), and NgC (C). 3
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Fig. 3. XRD patterns (A) and Raman spectra (B) of Ng (a), NgM (b), and NgC (c).
exhibits slightly broader distribution; 40% of the particles lie in the 5–10 nm range and another 40% are between 10–15 nm. NgC sample shows shift of particle size to higher values (38% in the range of 10–15 and 25% in the range of 15–20 nm). We concluded that using PVP as a composite forming agent raise particle size of NgC more than the increase in particle size of NgM when it is used as modifying agent. Fig. 5g, h and i show EDX analysis of the three solid samples, indicating that the weight % of magnetite content decreases in the following order: Ng (98.04%) > NgM (76.88%) > NgC (56.95%), and there is no any observable amount of carbon in case of Ng, while in NgM and NgC it was 4.91 and 13.66%, respectively. FTIR spectroscopy analysis is essential technique to investigate the surface chemistry of solid catalysts. Fig. 6 shows FTIR of the prepared nanocatalysts, where strong absorption peak at 564 cm−1 is related to stretching vibration of Fe-O [32,33]. The broad band at 3395 cm-1 was attributed to stretching vibrations of eOH groups, while peak located at 1619 cm−1 was attributed to the bending vibrations of HeOeH arising from physisorbed water molecules on the surface [31,34].
full width at 0.5 height. It was found to be 8.0, 8.2, 9.3 nm for Ng, NgM and NgC, respectively. Fig. 3B shows Raman spectra of Ng, NgM, and NgC. NgC material exhibits Raman spectrum of magnetite with characteristic band at ca 670 cm−1 accompanied by weak peaks at 510 and 310 cm−1. NgM and Ng exhibit Raman bands corresponding to product of magnetite oxidation: (i) maghemite with characteristic bands at ca 360, 500 and broad band between 620 and 710 cm−1 and (ii) hematite with the bands at 221 and 283 cm−1 while, nanomagnetite contents in NgC may be completely protected from oxidation by the effect of higher percentage of PVP. The presence of magnetite in case of Ng and NgM was confirmed by XRD and not indicated by Raman microscope due to different time spent on the air between XRD and Raman measurement, Raman spectroscopy brings information from surface and XRD from bulk of the particle. Morphology of the nanocatalysts was investigated by SEM (Fig. 4). It appears as agglomerated spherical globules in case of Ng and NgM. Nanomagnetite/PVP nanocomposite morphology shows a larger particle size and more agglomerations for the composite particles due to uniform incorporation of nanomagnetite spheres into the blend of PVP. Similar result was observed by Vunain et al. for ethylene-vinyl acetate (EVA)/polycaprolactone (PCL)–Fe3O4 composites [30]. TEM micrographs of Ng, NgM, and NgC are shown in Fig. 5 a, b, and c, respectively. It is obvious that most of the particles had an almost spherical shape with an average diameter 8.4, 9.5 and 10.8 nm for Ng, NgM and NgC, respectively. Two different regions of electron densities, especially for NgC sample, can be observed: the dense region is related to presumably magnetic nanoparticle core, and the less dense and more translucent region due to PVP shell [31]. Fig. 5 d, e and f show the histograms of nanocatalyst sizes as calculated, based on analysis of 100 particles in different regions of the micrographs. Ng shows that about 57% of the particles in the range between 5–10 nm. NgM sample
3.2. Degradation of nicotine by the heterogeneous Fenton process 3.2.1. Effect of catalyst dosage The effect of nanocatalysts dosage on nicotine degradation against time is illustrated in Fig.7. For all of the three nanocatalysts raising the catalyst dosage from 0.5 to 2.5 g L−1, there are increases in the catalyst efficiency for degradation of nicotine, and further increase in the catalyst dosage (3.0 g L−1) is accompanied by a decrease in degradation efficiency (Table 2). The last observation can be explained on the basis of increasing amount of the active sites with increasing the nanocatalysts dosage (0.5–2.5 g L−1) and more H2O2 molecules decomposed to % OH [35,36]. Further increase in nanocatalyst dosage (> 2.5 g L−1) leads to a decrease in nicotine degradation, which can be related to the
Fig. 4. SEM micrographs of Ng (a), NgM (b), and NgC (c). 4
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Fig. 5. TEM micrographs (a, b, c), histograms (d, e, f) and EDX spectra (g, h, i) of Ng, NgM, and NgC, respectively.
Fig. 6. FTIR spectra of Ng (a), NgM (b) and NgC (c).
scavenging effect of Fe+2 on ∙OH, as shown in Eq. 8 [37,38]. Fe+2 + %OH → Fe+3+ OH−
Fig. 7. Effect of initial catalyst dosage on the degradation of nicotine by Ng (a), NgM (b), and NgC (c). Reaction conditions: initial nicotine concentration = 100 mg L−1, temp. = 25 °C, [H2O2] = 15 mmol L−1, and pH = 3.
(8)
From Fig. 7 and Table 2 data, we concluded that: (i) the maximum nanocatalyst efficiency reached at time about 100 min, which can be explained by the low reduction rate of Fe+3 into Fe+2 (Eq. (2)) [39]. (ii) NgC shows a lower degradation efficiency compared with the other two nanocatalysts due to its lower iron content (56.95%) and lower surface area (3.1 m2 g−1). (iii) NgM nanocatalyst exhibited the most
nicotine degradation efficiency, which can be related to the more polarity of NgM, due to PVP addition which reduce the escape of H2O2 and ∙OH from the nanocatalyst surface, beside its higher surface area and higher iron contents. As a result, 100 min and 2.5 g L−1 5
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Table 2 Degradation % of nicotine by Ng, NgM, and NgC at 100 min using different nanocatalysts dosage. Sample
0.5 g L−1
1.0 g L−1
2.5 g L−1
3.0 g L−1
Ng NgM NgC
45.0% 73.0% 15.2%
53.0% 78.0% 17.5%
61.5% 89.0% 24.0%
60.0% 82.0% 20.5%
Fig. 9. Effect of initial nicotine concentration on degradation efficency by Ng (a), NgM (b), and NgC (c). Reaction conditions: pH = 2.5, temp. = 25 °C, [H2O2] = 15 mmol L−1, time = 100 min, and catalyst dosage = 2.5 g L−1.
reason we use nicotine concentration of 100 mg L−1 as the optimum value in the other experiments. 3.2.4. Effect of H2O2 concentrations Hydrogen peroxide concentration is the main factor in Fenton reaction, where it is the source of free oxidizing radical in degradation of organic pollutant for that Fig. 10 shows the effect of H2O2 concentration (varying in the range 2–20 mmol L−1) on the conversion of nicotine. As the concentration of H2O2 increases, there is observable increase in the degradation efficiency of nicotine, especially at the beginning, and that increase slows down at higher concentrations. For NgM removal % of nicotine at [H2O2] = 2 mmol L−1 was 25% and reached the maximum removal efficiency at 14 mmol L−1 (removal = 93%) but started to decrease after that value to reach 80% at 20 mmol L−1, and the same trend was observed for all the other two nanocatalysts (Ng, NgC). At certain catalyst dosage and low concentration of H2O2, the produced ∙OH is not sufficient to achieve higher degradation efficiency, and with increasing H2O2 concentration, the released oxidizing radical concentration increases (∙OH), which is accompanied with a sharp increase in nanocatalysts efficiencies. At higher concentrations of H2O2 > 14 mmol L−1, the decrease in efficiency was related to ∙OH scavenging, due to the deviation from the original mechanism of Fenton oxidation process and formation of less active oxidizing agent (O2), as described by Eqs. 11, 12 [40,49,50].
Fig. 8. Effect of pH on nicotine degradation by Ng (a), NgM (b), and NgC (c). Reaction conditions: initial nicotine concentration = 100 mg L−1, temp. = 25 °C, [H2O2] = 15 mmol L−1, time = 100 min, and catalyst dosage = 2.5 g L−1.
nanocatalyst dosage are the optimum conditions for the other experiments. 3.2.2. Effect of pH The effect of initial nicotine solution acidity was investigated in the pH range of 1.0–5.0 (Fig. 8). Removal % of nicotine increased in the range of pH from 1.0 to 2.5 when reached maximum efficiency. Further increase in pH value (> 3.0) is accompanied with a decrease in the degradation efficiency of nicotine. These observations are consistent with previously published results [40–43]. At pH values < 2, the degradation of nicotine is lower because H2O2 is probably stable, due to protonation with H+ forming oxonium ion (H3O2+), and that ion makes H2O2 electrophilic to raise the stability and probably reduce the reactivity with Fe+2 [43,44]. In addition, ∙OH will be converted into H2O (Eq. (10)) at lower pH values [45,46]. At higher pH values (> 3.0), the observable decrease in nicotine degradation efficiency can be related to the decomposition of H2O2 into O2 and H2O [47] and the more iron tendency to form iron hydroxide rather than incorporation in the formation of ∙OH [43]. H2O2 +H+ → H3O2+ %
+
OH + H
+ e → H2O
(9) (10)
3.2.3. Effect of initial nicotine concentration Fig. 9 shows the effect of initial nicotine concentration (20–120 mg L−1). It is observed that as the initial concentration of nicotine increases the degradation efficiency of nicotine by Fenton oxidation process increases. This can be explained by the increase in number of nicotine molecules which raises the probability of collision between nicotine molecules and unstable oxidizing species (responsible for degradation) [48]. At nicotine concentration > 80 mg L−1, the increase in degradation of nicotine is slow down due to the lack of oxidizing species. That confirms the dependence of degradation rate on concentration of organic molecules (nicotine) and oxidizing species and for this
Fig. 10. Effect of hydrogen peroxide concentration on nicotine degradation by Ng (a), NgM (b), and NgC (c). Reaction conditions: initial nicotine concentration = 100 mg L−1, pH = 2.5, temp. = 25 °C, Time = 100 min, and catalyst dosage = 2.5 g L−1. 6
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H2O2 + %OH → H2O +%OOH %
rising the temperature from 15 to 25 °C, there is sharp increase in degradation of nicotine, which is observed in case of NgM and Ng (4 and 3 times), while the maximum degradation was observed at 35 °C. This is related to the increase in reaction rate between H2O2 and nanocatalysts, which is accompanied by increasing in %OH and Fe+3 concentrations [43]. At temperature > 35 °C, the removal% of nicotine starts to decrease, which may be related to the instability of H2O2 and oxidizing species. Heretofore reported results indicated that 35 °C is the optimum temperature in degradation of nicotine with magnetite nanocatalysts. The activation energies for degradation of nicotine using Ng, NgC and NgM were determined by the application of the following Arrhenius equation [54].
(11)
%
OOH + OH → H2O+O2 (radical- radical recombination)
(12)
Rodriguez et al. [51] proved that complete and safe mineralization of nicotine with Fenton oxidation was applied at higher oxidation–reduction potential (ORP) which could be confirmed by using the amount of H2O2 more than two times the theoretically required for complete mineralization according to the following equation: C10H14N2 + 32H2O2 → 10CO2 + 38H2O + 2HNO3
(13)
In the present work higher [H2O2]: [nicotine] ratio than the theoretical (≈ 13 times) ratio is used to convert all nicotine into CO2, H2O and NO2 gases.
lnkapp = ln A‒
3.2.5. Degradation kinetics Kinetics of nicotine degradation by heterogeneous Fenton process was described according to the following pseudo-first order (PFO) equation [52]:
−
dc = kapp C dt
Where A is the frequency factor (min ), kapp is the calculated rate constant, T is the thermodynamic temperature of the solution (K), Ea is the activation energy (kJ mol−1) and R is the ideal gas constant (0.0083 kJ mol−1 K−1). Figures S1 A, B and C show the residual fraction of nicotine against degradation time while Figures S1 D, E and F show the linear PFO kinetic models (Eq. 15) in the presence of Ng, NgC, and NgM catalysts, respectively at 15, 25 and 35 °C. The obtained kapp values were used in the application of Eq. 16. Fig. 12 B displays the linearized plot of Arrhenius equation. The calculated Ea from the slope of Arrhenius equation plots were found to be 19.3, 29.1 and 9.3 kJ mol−1 while A as calculated from the intercepts equals 0.01811, 0.00910 and 0.0352 L g−1 min−1 for Ng, NgM and NgC, respectively. Activation energy required for oxidation of nicotine in the absence of any catalyst was calculated in previous work as 56.0 ± 7 kJ mol-1 [55] and it is observed that the presence of solid-liquid interfaces as heterogeneous catalysis reduce the required activation energy for nicotine decomposition to a lower values [56].
(14)
Where, C is the concentration of nicotine (mg L ) and kapp is a combined constant rate term (min−1). Integration of Eq. 14 gives the linear pseudo-first order equation
Co = kapp t Ct
(16) −1
−1
ln
Ea RT
(15)
Where, Co is the initial nicotine concentration and Ct is the concentraC tion at time t. Plotting ln Co against t we can obtain kapp. We applied the t first time range for pseudo-first order kinetic models (PFO) application to avoid the deviation at higher time [53]. Fig. 11 A shows the residual fraction of nicotine against degradation time in the presence of Ng, NgC, and NgM catalysts while, Fig. 11 B shows the linear PFO kinetic models. The calculated kapp for NgM > Ng > NgC (0.03325, 0.01861 and 0.00943 min−1, respectively) indicating the higher catalytic activity of NgM compared with the other two solid nanocatalysts. The higher correlation coefficient values (0.98092, 0.98819, and 0.97004) related to NgM, Ng, and NgC, respectively prove the applicability of PFO kinetic models.
3.2.7. Catalyst reusability Catalysts reusability was investigated by catalytic experiments after three cycles of applications of recovered catalyst. Reusability results are shown in Fig. 13. Catalyst efficiency slightly decreases with catalyst reusing where after three cycles of applications Ng, NgM and NgC efficiency decreased by about 11.1, 2.2, and 6.9%, which may be related to the coagulation of nanoparticles and decrease in surface area [57]. NgM exhibited the most stability and reusability catalyst among the others. Nicotine oxidation has been studied on wide set of catalysts such as Feᴼ/H2O2, FeSO4/H2O2, permanganate ion in acid perchlorate, goethite particles, and zeolite-supported platinum [3,51,58–60]. This study deals with Fenton oxidation of nicotine using polyvinylpyrrolidone
3.2.6. Effect of temperature Fig. 12 A shows the effect of temperature on degradation of nicotine by Fenton oxidation process at pH 3, 2.5 g L−1 as nanocatalyst dosage, an initial nicotine concentration of 100 mg L-1 and an initial hydrogen peroxide concentration of 14 mmol L−1. The degradation of nicotine was carried out at 15, 25, 35, 45, and 50 °C for all the nanocatalysts. By
Fig. 11. Effect of time on nicotine degradation (A) and pseudo-first-order plot (B) by Ng (a), NgM (b), and NgC (c). Reaction conditions: initial nicotine concentration = 100 mgL−1, pH = 3, temp. = 25 °C, time = 100 min, weight of catalyst = 0. 5 g, volume of solution = 200 mL. 7
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Fig. 12. Effect of temperature (A) and Linear Arrhenius plot (B) on nicotine degradation by Fenton oxidation process in the presence of Ng (a), NgM (b), and NgC (c).
nicotine concentration of 100 mg L−1, pH 2.5, 14 mmol L−1 H2O2, and 2.5 g L−1 as nanocatalyst dosage. Catalyst reusability showed the well applicability of NgM as a catalyst after a different application cycle in heterogeneous Fenton oxidation process. The presence of NgM nanocataly st reduces the energy barriers for nicotine degradation reaction from 56.0 ± 7 to 29.1 kJ mol-1 and proved the higher efficiency of the used nanocatalyst. Acknowledgments This research was financed by the Research Sector of Damanhour University, Egypt and partially supported by the Czech Science Foundation Grant No. P106/12/G015 (Centre of Excellence). Appendix A. Supplementary data Fig. 13. Catalyst reusability results after three cycles of applications for nicotine degradation by Ng (a), NgM (b), and NgC(c).
Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.jece.2019.102988.
Table 3 Comparison of the maximum removal percentage for nicotine onto NgM with other catalysts reported in previous researches. Catalysts
R%
References
Feᴼ/H2O2 FeSO4/H2O2 Permanganate ion in acid perchlorate Goethite particles Zeolite-supported platinum NgM
81.3 80.0 36.5 36.1 47.2 89
[3] [51] [58] [59] [60] This study
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modified nanomagnetite graphitic materials (NgM) as a solid catalyst. Upon inspection of data in Table 3 we can conclude that NgM reported here shows higher catalytic activity (R = 89%) compared with the other oxidation process.
4. Conclusion Polyvinylpyrrolidone modified nanomagnetite is efficient in removal of nicotine from aqueous medium by heterogeneous Fenton oxidation mechanism, where modification of nanomagnetite particles with PVP does not affect its textural structure, but raises the ability of particles to collect H2O2 and raises the production of ∙OH. Kinetic studies indicate that Fenton degradation of nicotine over polyvinylpyrrolidone modified nanomagnetite reaction obey pseudo-first order kinetic model. Nicotine degradation efficiency by Ng, NgM, and NgC was 61.5, 89 and 24%, respectively at 100 min, 25 °C, initial 8
Journal of Environmental Chemical Engineering 7 (2019) 102988
R. Bulánek, et al.
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