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Journal of Environmental Health Science and Engineering logoLink to Journal of Environmental Health Science and Engineering
. 2020 Mar 2;18(1):201–209. doi: 10.1007/s40201-020-00453-4

Removal of ethyl benzene vapor pollutant from the air using TiO2 nanoparticles immobilized on the ZSM-5 zeolite under UVradiation in lab scale

Azam Derakhshan-Nejad 1, Hossein Ali Rangkooy 2,✉,#, Mahboobeh Cheraghi 1,✉,#, Reza Jalillzadeh Yengejeh 1
PMCID: PMC7203389  PMID: 32399232

Abstract

Ethyl benzene is a volatile organic compound that is used in the many industries, including Oil and Gas, Oil colored and Insecticides. Due to the toxic effects of this chemical substance control and elimination of this vapor is necessary. Photo catalytic degradation is a possible method to remove organic compounds from air. This study was performed to determine the efficiency of photo catalytic removal of ethyl benzene vapor using TiO2 nanoparticles immobilized on the ZSM-5 zeolite under UV radiation. This was an experimental study. The surface and volume of the pores of the bed were determined by the Bruner–Emmett–Teller (BET) method and Surface structure was determined by Scanning Electron Microscope (SEM), EDAX and X-Ray Diffraction (XRD). Dynamic air flow and different concentrations of ethyl benzene (25, 75 and 125 ppm) and flow rates (0.5, 0.7, and 1.0 L/min) were produced and the removal efficiency of ethyl benzene vapor were investigated using ZSM-5 and TiO2/ZSM-5/UV processes. The temperature and relative humidity were set at 25 ± 2°c and 35%. Evaluations for BET showed the specific surface areas decreased after loading TiO2 on ZSM-5. XRD and EDAX analysis and SEM images showed that zeolite structure was stabled and nanoparticles were successfully stabilized on Ze. The results showed that the highest removal efficiency (52%) by the process of TiO2/ZSM-5/UV (5 wt%) at concentration 25 ppm and flow rate 0.5 L/min respectively. The result of this study showed that the TiO2/ZSM-5catalyst may be a applicable and hopeful method to removal of ethyl benzene from air flow under UV irradiation.

Keywords: VOC, Ethyl benzene, TiO2 Nano particle ZSM-5 zeolite, Removal efficiency

Introduction

Volatile organic compounds (VOCs), are emitted in the form of gases from certain solids or liquids and may have short- and long-term adverse health effects [1].Ethyl benzene is also a natural ingredient in crude oil, gasoline, and cigarette smoke. Among the aromatics hydrocarbons of BTEX, ethyl benzene (C6H5C2H5) critically affects the blood, liver, and kidneys.

Ethyl benzene is also a natural ingredient in crude oil, gasoline, and cigarette smoke [2]. Among the aromatics hydrocarbons of BTEX, ethyl benzene (C6H5C2H5) critically affects the blood, liver and kidneys [1, 3].According to Occupational Safety and Health Administration (OSHA), National Institute for Occupational Safety and Health (NIOSH), and American Conference of Governmental Industrial Hygienists (ACGIH), the threshold for ethyl benzene concentration in the atmosphere is 100 ppm [4, 5] . Photo catalysis processes is one of the newest and best methods and several studies have examined photo catalytic degradation of organic compounds including ethyl benzene [6]. It is highly efficient for improving photo catalytic reactions to eliminate VOCs and convert them into odorless and harmless compounds like CO2 and H2O [7–9]. Nanoparticles of TiO2 have optimized performance on the near-UV light region because of its large energy band gap between electron-hole pairs of 3.3 e V and wavelength of 365 nm [10]. Among these technologies, advanced oxidation processes have been drawing more attention because of the restraints in the production of secondary pollution [11, 12].Photo catalysis, defined as a promising technology, developed since 1972. Semiconductors, as Nano crystalline TiO2 has recently drawn enormous attention, because of its photosensitive, physicochemical stability, inexpensive, non-toxic, erosion resistance, and chemically stable characteristics [13]. A rapid increase in electron donation to the conductivity band with light radiation is the main oxidation factor with TiO2 in the disintegration of organic compounds, which in turn accelerates photo catalytic degradation [1, 13]. However, TiO2 has a limitation of being used as a photo catalyst, mainly due to its small specific surface area [14]. Therefore, TiO2 can be fixed on some substrate with high specific surface area (SSA), such as zeolite, to induce removal efficiency for VOC [15–17]. Over the past few years, zeolite has drawn a great deal of attention as a sorbent due to its unique characteristics such as crystallization, acidity, ionic exchange capacity, and high SSA [18–20]. Recently, a lot of studies have been conducted for the photo catalytic oxidation of VOCs with some for ethyl benzene [3, 21, 22]. Hence, the aim of this study was to investigate ethyl benzene photo catalytic degradation performance of TiO2 (5 wt%) nanoparticles coated on ZSM-5 [23].

Material and methods

Preparation of TiO2/ZSM-5 catalysts

The current experimental study was carried out in a lab-based scale. Nanoparticles of TiO2 with density of 3.9 g/cm3, purity of 99.5% and SSA of 35 m2/g as well as zeolite (ZSM-5) were purchased from Sigma Aldrich-USA. Ethyl benzene with 99% purity was purchased from Merck Company (Germany).

Immobilization of TiO2 nanoparticles on ZSM-5 surface

Synthesized ZSM-5 was purchased with Si/Al in a ratio of 35/1 and a particle size of 0.5–1 nm from the penta ncil family with a structural framework of MFI (Microfinance Institutions). The ZSM-5 was separated in a standard sizes of 20–40 nm (ASTM, PA, USA), [24]. Adsorption sites of the ZSM-5 was improved through loading TiO2 (5 wt%) [25]. For loading, 4.75 g ZSM-5 was added into 0.25 g of TiO2 into 50 mL of deionized water (DIW) and stirred for 10 min. Then, solution was agitated with sonication bath (T22, USA) for 30 min at 50 KHz to obtain a homogenous suspension. The above colloidal mixture was thoroughly stirred (150 rpm) for additional 24 h to stabilizing TiO2 on the ZSM-5 surface. Then, the above mixture was passed through a filter paper and dried at 80 °C. To ensure thermal stability, the colloidal mixture was calcined at 450 °C for 4 h in a furnace [26].

Characterization of photo catalysts

The fabricated catalysts were characterized using analysis of Bruner-Emmett-Teller (BET), X-ray diffraction(XRD) using X PERT PRO MPD (PANalytical company-Netherland)40 kV, 30 mA over the 2θ range 2θ = 10–80°, So scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDAX). The SSA and pore size of the photo catalysts were measured using a Multi-Point BET method. The SSA was determined according to the adsorbed N2 gas molecules (liquid nitrogen with -196 °C) on the surface of the samples. The morphology of the photo catalysts and the confirmation of nanoparticles immobilized on zeolites were measured using an SEM microscope (Philips-XL30 the Amsterdam, Netherlands), equipped with facilities of EDAX with a voltage of 15 K v for elemental composition of samples.

Photo catalytic vapor removal system set-up

A schematic of the experimental set-up is shown in Fig. 1. The system was divided into three main parts: 1) the input section, 2) gas removal section, 3) the sampling section. In this dynamic system, airflow was passed from inlet part by a 51 w pump with a pressure of 11.47 mmHg (Hitachi Ltd. Tokyo Japan), from the activated carbon and silica gel containers to control humidity in the system. To control air temperature during the experiment, the output air pipes were placed in glass containers filled with water and the temperature of the whole system was monitored using three alcohol thermometers. All of the effective factors in evaporation of ethyl benzene including ambient temperature, ethyl benzene exposure surface to air, and its volume were remained constant for whole the experiment. Varieties of flow rate (0.50, 0.75, and 1.00 L/min)) were applied using a pump to supply different concentrations for contaminator (25, 75, 125 ppm). Ethyl benzene vapor was injected into the mixing container and mixed with the humid and clean air, while a specific concentration is sent to the reactor containing the bed. This study employed a cylindrical photo reactor made of quartz glass (for full transfer of radiation of UV) with a length, diameter, and a thickness of 280, 20, and 2 mm, respectively. This reactor has an inlet and an outlet at a distance of 2 cm from both ends of the cylinder in a way that they placed in the opposite direction from each other. An 8 w UV-lamp was placed in the center of the reactor with three 6 w UV-lamps outside of the reactor. The distances of the lamps inside and outside of the reactor were set to 3 mm and 50 mm, respectively. The TiO2/ZSM-5 catalyst was placed within the reactors and around the inner lamp so that it would be exposed to UV light from both sides [27, 28]. To avoid exposure to ambient light, the reactor was covered with aluminum foil [29]. The air flow-containing ethyl benzene was then passed through different flow rates and concentrations, under optimum condition (temperature and humidity). The concentration of ethyl benzene was measured by using a portable reading instrument of Pho check Tiger (Model 5000, UK) and recorded time intervals of 5 min in the inlet and outlet of the reactor [11]. The precision of the measured concentration using Po check was evaluated through a comparison with a gas chromatography measurement device (GC, Agilent Model7890A, USA) equipped with an FID flame detector [3]. Results showed a high correlation (R2 = 0.98) between two devices. In addition, all the measurements were replicated three times [11].

Fig.1.

Fig.1

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A schematic of the pilot-scale lab experiment

Results and discussion

Samples characterization

As it was showed in Table 1 findings obtained from SEM and BET, SSA of the produced TiO2/ZSM-5 catalysts (335.70 m2/g) decreased compared with the raw ZSM-5 (356.40 m2/g). The main reason may attribute to the blocking some of the meso porous and microspores of the raw ZSM-5 with coating TiO2 on the surface, which caused a reduction of the surface area and the average pore diameter of the zeolite. Additionally, nanometer scales were at the 40 nm range, which means an increase in the SSA and adsorption capacity [11, 30]. Indeed, the surface area of a catalyst is the most important factor for the catalytic activity of a catalyst. The higher surface area has higher efficiency to adsorb a pollutant. However, the destruction of organic pollutants, such as ethyl benzene, in TiO2 coating on the surface of ZSM-5 can induce removal efficiency much more than raw ZSM-5 [11].

Table 1.

Result of the BET tests

Parameters TiO2 Zeolite (ZSM-5) TiO2/ZSM-5 ZSM-5/TiO2
Special surface(m2/g 35 356.40 335.70 335.70
The average diameter of the cavities(A°) 6.92 4.98 0.18 0.19
Total volume (cm3/g 0.12 0.27 0.13 0.13
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SEM analysis was used to determine the morphology, shape, and particle size distribution in Nano and micro. Figure 2 shows SEM images of raw ZSM-5, raw TiO2, and bed after the immobilization process of TiO2 nanoparticles on it [31, 32]. Results of the SEM analysis represent a uniform-coating photo catalyst TiO2 nanoparticle on ZSM-5, which is the main factor to induce photo catalytic reactions (Fig. 2).

Fig. 2.

Fig. 2

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SEM images of: (a) raw ZSM-5 zeolite; (b) TiO2; and (c) ZSM-5/TiO2 5 wt.%

Photo catalytic activity mechanism

The chemical decomposition of volatile organic compounds in PCO is achieved with the use of hydroxyl radicals (OH). These radicals are strong oxidants and are created from the oxidation of water or the absorbed OH on the surface of the photo catalyst. The positive hole that is created can directly oxidize the pollutant and also react with water and create OH. The electron within the conduction band can also reduce the oxygen absorbed on the surface of TiO2. This process can be depicted using the relations bellow. Figure 3 show the process of photo catalytic decomposition of volatile organic compounds using TiO2 as the catalyzer. In this reaction, UVA radiation causes an electron to be exited in the valance band and move to the conduction band creating an empty positive hole in the valance band. These electrons and positive holes cause the oxidation and reduction of the absorbed compounds on the photo catalyst surface [33]. H+ and e− are considered to be strong oxidative and reductive factors respectively. The oxidative and reductive reactions are shown in reactions Fig. 3 Further; it should be pointed out that on zeolite coated with nanoparticles, processes, adsorption of ethyl benzene by zeolite and its degradation by TiO2 photo catalysts occur at the same time [4, 34, 35]. At the process of photo catalytic + adsorption after some time, Degradation rate almost reaches to steady state [36]. The oxidative and reductive reactions are shown in reactions 1.1 to 5.1.

Fig. 3.

Fig. 3

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A schematic of Photocatalytic activity mechanism

SEM-EDAX was also used to determine the elemental composition of the samples. Results showed silica and aluminum as the major elements in the ZSM-5 (Fig. 4 and Table 2). It is known that the ratio of Si/Al is crucial for the adsorption of pollutants on the surface of zeolite Therefore a significant increase of Si/Al was shown in the zeolite surface area, the average pore diameter, and the total volume of zeolite, which can induce ethyl benzene adsorption capacity on the surface of the zeolite [37].

Fig. 4.

Fig. 4

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XRD patterns of the ZSM-5 and coated ZSM-5 with TiO2 (5 wt.%)

Table 2.

Elemental analysis of the based on EDAX

Element Zeolite (ZSM-5) (wt.%) TiO2/ZSM-5(5%) (wt.%)
O 59.2 72.7
Na 0.1 0.1
Al 1.6 1.2
Si 34.6 24.2
Ti 4.4 1.8
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XRD analysis was conducted to identify mineralogy as well as any changes in the crystalline structure of the samples. As it is shown in Fig. 5, the raw ZSM-5 was mainly composed of quartz (SiO2) and aluminum silicate (SiO2/Al2O3) as the dominant crystalline phases. The XRD patterns of the coating of the TiO2 nanoparticles on the ZSM-5 surface showed sharp induced peaks at 2θ =24, 2θ =37, and 2θ =47, which related to the successfully loading crystals of TiO2 (Fig. 5).

Fig. 5.

Fig. 5

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Adsorption of ethylbenzene on the surface of raw ZSM-5 zeolite (25 ± 1oC, humidity: 35 ± 1) at different flow rate with UV lamp

The effects of concentration and gas flow rate on the adsorption efficiencey of ethyl benzene

Rresults of the effects of concentration and gas flow rate on the adsorption efficiency of ethyl benzene on the surface of the raw ZSM-5 (2 g) and UV light are shown in Fig. 4. Results showed that the adsorption of the ethyl benzene on the surface of raw ZSM-5 speeded up with an increasing concentration of ethyl benzene and flow rate increasing the gas flow rate significantly induced the saturation state of the ZSM-5 surface in a shorter period of time [26]. Sorption sites on the surface of the raw ZSM-5 were saturated with 25, 75, and 125 ppm of ethyl benzene after 680, 460, 370 min for gas flow rate of 0.50 L/min, respectively, while they were saturated after 280, 220, and 170 min for gas flow rate of from 0.50 to 1.00 L/min, respectively [37]. Noteworthy, adsorption of ethyl benzene using ZSM-5 in the condition of UV lamp on, showed no meaningful difference with that of UV lamp off [28].

The photo catalyst of TiO2/ZSM-5 was prepared with 5 w t% loading of TiO2 to increase the efficiency of the ethyl benzene removal as well as adsorption capacity [23, 26, 37]. Figure 6 shows the effect of TiO2 loading on the surface of ZSM-5 to remove ethyl benzene. Results showed that the removal efficiency of the ethyl benzene on the surface of TiO2/ZSM-5 decreased with increasing concentration and flow rate [11, 38]. However, ethyl benzene removal by TiO2/ZSM-5 catalyst with UV at a flow rate of 0.50, L/min, and different concentrations of 25, 75, and 125 ppm were 52%, 34%, and 24%, respectively. The results indicated that increasing ethyl benzene concentration led to an increase in removal efficiency, but for a shorter period of time. Sorption sites on the surface of the photo catalyst of TiO2/ZSM-5 could not reach to the saturation state either at different concentrations nor flow rates [14]. That means TiO2/ZSM-5 sorption sites remained active to adsorb more ethyl benzene for a longer period of time. Overall, degradation increased far more than adsorption using TiO2/ZSM-5, which means the removal efficiency is superior to normal adsorption (Fig. 7). This study demonstrated that the photo catalyst such as TiO2 was needed for the effective destruction of ethyl benzene. Other studies have illustrated this reduction as a result of catalyst penetration into the adsorbent porosities [37].

Fig. 6.

Fig. 6

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Adsorption of ethylbenzene on the surface of TiO2/ZSM-5 (25 ± 1 °C, humidity: 35 ± 1) with UV lamp (25 ± 1 °C, humidity: 35 ± 1)

Fig. 7.

Fig. 7

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A comparison between adsorption efficiency of ethylbenzene on the surface of TiO2/ZSM-5 (25 ± 1 °C, humidity: 35 ± 1) with/without UV lamp at flow rate 0.5 L/min

To evaluate photo catalytic removal of ethylbenzene, adsorption efficiency using TiO2/ZSM-5 under UV lamp on was compared with the condition of UV lamp off (Fig. 6). Results showed also, by TiO2/ZSM-5/UV that increasing ethyl benzene concentration led to an increase, in degradation (photo catalytic) and for a longer period of time. 52%, 34%, and 2 4% a meaningful difference between the t -wo different conditions. Sorption sites were saturated in a shorter period of time with higher adsorption efficiency under UV lamp off, while TiO2/ZSM-5/ UV surface remained active to remove as well as adsorbing more pollutants for a longer period of time under UV lamp on [39, 40]. Overall, an increase in concentration and flow rate caused an increase in degradation ratio but a decrease in performance efficiency [39, 41].

Removal efficiency ratio at 25 ppm was 52% at a flow rate of 0.50 L/min in TiO2/ZSM-5, while for 125 ppm it was 40% at a flow rate of 0.50 L/min (Fig. 8). That means a 12% reduction of the performance at different concentrations However, for the flow rate of 0.75 L/min, TiO2/ZSM-5 removal efficiency decreased from 46% to 18.5% in TiO2/ZSM-5/ UV at different concentrations. For the flow rate of 1.0 L/min, the degradation ratio decreased from 41% to 16.5% in TiO2/ZSM-5/ UV at different concentrations causing a slight decrease performance from 27.5% to 24.5% removal efficiency at different concentrations and different flow rates. Therefore, with an increase in the flow rate (0.50, 0.75, and 1.00 L/min) the performance decreased from 52% to 46% and 40% at a concentration of 25 ppm, despite an increase in the removal efficiency [18]. There was a significant difference in degradation ratio of the pollutant with and without TiO2 nanoparticles at different concentrations and flow rates [37].

Fig. 8.

Fig. 8

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TiO2/ZSM-5 photocatalytic degradation performance based on the concentration (25, 75, 125 ppm) and flow rate

Adsorption capacity

Catalyst adsorption the breakthrough capacities were obtained using Eq. (1). In this equation, (BC) mass of contamination adsorbed by the catalyst (mg/g)، Q:the air flow rate (m3/min), C) the concentration of contamination adsorbed (mg/m3), Tb k) breakthrough time.

BC=Q.C.TbkMadsorbent

The results related to, Table 3 was showed contamination ethyl benzene breakthrough capacities increases in the ZSM-5 with TiO2 (5 wt.%) than alone Ze. After, breakthrough capacities of the deactivated supports were indicated using raw ZSM-5/UV, more than 50% lower compared with the breakthrough capacities of ZSM-5/ TiO2/UV at optimum conditions(concentration 25 ppm and flow rate 0.5 L/min) respectively. However, this could be due to the absence of a crystalline structure within ZSM-5.Morphology of the catalysts are very important parameters that affect photo catalytic activity. FESEM images clearly showed that TiO2 nanoparticles were coated on the activated ZSM-5. Also, the images are indicators of uniform coating of photo catalyst TiO2 pores.This shows that Photo catalytic activity of has been made more effective. Also, the results of concentration and flow rate show that with increasing concentration, the adsorption capacity increases in all samples [42, 43]. In the other study, the best rate of loading of TiO2on the Ze in order to remove vocs, was reported 5% and increasing the more percentage of TiO2 (>5%) loading on Ze, the less rates of adsorption and elimination. This reduction is due to blocked pores (some of mesopores and micropores), thus the surface area of zeolite and the adsorption rate greatly reduced and cavities of the substrate by TiO2 nanoparticles reduces the surface of bed. Therefore in this study amount of fixed TiO2 on the ZSM-5 was selected, weight percentages (5%) [11]. So in this study, maximum activity of ZSM-5/TiO2/UV catalysts was achieved. The optimum temperature and humidity for photo catalytic degradation were 25 ± 1 °C and 35 ± 1%, respectively [24]. Studies show that with increasing of concentration and flow rate, more mass of pollutants per unit of time was removed from the air current, Therefore, the breakthrough time and saturation of adsorbent was reduced by the process of TiO2/ZSM-5/UV (5 wt%). It can be concluded that in all catalysts, increasing the concentration of ethylbenzene, leads to a decrease in the breakthrough time and an increase in the adsorption capacity. Rangkooy et al. also reported that by reducing the concentration of the input pollutant, breakthrough times increases while adsorption capacity decreases [44]. In this study Similar to previous studies is investigated, by increasing the concentration of ethyl benzene, the ratio of the number of ethyl benzene molecules to the number of active sites on the catalyst surface increases [10]. So due to the increase in the speed of propagation and penetration into the pores of the catalyst, adsorption would occur faster [17] .This means that full saturation of the active sites on the surface of the adsorbent occurs in a shorter time [26]. The results of this study showed that increasing input concentration leads to the faster saturation of the absorbent and hastens the breakthrough point, which is consistent with the results of other studies [45, 46]. It was observed that an increase in the concentration of contaminant decreased adsorption efficiency [21]. In addition, an increase in photo catalytic degradation volume decreased for all flow rates, namely, 0.50, 0.75, and 1.00 L/min with an increase of concentration [40, 47]. Therefore, the saturation of the active sites on the catalyst surface occurred faster [32]. This might be effective in the removal of ethyl benzene using immobilized nanoparticles in a shorter period of time so that with complete saturation of the active adsorption sites, excessive contaminators cover the Nano catalyst and block the UV light that is needed for photo catalytic degradation [37]. Results of the degradation at the three concentration levels showed that an increase in ethyl benzene concentration decreased degradation performance on photo catalytic substrates It has been reported that to improve photo catalytic reactions of solid-gas hybrid substrates, the reaction system needs constant exposure of UV photons to photo catalytic particles [48]. In general, with an increase in the flow rate of the contaminator, the chance for penetration into the catalyst substrate decreases and the contaminator molecules are less probable to bond with active catalyst spots [24, 49].This study focuses on the efficacy of photo catalytic degradation of ethyl benzene,steam pollutants in the air and demonstrates the efficacy of TiO2 combination and ZSM-5 on the photo catalytic removal of ethyl benzene vapor. However, the saturation capacity of this TiO2 nanoparticles and hybrid photo catalytic system could be assess at future [27, 28].

Table 3.

Results of the breakthrough and catalyst adsorption capacity ethyl benzene

Sample Flow rate L/min Concentration (ppm) Breakthrough time (min) Adsorption capacity (mg/g)
ze 0.50 25 660 18.3
75 440 35.1
125 320 44.2
ZSM-5 TiO2 5% 0.50 25 800 22.1
Flow rate (0.5) 75 540 44.8
l/min 125 440 60.8
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Conclusion

There are varieties of technologies to remove organic air pollutant such as ethyl benzene. Among those, advanced oxidation processes using a photo catalyst is a promising approach to clean a polluted atmosphere. Our data suggest that photo catalyst based on titanium supported on ZSM-5 is a proper system to remove and more important for degradation of ethyl benzene from air to eliminate its toxicity by 50% at these optimum conditions. In particular, the photo catalytic performances of the TiO2/zeolite hybrid system are more efficient to remove ethyl benzene at low concentrations. In general, and given the results here and other similar studies, it can be concluded that substrates with high specific surface yield better results in terms of remove efficiently. Such hybrid substrates can be used with lower operation costs comparing catalytic methods and other available methods; however, as another benefit of this system, it can be readily manufactured by loading photo catalytic nanoparticles on a sorbent with a suitable and specific surface area. The results revealed that the best further investigations on the treatment of VOCs mixtures are highly recommended. A synergistic effect was also observed when TiO2and zeolite were simultaneously used for the photo catalytic degradation of ethyl benzene.

Acknowledgments

The present paper is extracted from a Ph.D. dissertation in Environmental Engineering, Khouzestan Research and Science Branch, Islamic Azad Univerity, by Ms. Azam Derakhshannezhad. The authors express their gratitude toward the professors and officials of the supporting entities.

Abbreviations

XRD

X-ray diffraction

SEM

scanning electron microscopy

EDAX

energy-dispersive X-ray spectroscopy

BET

Bruner-Emmett-Teller

TiO2

Titanium dioxide nanoparticles

Valance band

Valance band

Conduction band

Conduction band

Funding information

The present work was part a Ph.D. thesis entitled “Evaluation of Zeolite-based Nano sized TiO2 for photo catalytic degradation in gas phase ethyl benzene from atmosphere, which was financially supported by Ahvaz University of Medical Sciences.

Compliance with ethical standards

Conflict of interest

The authors confirm no conflicts of interest associated with this publication.

Consent for publication

All authors agreed to publish this article.

Ethics approval and consent to participate

No human samples were used in this study and all experiments were chemically and in laboratory scale.

Footnotes

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Hossein Ali Rangkooy and Mahboobeh Cheraghi contributed equally to this work.

Contributor Information

Hossein Ali Rangkooy, Email: Rangkooy@gmail.com.

Mahboobeh Cheraghi, Email: mahboobeh.cheraghi82@yahoo.com.

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