Prussian Blue Modified Magnetite Decorated MW-CNT Nanocomposite: Synthesis, Characterization and Potential Use as Photo-Fenton Catalysts for Phenol Degradation

doi:10.21203/rs.3.rs-2987292/v1

Removal of organic pollutants with green and efficient methods is an important goal for researchers studying environmental pollution. Photo-Fenton systems with heterogeneous catalysts are a promising alternative for efficient water treatment. In this study, Prussian blue modified magnetite decorated multi-walled carbon nanotubes (MW-CNT) nanocomposite was prepared and for the first time applied to the photo-Fenton degradation of phenol. The catalyst was prepared by rapid hydrothermal method. XPS, SEM-EDX, XRD, FTIR methods were used for characterizing the functionalities and morphology of the catalyst. The effect of initial H₂O₂ concentration, catalyst mass, and initial pH of the phenol solution was investigated. Experimental results showed that 100 mg dm^-3 of phenol could be degraded completely in 15 minutes at pH 7. This study describes the synthesis of the new Photo-Fenton catalyst for highly effective phenol treatment.

Prussian Blue Modified Magnetite

MW-CNT

Photo-Fenton Reaction

Phenol

As a result of tremendous global economic growth, the use of chemicals with rapid urbanization and industrialization has caused environmental pollution and has negative effects on soil and water systems (Gu et al., 2022; Li et al., 2022). Water pollution has harmful impacts on environment and human health, especially due to some toxic organic pollutants (Liu et al., 2022). Phenols have become one of the most abundant organic pollutants in industrial wastewater due to their widespread use in various industries such as resin production, petrochemistry, oil refining, papermaking, textiles, etc. (Feng et al., 2022). Removal of environmental pollution and remediation of polluted areas is still a topic of current interdisciplinary research. There are many conventional methods to treat phenol, such as adsorption, flotation, membrane separation, and biodegradation. The high solubility and stability of toxic phenolic wastewater makes it practically impossible to bring it to a harmless level with these processes. By physical methods, waste components are only transferred from one phase to another. The biodegradation process is one of the most used methods for the removal of organic wastes. However, the applicability of this method is limited since many pollutants are powerful biocides; high concentrations of phenol can inhibit or eliminate the bacteriological population in the biodegradation process. In addition, during chemical treatment methods such as chlorination, chlorinated phenols and toxic by-products are formed (Kim and Kan, 2015; Nie et al., 2017; Nawaz et al., 2020; Nemakal et al., 2021). However, in oxidation processes, which are an efficient removal method, organic pollutants are decomposed to CO₂ and H₂O and the pollutants are completely mineralized. Among the available oxidation technologies, advanced oxidation processes (AOPs) have been recognized as an attractive alternative process for the removal of toxic and non-biodegradable pollutants such as pharmaceuticals, pesticides, and other organic compounds from wastewater with its high efficiency (Kim and Kan, 2015; Emídio, Hammer and Nogueira, 2020; Nawaz et al., 2020; Feng et al., 2022). AOPs, which has fewer operating problems and provides higher treatment efficiency compared to other advanced treatment methods, have recently taken an important place in the treatment of industrial wastewater (De Jesus, Lima and Pupo Nogueira, 2022). Various AOPs like ozonation, electrochemical oxidation, Fenton, Photo-Fenton and Sono-Fenton were successfully used for the removal of phenol from wastewater. Due to its superior efficiency and economic feasibility, the Photo-Fenton process has been accepted as a more efficient alternative process for wastewater treatment compared to other AOP techniques. However, the homogeneous Fenton process has several problems including the acidic pH values and additional H₂O₂, that prevent its widespread application to waste water treatment. For these reasons, heterogeneous Photo-Fenton systems, which can operate in wider pH ranges and reuse of the catalyst, have a become very promising alternative for water treatment.

Synthesizing the catalyst with desired structural, morphological, and electronical properties is one of the key steps to advance the reaction kinetics of a Photo-Fenton catalyst. According to this strategy, various kinds of components were investigated by researchers (Wu, Chiu and Lin, 2018; Shoaib Ahmad Shah et al., 2022). Heterostructures, in which one component is combined with at least one other material, such as metal, metal oxide, polymer, graphene, carbon nanotube etc. are a new form of unique materials. Many heterostructures based on carbon nanotubes as supporting material were formed and preferred as catalyst component in Photo-Fenton reaction (Yin et al., 2019; Gu et al., 2022; Thi et al., 2022). In addition, one of the most favorable catalyst components is metal oxides (Zhang et al., 2022). Magnetite (Fe₃O₄) is an iron oxide particle that has high abundance, chemical stability, and good photochemical activity (Nemakal et al., 2021). Magnetite has an important role in Photo-Fenton processes by degradation of various organic pollutants (Wu, Chiu and Lin, 2018; Emídio, Hammer and Nogueira, 2020; De Jesus, Lima and Pupo Nogueira, 2022). Prussian Blue (PB), Fe₄[Fe(CN)₆]₃, is a coordination compound that is used for many applications due to its special properties (Wu, Chiu and Lin, 2018; Yin et al., 2019; Najam et al., 2020; Shoaib Ahmad Shah et al., 2022). PB is also preferred component for Photo-Fenton reactions due to its porous and unique structure (Thi et al., 2022). As shown in the literature, CNT, Magnetite and PB are the components used separately as catalysts in the Photo-Fenton reaction. However, these three components were combined for the first time and used as a novel catalyst in the Photo-Fenton reaction for the degradation of phenol, a critical pollutant.

In this study, magnetite nanoparticles modified with Prussian blue (PMM) were decorated on multi-walled carbon nanotubes (CNT-PMM) were synthesized by using one pot hydrothermal method. The obtained nanocomposite was characterized by SEM-EDX, XRD, FTIR, XPS techniques and used as a heterogeneous catalyst in the degradation of a well-known pollutant, phenol molecule, by Photo-Fenton reaction. The conditions of the Photo-Fenton reaction (catalyst amount, pH, H₂O₂ concentration) were optimized.

Synthesis of PMM and PMM-CNT

Prussian blue (PB) modified magnetite nanoparticles were synthesized using one step hydrothermal method as described by Jomma et al. (Jomma and Ding, 2016). Briefly, (Fe(NO₃)₃.9H₂O (8.0 mmol; 1.939 g) dissolved in 40 cm³ of ethylene glycol (EG) and then 1.0 g of PEG-600 was added under mechanical stirring. Subsequently, 0.67 g of potassium ferric cyanide was added into the solution, stirred vigorously for 1 hour on a magnetic stirrer. Then the solution was transferred into a teflon lined stainless steel hydrothermal reactor. The mixture was heated at 190°C for 12 hours under hydrothermal conditions. Finally, the precipitate was separated from the solution with the help of a magnet. The sample was thoroughly washed 3 times with distilled water, and 3 times with ethyl alcohol. Then the sample was dried at 60 ^oC for 3 hours and labeled as PMM. For the synthesis of MW-CNT/PMM composite, 100 mg of HNO₃-treated MW-CNT(Özdokur, 2020) was added into 40 mL EG, and ultrasonicated for 1 h. Then, Fe(NO₃)₃.9H₂O and K₃Fe(CN)₆ was added and same synthesis procedure was followed as described above. The bare magnetite as synthesized by using 8 mmol of Fe(NO₃)₂.6H₂O instead of K₃Fe(CN)₆ and the same hydrothermal conditions were applied.

Characterization of nanocomposite

Morphology of the composite materials were investigated with Field Emission Scanning Electron Microscopy (FEI Quanta 450) using Everhart–Thornley detector (ETD). The crystalline structure of the synthesized materials was investigated with PANalytical Empyrean diffractometer using Ni filtered CuKα radition (λ = 1.54050 Å; 45kV and 40 mA) at room temperature. The chemical composition of synthesized materials was examined by X-ray photoelectron spectroscopy (XPS) and high-resolution X-ray photoelectron (HRXPS) measurements. Thermo Scientific Model K-Alpha XPS (Thermo Fisher Scientific, U.K.) equipped with monochromatic Al K radiation were used for the XPS analyses (1486.7 eV). Based on the C 1s peak's at 284.8 eV binding energy, the photoelectron binding energy scale was optimized. High-resolution scans for each element were collected using a pass energy of 50 eV with a 0.05 eV step size whereas survey spectra (pass energy of 200 eV with 1.0 eV step size) were obtained using an analyzer with a pass energy of 200 eV. The X-ray spot size was changed for single-point analysis to 300 µm. Five separate point analyses conducted for each sample in order to ensure the homogeneity of the samples. A Shirley/Smart type background and Gaussian/Lorentzian peak shapes were used to complete the peak fitting process.

Phenol amount in the Fenton experiment was monitored with both HPLC-UV and UV-Vis measurement. Thermo Dionex Ultimate 3000 HPLC system was used for quantification. The mobile phase was consisted of aqueous solution of 0.05% TFA (10%, v/v) and methanol (90%, v/v). Chromatographic separation was achieved under isocratic flow with a rate of 1.0 cm³min^-1 the quantification wavelength was chosen as 274 nm while the injection volume was 20 mm³. On the other hand, the absorbance at 274 nm was monitored for the analysis phenol by using Perkin Elmer UV – Vis spectrometer. The limit of quantification of the UV method was calculated as 0.1 mg dm^-3. The samples were centrifuged at 10000 rpm and filtered through a syringe filter prior to HPLC and UV measurements, in order to avoid obtaining turbid samples. The both results were compared with student’s t-test and not statically difference was found between results. Accordingly, UV method was used for entire experiments.

SEM-EDX Studies

SEM images of the bare carbon nanotube appearing as long rods are given in Fig. 1A and these images agree with the literature (Acar And Ertugrul, 2021). The SEM images of magnetite nanoparticles modified with Prussia blue is given in Fig. 1B. and the PMM particles were in a spherical structure and their average diameter is around 250 nm. Figure 1C shows the SEM images of PMM-CNT composite, it was observed that the carbon nanotubes wrapped around the spherical Prussian blue-modified magnetite nanoparticles like a spider silk. The radius of the Prussian blue modified magnetite nanoparticles formed on the nanocomposite was measured as approximately 170 nm. According to the obtained SEM images, it is seen that the nanocomposite was successfully synthesized. On the other hand, EDX spectrum of the nanocomposite is given in Fig. 1D. The composite material was consisted of C, N, O and Fe with atomic ratio of 46%; 8%; 26% and 19%, respectively. On the other hand, the atomic percentages of C, N, O, and Fe was found as 31%; 10%; 50% and 8.6% in PMM, respectively. Considering the elemental results, the amount of C in the CNT-PMM was much higher than PMM. It is seen that the incorporation of MW-CNT into the structure increases the C atomic percentage. This confirms that only C-containing CNT enters the structure. Among them, a small K peak was observed in the EDX spectrum belonging the starting material.

XRD Studies

The crystal structure of the obtained nanocomposite was investigated using the XRD technique. For this purpose, comparative diffraction patterns of plain MW-CNT, Prussian blue modified magnetite nanoparticles and Prussian blue modified magnetite nanoparticles decorated carbon nanotubes were recorded and given in Fig. 2. As can be followed from the Fig. 2a the peaks of the bare multi-walled carbon nanotube (002) and (100) planes appeared at 26.1 and 42.71 (Soleimani, H., Yahya, N., Baig, M K., Khodapanah, L., Sabet, M., Burda, M., Oechsner, A., Awang, 2015). The diffraction pattern of PMM was given in Fig. 2c. In the spectrum, the diffraction peaks of magnetite were observed at 18.40^o; 30.29^o; 35.65^o; 43.33^o; 53.73^o; 57.30^o and 62.93^o (2Ɵ) corresponds to the crystal planes of (111), (220), (311), (400), (422), (511) and (440), respectively (Fig. 2b). On the other hand, the diffraction peaks of magnetite (Fe₂O₃) peaks were not observed at 23.84^o and 26.11^o in any diffraction pattern. The peak positions and relative intensities match well with the crystal structure of Fe₃O₄ with a face centered cubic structure (JCPDS cards No 89–0691, 88–0866 and 75–0033) (Caglar et al., 2018). In addition to the peaks of magnetite, the diffraction peaks at 17.40^o; 24.76^o and 35.60^o (2Ɵ) was observed that peaks can be assigned to the Prussian Blue (Zhao et al., 2005). The XRD spectrum of CNT-PMM composite was given Fig. 2c and XRD peaks of both PMM and CNT was observed in the diffraction pattern. In addition, the grain size of the PMM moieties in the composite was calculated from Scherrer Equation and found as 158.6 nm. This value is in good agreement with the SEM images.

FTIR Studies

FTIR method is frequently used for characterization in order to take measurements easily and to determine the functional groups of the molecules studied. FTIR spectroscopy is a very practical method in the characterization of composite materials, and it provides the comparison of the product formed after modification with the original product. Comparative FTIR spectra of bare MW-CNT, Prussian blue modified magnetite nanoparticles and Prussia blue modified magnetite nanoparticles decorated carbon nanoparticles are given in Fig. 4. The bands with a wave number of 3421 cm^-1 belong to the stretching vibrations of the surface hydroxides and/or OH of the water adsorbed on the surface. Vibrations of 1638 cm^-1 and bands in the range of 1100–950 cm^-1 indicate the presence of C = C in aromatic rings and C–O bonds in various chemical environments, respectively. On the other hand, stretching vibrations of the C-H bonds on the MW-CNT are observed at the wave number of 2918 cm^-1 (Ţucureanu, Matei and Avram, 2016). The IR spectrum of the PMM is given in Fig. 4b, and the vibrations of Fe-O and Fe-O-Fe stretching in the magnetite crystal lattice showed IR bands at 573 and 452 cm^-1. Looking at the peaks obtained from the images, it is understood that the results are in good agreement with the literature (Caglar et al., 2018). While the band at 593 cm^-1 is attributed to the Fe-O stretching in the tetrahedral and octahedral areas, the band at 452 cm^-1 is only associated with the Fe-O stretching of the octahedral sites in the crystalline lattice of magnetite (Gotić, Koščec and Musić, 2009). On the other hand, it has been reported in the literature that the shapes of these peaks and their locations in the spectrum are affected by the cation vacancies and particle size in the magnetite lattice (Márquez et al., 2011). Considering the data obtained from SEM images, the dimensions of the particles obtained are in full agreement with the literature. In addition, broad bands in the 3450 − 3100 and the IR peaks at 1623, 1426, 1055 and 702 cm^-1 can be attributed to the in-plane and out-of-plane bending of the hydroxyls in the water molecules attached to the magnetite surface. The peak at 2073 cm^-1 was due to the CN group, while the absorption band at 476 cm^-1 and the peak at 593 cm^-1 corresponded to Fe–CN–Fe and to the Fe–O bond, respectively. The peaks at 2073, 476 and 593 cm^-1 confirm the formation of magnetite PB nanoparticles. In nanocomposite, MW-CNT and PMM were observed this indicating the obtained composite was successfully synthesized.

Photo-Fenton Degradation Studies

The photocatalytic activity of the synthesized nanocomposite catalyst was evaluated using the decomposition reaction of phenol with the Photo-Fenton process. The photocatalytic activity tests of the samples were carried out under a UV lamp with a power of 100 W and a wavelength of 350 nm. The photocatalytic reaction solutions were mixed in the dark for 30 minutes to achieve the adsorption/desorption equilibrium on the catalyst surface. At the end of this period, after the initial concentration of adsorption/desorption equilibrium was completed, 1 cm³ of solution was taken and measured in a spectrophotometer, and the absorbance value was recorded. Afterwards, the UVA lamp was turned on and H₂O₂ was added to the solution to initiate the Photo-Fenton reaction. Then, in order to evaluate the degradation of phenol, 1 cm³ of solution was taken at determined time intervals using UV-Visible spectrophotometer, centrifuged at 10000 rpm for 5 minutes, absorbance was measured at 274 nm wavelength and their concentrations were determined. The effect of catalyst load on Photo-Fenton performance of the developed nanomaterial was tested by varying the amount between 5 to 30 mg. According to the results given in Fig. 5a the degradation efficiency was increased by increasing catalyst load. However, in the presence of 30 mg of catalyst, it has been observed that there is a slight decrease in the decomposition efficiency compared to 20 mg. This situation can be explained by two factors. The first of these is that when the amount of catalyst increases, the turbidity of the solution increases, and the UV light was prevented from spreading homogeneously all over the solution. Therefore, this caused a decrease in the degradation rate. Another problem was that the increased amount of catalyst causes the catalysts coagulation. Because of the decrease in the catalytic surface area by coagulation, and the performance of the catalyst were affected negatively (Sakthivel et al., 2003). As, it was observed that the best result was obtained for 20 mg, and further studies were conducted by using this amount in the next experiments. The pH of the working solution is another important parameter that affect the formation of radical species and physico-chemical properties of targeted molecule (Davaslıoğlu et al., 2021). In order to evaluate the effect of pH on degradation efficiency, the pH of solutions was changed between 2.0 to 12.0. The obtained data were given in Fig. 5B. the maximum degradation was achieved while the pH value was set at 7.0. In the Fenton process, the pH has a restrictive property, when the pH is higher than 4, the formation of different iron species and even inactive species such as Fe(OH)₃, prevents the formation of hydroxyl radicals. On the other hand, when the pH is below 3, hydroxide radical formation is slow (Bayat, Sohrabi and Royaee, 2012). However, when heterogeneous catalysts are used, the charge of the catalyst surface becomes more important than the efficiency of Fe ions. In this case, it affects the optimum working pH. The zeta potential of the magnetite structure is positive up to pH 5 and negative at higher pHs (Ucbas et al., 2014). On the other hand, the phenol compound forms a phenolate ion after pH 10 and this ion is repelled by the negatively charged catalyst surface (Rangumagar et al., 2018). Therefore, the obtained result seems to be compatible with the literature data considering both the charge of the catalyst surface and the chemical structure of the target pollutant. The amount of hydrogen peroxide is another important parameter molar concentration of 0.0088, 0.0176 and 0.0256 M hydrogen peroxide were studied, and the results were presented in Fig. 5C. It was observed that the best result was obtained by using 0.0176 M H₂O₂. After the optimization studies, different phenol concentrations were tested under optimum conditions and the results are given in Fig. 5D. According to the results obtained, it was observed that a similar degradation profile was observed up to 500 mg dm^− 3 phenol.

Also, comparative degradation profiles were given in Fig. 6. As can be seen from the figure, the phenol solution remains stable under UV light for 60 minutes. As the hydrogen peroxide is added to the phenol solution and exposed to UV light, it is observed that there is a small decrease in the absorbance of the phenol. However, when magnetite is used as a catalyst, it is observed that 60% degradation occurs after approximately in one hour. In the control experiment with plain MW-CNT, it was observed that 70% of the phenol was degraded in 60 minutes. A superior degradation profile was observed when the CNT decorated PMM was used that the phenol was completely decomposed in 15 minutes. The individual data of the comparison graph was fitted to first order kinetic according to the Eq-1.

ln (C/C_in) = -k_appt (1)

The calculated linear regression equation, regression coefficient and degradation constants were given in Table 1.

Table 1

Individual data for CNT, PMM and PMM-CNT obtained at optimized conditions and degradation rate constants.
Catalyst	C/C_in								R²	k_app(Ms^− 1)
Catalyst	Time (min.)	0	5	10	15	30	45	60
CNT		1.0	0.6	0.5	0.4	0.4	0.3	0.3	0.8149	0.0189
PMM		1.0	0.7	0.6	0.5	0.4	0.4	0.3	0.9046	0.0154
PMM-CNT		1.0	0.2	0.1	0.1	0.0	0.0	0.0	0.9741	0.0605

According to the Table 1 the highest degradation coefficient was achieved for the PMM-CNT composite catalysis. These results revealed that the obtained catalyst was highly effective in the degradation of phenol by the Photo-Fenton process.

The obtained results were compared with the proper literature data and given in Table 2. According to the Table 2 the modification magnetite structure with Prussian Blue enhanced the photocatalytic activity of catalyst towards photo-Fenton degradation of phenols.

Table 2

Summary of relevant publications comparing the development of photocatalysts using in the degradation of phenol.
Material	Phenol Concentration (mg.dm^− 3)/ pH	Time (min.)	Phenol Removal (%)	References
Ferric ion	207 /3	120	95–99	(Kavitha and Palanivelu, 2004)
CdS/rGO/Fe²⁺	10 /7	60	100.0	(Jiang et al., 2019)
Fe₃O₄-GO	20 /5	120	98.8	(Yu et al., 2016)
GO and g-C₃N₄ / Fe₃O₄	50 /-	480	97.0	(Rehman et al., 2019)
PMM-CNT	100/ 7	15	99.7	This study

Reusability of the catalyst

Reusability of the catalyst was tested using catalysts five subsequent degradation experiments. After the 5th cycle the catalyst exhibited 90% of its initial activity. The used catalyst morphology was investigated by using SEM image. Figure 7 shows the SEM image of PMM-CNT at magnification of 100000X. It is clearly seen from the image that the catalyst remains its initial morphology.

In this study, composite modified magnetite nanoparticles were synthesized by hydrothermal method. Prussian blue modified magnetite nanoparticles were decorated on multi-walled carbon nanotubes and used for the degradation of a well-known pollutant, phenol molecule. The structural and morphological characterizations of the synthesized nanocomposite were made, and its photocatalytic activity was tested on the decomposition reaction of phenol using the Photo-Fenton reaction. Photo-Fenton parameters were optimized by using a phenol standard and phenol quantification was performed by using a UV-Vis spectrophotometer. 100 mg dm^-3 phenol was completely decomposed in 15 minutes under UV light. The catalyst retains 90% of its activity up to 5 times of use (data not shown). Under the optimized conditions, the experimental studies resulted a successful phenol removal process by Photo-Fenton reaction.

Acknowledgements. This work was produced from a master thesis of Yusuf GÖGEN.

Conflict of interest There are no conflicts to declare.

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Prussian Blue Modified Magnetite Decorated MW-CNT Nanocomposite: Synthesis, Characterization and Potential Use as Photo-Fenton Catalysts for Phenol Degradation

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Abstract

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Introduction

Experimental