Preparation of magnetic Co3O4/TiO2 nanocomposite as solid-phase microextraction fiber coupled with chromatography for detection of aromatic compounds in environmental samples

Awat Ali Pouramjad; Hossein Khojasteh; Omid Amiri; Asma Khoobi; Masoud Salavati-Niasari

doi:10.1016/j.arabjc.2021.103262

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Original article

2021

:14;

202108

doi:

10.1016/j.arabjc.2021.103262

Preparation of magnetic Co₃O₄/TiO₂ nanocomposite as solid-phase microextraction fiber coupled with chromatography for detection of aromatic compounds in environmental samples

Awat Ali Pouramjad^{^a}, Hossein Khojasteh^{^b}, Omid Amiri^{^c,^d}, Asma Khoobi^{^e}, Masoud Salavati-Niasari^{^f,⁎}

a Department of Chemistry, Faculty of Science, Mahabad Branch, Islamic Azad University, Mahabad 59135-443, Islamic Republic of Iran

b Department of Chemistry, Faculty of Science, Soran University, P.O. Box 624, Soran, Kurdistan Regional Government, Iraq

c Faculty of Chemistry, Razi University, Kermanshah 6714414971, Iran

d Department of Chemistry, College of Science, University of Raparin, Rania, Kurdistan Region, Iraq

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

f Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 87317–51167, Islamic Republic of Iran

⁎Corresponding author. salavati@kashanu.ac.ir (Masoud Salavati-Niasari)

Received: 2021-4-14, Accepted: 2021-6-9,

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Abstract

A solid-phase microextraction (SPME) fiber using cobalt titanate nanocomposite (Co₃O₄/TiO₂) as sorbents is reported. The characterization of Co₃O₄/TiO₂ is performed by various methods such as FT-IR, XRD, and HRTEM. Then, the titanate nanostructures are placed in polyvinyl chloride (PVC) matrix and are coated on a copper wire. The sorbent is used for headspace microextraction of BTEX hydrocarbons from soil samples. Also, the optimization of all effective parameters on the SPME fiber is performed. The results show calibration curves are linear in the broad ranges from 5.0 to 500.0 µg L⁻¹ for benzene, ethylbenzene, and xylenes. Also, for toluene a linear calibration curve is obtained between 5.0 and 100.0 µg L⁻¹. Therefore, the lower limit of quantification (LOQ) is obtained 5.0 µg L⁻¹ for the analytes. The data indicate that the limit of detections (LOD) are obtained 0.84 µg L⁻¹ for benzene, 2.94 µg L⁻¹ for toluene, 1.53 µg L⁻¹ for ethylbenzene, 2.44 µg L⁻¹ for (m and p)-xylene, and 2.12 µg L⁻¹ for o-xylene. On the other hand, the results obtained from gas chromatography analysis show that the relative standard deviations (RSDs) are < 8.82%.

Keywords

Headspace microextraction

Gas chromatography

BTEX

Nanosorbent

Cobalt titanate nanocomposite

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1 Introduction

One category of usual compounds in groundwater contamination is volatile aromatic materials containing BTEX (benzene, toluene, ethylbenzene, and xylenes). These compounds have an aromatic ring as which is highly dangerous due to their harmful effects on health. The detection of BTEX is commonly performed using chromatography techniques and contains primary stages (Fustinoni et al., 1999; Kubinec et al., 2004; Farhadi et al., 2008 ). Improvement and modification of sample preparation methods typically create more reproducible results, decrease in toxic organic solvents, and leads to obtain cleaner extracts for analysis.

Standard methods for detecting of BTEX have some drawbacks, such as lack of selectivity and time-consuming procedures (Riboni et al., 2016). To solve the selectivity problem, most of the proposed solutions rely on gas chromatography-mass spectrometry (GC–MS) which demanding the preconcentration steps of analysts before separation stages and analysis (Brown, 1996).

The solid-phase microextraction (SPME) process is performed by distributing analytes among the stationary phase and the sample matrix (Pawliszyn, 1999). As it is known, SPME is a rapid and precise analysis for the determination of analytes in trace amounts. The SPME has been broadly applied in various fields such as food, environmental, and biological systems because the method is an adequate sample pretreatment process (Souza-Silva et al., 2015; Zhang et al., 2018). The central part of the method is the coating of fiber for separation steps. Therefore, the advancements in the SPME process would increase significantly relative to novel advances in the field of sorbents and coating materials (Feng et al., 2021; Tian et al., 2019).

Beside the commercially SPME fibers, there are several kinds of modified fibers such as non-polar silica particles (Liu et al., 1997), polymer materials (da Silveira et al., 1999), activated charcoal (Vaes et al., 1996), inorganic carbo pack (Wu et al., 2002), gold (Koster et al., 2001), aluminium wire (Gbatu et al., 1999), lead (Djozan and Assadi, 1999), modified alkyldiol-silica (Potter and Pawliszyn, 1994), polymeric fullerene (Ackerman and Hurtubise, 2002), carbon nanotubes (Metcalfe and Schmitz, 1961), nanostructured lead dioxide (Djozan et al., 2001), and silica nano particles (Wan et al., 1994).

Nevertheless, the conventional capillary columns manufactured with different coatings such as, Teflon, nylon, metals, etc., have some disadvantages containing low stability, low extraction efficiency, and in some fields, the diffusion of the analytes with slow rate cause lengthy extraction times (Mullett and Pawliszyn, 2002; Feng et al., 2020).

It is due that the polyvinyl chloride (PVC) is solid with brittle property and is available with a melting point between 100 and 260 °C with glass a transition temperature of 82 °C. These properties convert PVC inappropriate for use at high temperatures. Previously, PVC-based SPME fibers have been applied to detect of ethanol, methanol, and acetone in actual samples (Maleki et al., 2006; Matin et al., 2007). In a typical recent work, (Bodur et al., 2020); reported efficient microextraction strategy for the preconcentration and extraction of profenofos at trace levels prior to high performance liquid chromatography with ultraviolet detector and gas chromatography-flame ionization detector systems. They used magnetic Fe₃O₄/reduced graphene oxide nanocomposites based dispersive solid phase microextraction (DSPME) to extract and enrich the analyte from white rice flour samples. Their developed method provided a practicable, sensitiveand accurate determination of the analyte (Bodur et al., 2020).

In another recent works, (Chen et al., 2020); prepared fibrous TiO₂@graphitic carbon nitride nanocomposites (FTGCNCs) and applied it as a new adsorbent for dispersive micro-solid phase extraction of arsenic speciation. Results indicated that the sorbent has a good selectivity towards As(V) ions in the pH range of 2.0–4.0 (Chen et al., 2020).

The work is introduced a novel nanofibre based on magnetic nanostructures for solid-phase microextraction. Among magnetic materials, titanium-metal oxide nanostructures are very interesting compounds because of their properties (Ryu et al., 2018; Kojima et al., 2009; Kim et al., 2012; Burschka et al., 2013 ). Titanium-based oxide materials containing metals, such as Co, Ni, Fe, Pb, Cu, and Zn, are generally known as inorganic functional compounds with broad applications. For example, in industries, metal-air barriers, electrodes of the solid oxide, gas sensors, fuel cells, high-performance catalysts, trace analysis, and ferroelectric random access memories (Tang et al., 2018; Dadigala et al., 2021; Shaterian et al., 2015; Enhessari et al., 2017; Khoobi et al., 2021 ). In the present work, a sol–gel method was applied for the synthesis of Co₃O₄/TiO₂ nanocomposite. The technique is a low-cost, convenient, and uncomplicated procedure compared to the other previous works (Sanatkar et al., 2021).

In the present study, for the first time incorporating Co₃O₄/TiO₂ nanocomposite to PVC matrix (PVC/Co₃O₄/TiO₂) is reported. The presence of the Co₃O₄/TiO₂ can reinforce the performance of PVC and leads to the enhancement of its thermal characteristics. So, it is estimated that PVC/Co₃O₄/TiO₂ nanocomposite can show excellent adsorptive properties as an appropriate coating phase in SPME. Therefore, the study reports developing of a novel SPME fiber using a mixture of Co₃O₄/TiO₂ nanocomposite in a PVC matrix coated onto a copper wire. This has been used for headspace sampling of aromatic hydrocarbons from complicated actual samples.

2 Experimental

2.1

2.1 Instruments

Chromatographic tests were performed using Agilent 6890 N gas chromatograph-flame ionization (FID) detector, split/splitless injector. An HP-5 5% phenyl siloxane capillary column (i.d. 30 m × 320 µm, film thickness 0.25 µm) was used. An SPME device as laboratory-made was applied in the tests. Copper wires were prepared from SIMRAD AFSHAN SAHAR CABLE CO. (IRAN). Characterization of the Co₃O₄/TiO₂ was studied by a Fourier transform infrared (FT-IR, Shimadzu Varian 4300 spectrophotometer) and X-ray diffraction (XRD, condition: Cu Kα radiation, Rigaku D-max C III). Also, high-resolution transmission electron microscopy (HRTEM, Philips EM208 transmission electron microscope) micrographs were achieved by a Philips EM208 transmission electron microscope (Germany).

2.2

2.2 Reagents

Cobalt nitrate hexahydrate, tetraethyl orthotitanate, citric acid monohydrate, THF, PVC, and other chemicals were purchased from Merck. Helium, 99.999% purity was obtained from Roham Gas Co. (Arab Emirates), and H₂ as fuel gas for the FID (delivered Hydrogen of Generator from cfh200 model peak scientific instruments LTD) was used.

2.3

2.3 Synthesis of Co₃O₄/TiO₂

The synthesis procedure was developed according to the previous literature (Enhessari et al., 2010). First, the appropriate amount (0.4 mol) of citric acid monohydrate was melted at 73 °C. Next, Co(NO₃)₂·6H₂O (0.1 mmol) was mixed to the above solution and dissolved to prepare a transparent solution. Then, o.1 mmol of tetraethyl orthotitanate (stoichiometric amount) was transferred to the above mixture, and a stirrer was applied for the formation of a homogeneous sol (light red-brown). Then, the temperature was decreased to room temperature, and the product was dried for 12 h for drying the gel. Next, calcination of the gel was performed in four steps. First, heating of the gel was achieved to 400 °C (rate: 3 °C min ⁻¹). In the second step, a continuance of heating was performed at 400 °C (40 min). In the next step, 600 °C heating was applied. Finally, the temperature was held at 600 °C for two hours to obtain Co₃O₄/TiO₂ crystals.

2.4

2.4 Conditions of GC

The primary column temperature was adjusted at 50 °C (1 min) and increased to 75 °C (5 °C min⁻¹) and remained for 4 min. Helium was applied as makeup and carrier gas, which flow rates of 1.2 and 43 mL min⁻¹, respectively. The adjusting of temperature for injector and detector was performed at 190 and 300 °C, respectively. The splitless mode was applied for all injections.

2.5

2.5 Fabrication of SPME fiber

First, 30 mg of PVC powder was dissolved in THF solvent (5 mL). Then, 70 mg of Co₃O₄/TiO₂ was added to the solution. The suspension was kept for a few minutes to evaporate the THF solvent and to achieve more viscosity. Then, 1.5 cm of the length of the copper wire with an external diameter of 230 μm (the total length of 2 cm) was placed at the syringe and was entered several times into the suspension to create a homogeneous coating fiber. Next, the fiber was put into the injection port of the gas chromatography (250 °C, 20 min) to remove any pollution.

2.6

2.6 Headspace process

Eight milliliters of water sample was transferred in a vial containing 0.641 mol L⁻¹ of sodium chloride. Next, a silicone septum was applied, and the vial is sealed. The above vial was agitated (5 min) to stabilization adsorption of the analytes takes place onto the sample and therefore, an equilibration among the headspace and the sample matrix is created. Next, SPME was performed from the headspace of the water sample at 40 °C. After 35 min, the fiber was eliminated and instantly embedded into the hot injection port of GC and remained for 20 s (Fig. 1). Then, thermally desorption of the analytes was happened and moved through the capillary column by Helium gas. Finally, analysis of the analytes was accomplished by FID.

Schematic illustration of as prepared SPME fiber operation.

3 Results and discussion

3.1

3.1 Study and characterization of Co₃O₄/TiO₂

The chemical bonding of Co₃O₄/TiO₂ was investigated by FT-IR. Fig. 2 shows the vibrational spectra of the nanostructured composite. The broadband at 3430.66 cm⁻¹ is attributed to the —OH bonds of surface-adsorbed H₂O molecules (Yan et al., 2015). The sharp peaks that are observed at 566.64 as well as 663.73 cm⁻¹, can be related to M⚌O as well as M—O—M bond (Yang et al., 2016).

The XRD was applied to study the crystalline phase of the Co₃O₄/TiO₂ composite. Fig. 3 presents the XRD pattern of the Co₃O₄/TiO₂ prepared by the sol–gel route. The XRD pattern exposes the existence of a single phase of Co₃O₄ and TiO₂ in the Co₃O₄/TiO₂ composite. The pattern corresponds well with the standard JCPDS card of Co₃O₄ (card No. 01-073-1701) and TiO₂ (No. 00-004-0477). Also, the presence of strong and sharp patterns shows good crystallinity and high purity of the nanocomposite. The crystallite size of Co₃O₄/TiO₂ was obtained by Scherer’s equation (Shaterian et al., 2020). Therefore, the average crystallite size of the Co₃O₄/TiO₂ has calculated at about 24 nm.

The morphology of the Co₃O₄/TiO₂ nanocomposite was studied by HRTEM. Fig. 4 displays the typical morphology of the nanocomposite. The color contrast in the cross-section micrograph of Fig. 4 approves heterojunction formation between Co₃O₄ and TiO₂. The aggregates are observed in TiO₂ nanostructures with a diameter of 32 nm. Also, the Co₃O₄ nanostructures display a diameter of about 47 nm in Co₃O₄/TiO₂ nanocomposite with a rough surface, proving that the TiO₂ has uniformly coated on the Co₃O₄ surface (Fig. 4 (A, B)). Furthermore, a lattice spacing of 0.35 and 0.24 nm are observed for the TiO₂ and Co₃O₄ nanostructures, which is corresponding to the d-spacing of (1 0 1) plane of anatase TiO₂ and the (3 1 1) plane of cubic Co₃O₄ in Co₃O₄/TiO₂ nanocomposite, respectively (Fig. 4 (C)).

HRTEM micrographs of Co3O4/TiO2 in different scales.

3.2

3.2 Optimization of the coating composition

One of the important parameters on selectivity and efficiency is coating composition. Therefore, for obtaining higher sensitivity and better repeatability, the effect of the materials in coating composition on the efficiency of extraction was studied using BTEX. For completing the purpose, seven different percentages of Co₃O₄/TiO₂ nanopowders and PVC were prepared for SPME fiber coatings and estimated to choose the most appropriate modified fiber for headspace SPME-GC detection of (BTEX). The efficiency of the coating (90:10), (80:20), (70:30), (60:40), (50:50), (40:60) and (30:70) by weight percentage from Co₃O₄/TiO₂:PVC was investigated. The most appropriate coating composition was obtained at 70:30 (Co₃O₄/TiO₂:PVC). Therefore, a fiber of the composition (Co₃O₄/TiO₂:PVC, 70:30) was fabricated and applied in all of the experiments. The results are shown in Fig. 5.

Effect of coating composition (%w/w) on BTEX extraction (fiber 1, 30% Co3O4/TiO2, 70% PVC; fiber 2, 40% Co3O4/TiO2, 60% PVC; fiber 3, 50% Co3O4/TiO2, 50% PVC; fiber 4, 60% Co3O4/TiO2, 40% PVC; fiber 5, 70% Co3O4/TiO2, 30% PVC; fiber 6, 80% Co3O4/TiO2, 20% PVC; fiber 7, 90% Co3O4/TiO2, 10% PVC).

3.3

3.3 Investigation of the different temperatures

Application of high temperature in headspace SPME method causes an increase in the volatility of analytes is observed. The process also is appropriate to establish the distribution equilibrium of the analytes among the sorbent and gaseous. Nevertheless, the study about optimization of the temperature in the extraction stage is a necessary step. For achieving the goal, extraction of BTEX was accomplished by 8 mL aqueous samples with 100 µg L⁻¹ of each compound at different temperatures. Then, the area of each peak vs. temperature was achieved and is shown in Fig. 6 (A). As can be observed, most of the components have been extracted by the modified nanostructured fiber at 40 °C. Thus, 40 °C was considered as an appropriate temperature for the next steps.

Effect of (A): temperature, (B): time and (C): desorption temperature on the transfer of BTEX to headspace of water samples.

3.4

3.4 Microextraction time optimization

One of the critical parameters for improving the efficiency of extraction is the time of exposure of the sorbent in gaseous samples due to obtaining the appropriate distribution equilibrium of the analytes among the sorbent and sample. Thus, the proposed extraction method was performed several times (5–60 min). The plot of areas of peak vs. time is shown in Fig. 6 (B). According to the data, it has been decided that the equilibrium time was achieved in 40 min. Thus, the time was considered for further studies.

3.5

3.5 Desorption temperature and desorption time studies

Different temperatures of injections (120–210 °C) were considered for optimization of desorption temperature. According to Fig. 6 (C), desorption of all components happen at 180 °C. Therefore, 180 °C was designated as optimal temperature. Fig. 7 (A) shows desorption time profiles. All analytes that were adsorbed using the absorbent diffuse quickly from the porous layer into Helium (carrier gas). As can be observed in Fig. 7 (A), the mandatory time for completion of the desorption process is 15 s for the analytes. The porous structure of the Co₃O₄/TiO₂:PVC fiber causes short desorption equilibration times. The matter creates a decrease in the time of analysis and forms sharp chromatographic peaks.

(A): Effect of time on desorption of the analytes from the fiber at 180 ◦C and (B): influence of NaCl concentration on micro extraction efficiency of the SPME fiber.

3.6

3.6 Optimization of salt effect

It is demonstrated the solubility of organic compounds is decreased in the presence of salt. It is due to the attraction of water molecules by salt ions. The phenomenon causes that the interaction of water molecules with the solute is reduced. Therefore, the solubility of the analytes is reduced, and consequently, their separation or precipitation is reduced. For investigation of the effect of salting-out, the extraction is carried out by changing in NaCl concentration. The results are shown in Fig. 7 (B) and demonstrate that the salting out process is most effective in the presence of 0.641 mol L⁻¹ NaCl (0.299 g). Therefore, the concentration of NaCl was selected for each vial for further investigations.

3.7

3.7 Repeatability, reproducibility and stability studies

Additional studies were carried out to evaluate the repeatability of the proposed approach. Therefore, four replicate tests were performed using one single fiber, and then, the relative standard deviations (RSD) were obtained. The studies displayed that the RSD% of the proposed approach was ≤ 8.81% for all analytes (BTEX compounds) (Table 1). The results indicate that the method is a repeatable process. Furthermore, reproducibility investigations were implemented by three fabricated fibers, and then, fiber-to-fiber RSDs for all of the analytes (10.0 µg L⁻¹) were obtained between 6.5 and 12.23%.

Table 1 Repeatability of proposed method.

Compound	Concentration (µg L⁻¹)	^aRSD%	^bRSD%
Benzene Toluene Ethylbenzene m,p-Xylene o-Xylene	10 10 10 10 10	8.28 5.7 5.68 8.81 7.10	6.5 12.23 7.45 7.60 6.95

a n = 4, four replicate microextractions by a single fiber.

b n = 3, three replicate microextractions by three fibers with similar dimensions.

The fiber showed good mechanical stability, and the sorbent layer firmly adhered at the surface of the wire. Therefore, the copper wire was robust, flexible, and unbreakable support. Furthermore, the fiber-based on Co₃O₄/TiO₂ showed a very high thermal stability. Also, the sorbent was recycled fifteen times without any impressive decrease in the yield of extraction. The fifteen extractions were successful, and after fifteen cycles, the reduction in the efficiency was observed, probably due to the destruction of the foam structure. Moreover, the preparation of the modified foam was fast, cost-effective, and without memory effect.

3.8

3.8 Quantitative studies

After optimization of all effective variables, calibration equations along with their correlation coefficients, limit of quantifications (LOQ), limit of detections (LOD, S/N = 3) and Linear dynamic ranges (LDR) were determined. The data are presented in Fig. 8 and listed in Table 2. The excellent correlation coefficients (0.990–0.997), low LOQ (5.0 µg L⁻¹), and low LODs (0.84, 2.94, 1.53, 2.44 and 2.12 µg L⁻¹, for benzene, toluene, ethylbenzene, m-p-xylene, and o-xylene, respectively) show that the proposed approach is a proper route for trace analysis of BTEX. Also, a comparison was performed with previous literature for the determination of BTEX and is reported in Table 3 (Moliner-Martínez et al., 2013; Arambarri et al., 2004; Bianchin et al., 2012; Khezeli et al., 2015 ). The data demonstrate that the analytical responses of the proposed work are superior to the previous works of literature.

Chromatogram obtained from BTEX sample (10 µg L−1) using the proposed HS-SPME -GC-FID procedure.

Table 2 Quantitative characteristics of the proposed method for analysis of aromatic hydrocarbons.

Compound	Calibration curve equation	R^a	LOQ^b	LOD^c	LDR^d
Benzene Toluene Ethylbenzene m,p-Xylene o-Xylene	Y = 0.289X + 0.05 ^e Y = 0.727X + 0.754 Y = 0.414X + 0.335 Y = 0.634X + 0.658 Y = 0.439X + 0.861	0.990 0.997 0.993 0.990 0.992	5.0 5.0 5.0 5.0 5.0	0.84 2.94 1.53 2.44 2.12	5.0–500.0 5.0–100.0 5.0–500.0 5.0–500.0 5.0–500.0

a Correlation coefficient.

b Limit of quantification (µg L⁻¹).

c Limit of detection (µg L⁻¹).

d Liner dynamic range (µg L⁻¹).

e Y and × are peak area and concentration of the analytes (µg L⁻¹), respectively.

Table 3 The comparisons of the present work with previous reports for analysis of BTEX.

Method	LDR (μg L⁻¹)	LOD (μg L⁻¹)	Reference
HS-SPME ^a	_	0.3–5.0	43
PDMS-DVB SPME ^b	0.25–2.5	0.02–0.07	44
DI and HS-SPME-GC-MS ^c	0.3–10.0	0.07–0.3	45
ELLME-DES-HPLC-UV ^d	1.0–400.0	0.8–6.8	46
PVC/Co₃O₄/TiO₂ SPME	5.0–500.0	0.84–2.94	This work

a Hollow-fiber liquid phase microextraction.

b Poly(dimethylsiloxane)-divinylbenzene.

c Direct-immersion and headspace solid-phase microextraction coupled with GC–MS.

d Emulsification liquid–liquid microextraction based on deep eutectic solvent (ELLME-DES) coupled with HPLC-UV.

3.9

3.9 Real samples studies

For the applicability of the present work in the analysis of complicated samples, 2.0 g of soil samples from a Mahabad oil products distribution company were transferred to a 15 mL vial and, 8 mL of water assigned to extract the analytes to the water phase. Then, the micro-extraction of the solid phase from the headspace of the water phase was performed in optimal conditions. Finally, the concentration of BTEX compounds was calculated by calibration equations, and the results are shown in Fig. 9 and Table 4.

Typical gas chromatogram of BTEX assay in headspace of soil sample.

Table 4 Results from the analysis of soil sample of Mahabad's oil products distribution company.

Compound	Concentration in soil sample (µg Kg⁻¹)	Recovery (%)	RSD (%)
Benzene Toluene Ethylbenzene m,p-Xylene o-Xylene	0 22.78 26.65 29.84 25.33	101.8 97.6 103.2 97.8 98.4	±6.2 ±7.3 ±9.2 ±8.3 ±9.6

4 Conclusions

In summary, the Co₃O₄/TiO₂ nanocomposites were synthesized by a facile approach. Structural and morphological investigations of the nanocomposites were studied using different techniques. At first, the chemical bonding of the nanocomposites investigated by FT-IR. Also, the formation of the Co₃O₄/TiO₂ nanostructures was confirmed by XRD. Morphological evaluations of the Co₃O₄/TiO₂ nanocomposites were accomplished by HRTEM. Next, a new SPME fiber with high durability and high affinity toward non-polar compounds such as BTEX has been developed by the nanocomposites. It is based on Co₃O₄/TiO₂ nanocomposites fiber with high adsorption capacity. In the next step, the optimization of all effective parameters on the SPME fiber was performed. The headspace microextraction approach was used for preconcentration and solid-phase microextraction of BTEX. Using Co₃O₄/TiO₂ nanocomposite as a coating, the fiber provided a fast, cheap, and sensitive method to extract the volatile organic materials from natural samples.

CRediT authorship contribution statement

Awat Ali Pouramjad: Investigation, Formal analysis, Software, Methodology. Hossein Khojasteh: Software, Methodology, Writing - original draft. Omid Amiri: Software, Writing - review & editing. Asma Khoobi: Writing - original draft, Software, Resources. Masoud Salavati-Niasari: Writing - review & editing, Writing - original draft, Methodology, Conceptualization, Supervision, Project administration, Visualization, Data curation, Validation, Resources.

Acknowledgment

Authors are grateful to the council of Iran National Science Foundation (INSF; 97017837) and University of Kashan for supporting this work by Grant No (159271/V1).

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Sanatkar F., Khoobi A., Salavati-Niasari M., . An eco-friendly and simple sol-gel autocombustion method for synthesis of copper hexaferrite nanostructures: characterization and photocatalytic activity for elimination of water contaminations. Environ. Sci. Pollut. Res.. 2021;28:10791-10803.
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Zhang J., Zeng B., Zhao F., . Fabrication of bi-monomer copolymer of pyrrole-indole for highly efficient solid phase microextraction of benzene derivatives. Talanta. 2018;176:450-455.
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Show Sections

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[18] Gbatu T.P., Ceylan O., Sutton K.L., Rubinson J.F., Caruso J.A., Mark H.B. Jr, . Electrochemical control of solid phase micro-extraction using unique conducting polymer coated fibers. Anal. Commun.. 1999;37:203-205.
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[19] Khezeli T., Daneshfar A., Sahraei R., . Emulsification liquideliquid micro-extraction based on deep eutectic solvent: an extraction method for the determination of benzene, toluene, ethylbenzene and seven polycyclic aro-matic hydrocarbons from water samples. J. Chromatogr. A. 2015;1425:25-33.
[Google Scholar]

[20] Khoobi A., Salavati-Niasari M., Amiri O., . Ultrasonic synthesis and characterization of SnFe₁₂O₁₉/GO nanocomposite: Application of multivariate optimization in magnetic solid-phase extraction. J. Alloys Compd.. 2021;858:157745
[Google Scholar]

[21] Kim H.-S., Lee C.-R., Im J.-H., Lee K.-B., Moehl T., Marchioro A., Moon S.-J., Humphry-Baker R., Yum J.-H., Moser J.E., Grätzel M., Park N.-G., . Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%. Sci. Rep.. 2012;2:591.
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[22] Kojima A., Teshima K., Shirai Y., Miyasaka T., . Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc.. 2009;131:6050-6051.
[Google Scholar]

[23] Koster E.H.M., Crescenzi C., den Hoedt W., Ensing K., de Jong G.J., . Fibers coated with molecularly imprinted polymers for solid-phase microextraction. Anal. Chem.. 2001;73:3140-3145.
[Google Scholar]

[24] Kubinec R., Berezkin V.G., Górová R., Addová G., Mračnová H., Soják L., . Needle concentrator for gas chromatographic determination of BTEX in aqueous samples. J. Chromatogr. B.. 2004;800:295-301.
[Google Scholar]

[25] Liu Y., Shen Y., Lee M.L., . Porous layer solid phase microextraction using silica bonded phases. Anal. Chem.. 1997;69:190-195.
[Google Scholar]

[26] Maleki R., Farhadi K., Matin A.A., . Analysis of ethanol and methanol in human body fluids by headspace solid phase microextraction coupled with capillary gas chromatography. Anal. Sci.. 2006;22:1253-1255.
[Google Scholar]

[27] Matin A.A., Maleki R., Farajzadeh M.A., Farhadi K., Hosseinzadeh R., Jouyban A., . Headspace SPME-GC method for acetone analysis and its biomedical application. Chromatographia. 2007;66:383-387.
[Google Scholar]

[28] Metcalfe L.D., Schmitz A.A., . The rapid preparation of fatty acid esters for gas chromatographic analysis. Anal. Chem.. 1961;33:363-364.
[Google Scholar]

[29] Moliner-Martínez Y., Herraez-Hernandez R., Verdú-Andres J., Campíns-Falcó P., Garrido-Palanca C., Molins-Legua C., Seco A., . Study of the influence of temperature and precipitations on the levels of BTEX in natural waters. J. Hazard. Mater.. 2013;263P:131-138.
[Google Scholar]

[30] Mullett W.M., Pawliszyn J., . Direct determination of benzodiazepines in biological fluids by restricted-access solid-phase microextraction. Anal. Chem.. 2002;74:1081-1087.
[Google Scholar]

[31] Pawliszyn J., . Applications of solid phase microextraction. Cambridge: Royal Society of Chemistry; 1999.

[32] Potter D.W., Pawliszyn J., . Rapid determination of polyaromatic hydrocarbons and polychlorinated biphenyls in water using solid-phase microextraction and GC/MS. Environ. Sci. Technol.. 1994;28:298-305.
[Google Scholar]

[33] Riboni N., Trzcinski J.W., Bianchi F., Massera C., Pinalli R., Sidisky L., Dalcanale E., Careri M., . Conformationally blocked quinoxaline cavitand as solid-phase microextraction coating for the selective detection of BTEX in air. Anal. Chim. Acta.. 2016;905:79-84.
[Google Scholar]

[34] U. Ryu, S. Jee, J.-S. Park, I.K. Han, J.H. Lee, M. Park, K.M. Choi, Nanocrystalline titanium metal-organic frameworks for highly efficient and flexible perovskite solar cells, ACS Nano (12) 2018, 4968-4975.

[35] Sanatkar F., Khoobi A., Salavati-Niasari M., . An eco-friendly and simple sol-gel autocombustion method for synthesis of copper hexaferrite nanostructures: characterization and photocatalytic activity for elimination of water contaminations. Environ. Sci. Pollut. Res.. 2021;28:10791-10803.
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[36] Shaterian M., Khoobi A., Enhessari M., Ozaee K., . A new strategy based on thermodiffusion of ceramic nanopigments into metal surfaces and formation of anti-corrosion coatings. Microporous Mesoporous Mater.. 2015;218:62-68.
[Google Scholar]

[37] Shaterian M., Aghaei A., Koohi M., Teymouri M., Mohammadi-Ganjgah A., . Synthesis, characterization and electrochemical sensing application of CoFe₂O₄/graphene magnetic nanocomposite for analysis of atenolol. Polyhedron. 2020;182:114479
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[38] Souza-Silva É.A., Jiang R., Rodríguez-Lafuente A., Gionfriddo E., Pawliszyn J., . A critical review of the state of the art of solid-phase microextraction of complex matrices I. Environmental analysis, TrAC Trends. Anal. Chem.. 2015;71:224-235.
[Google Scholar]

[39] Tang Y., Wu L., Xiao L., Wen Di, Guo Q., Liang W., . Porous CoTiO3 microbars as super rate and long life anodes for sodium ion batteries. Ceram. Int.. 2018;44:18025-18031.
[Google Scholar]

[40] Tian Y., Feng J., Wang X., Luo Ch., Sun M., . Ionic liquid-functionalized silica aerogel as coating for solid-phase microextraction. J. Chromatogr. A. 2019;1583:48-54.
[Google Scholar]

[41] Vaes W.H.J., Hamwijk C., Urrestarazu Ramos E., Verhaar H.J.M., Hermens J.L.M., . Partitioning of organic chemicals to polyacrylate-coated solid phase microextraction fibers: kinetic behavior and quantitative structure-property relationships. Anal. Chem.. 1996;68:4458-4462.
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[42] Wan H.B., Chi H., Wong M.K., Mok C.Y., . Solid-phase microextraction using pencil lead as sorbent for analysis of organic pollutants in water. Anal. Chim. Acta. 1994;298:219-223.
[Google Scholar]

[43] Wu J., Mullett W.M., Pawliszyn J., . Electrochemically controlled solid-phase microextraction based on conductive polypyrrole films. Anal. Chem.. 2002;74:4855-4859.
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[44] Yan H., Zhao T., Li X., Hun C., . Synthesis of Cu-doped nano-TiO₂ by detonation method. Ceram. Int.. 2015;41:14204-14211.
[Google Scholar]

[45] Yang Y., Xu L., Wang H., Wang W., Zhang L., . TiO₂/graphene porous composite and its photocatalytic degradation of methylene blue. Mater. Des.. 2016;108:632-639.
[Google Scholar]

[46] Zhang J., Zeng B., Zhao F., . Fabrication of bi-monomer copolymer of pyrrole-indole for highly efficient solid phase microextraction of benzene derivatives. Talanta. 2018;176:450-455.
[Google Scholar]