Fenton-like nanocatalyst for photodegradation of methylene blue under visible light activated by hybrid green [email protected]@MnFe2O4

Accepted Manuscript Title: Fenton-like Nanocatalyst for Photodegradation of Methylene Blue under Visible Light Activated by Hybrid Green DNSA@Chitosan@MnFe2 O4 Authors: Kamel Shoueir, Hamdy El-sheshtawy, Mohammed Misbah, Hamza El-hosainy, Ibrahim El-mehasseb, Maged El-kemary PII: DOI: Reference:

S0144-8617(18)30630-1 https://doi.org/10.1016/j.carbpol.2018.05.076 CARP 13658

To appear in: Received date: Revised date: Accepted date:

8-3-2018 27-4-2018 25-5-2018

Please cite this article as: Shoueir, Kamel., El-sheshtawy, Hamdy., Misbah, Mohammed., El-hosainy, Hamza., El-mehasseb, Ibrahim., & El-kemary, Maged., Fenton-like Nanocatalyst for Photodegradation of Methylene Blue under Visible Light Activated by Hybrid Green DNSA@[email protected] Polymers (2018), https://doi.org/10.1016/j.carbpol.2018.05.076 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Fenton-like Nanocatalyst for Photodegradation of Methylene Blue under Visible Light Activated by Hybrid Green DNSA@Chitosan@MnFe2O4

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Kamel Shoueir1*, Hamdy El-sheshtawy2, Mohammed Misbah3, Hamza El-hosainy4, Ibrahim El-mehasseb2, Maged El-kemary1,2

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Institute of Nanoscience & Nanotechnology, Kafrelsheikh University, 33516 Kafrelsheikh, Egypt. Faculty of Science, Kafrelsheikh University, 33516 Kafrelsheikh, Egypt.

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AUTHOR INFORMATION

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Corresponding Author

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*E-mail: [email protected]

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Graphical abstract

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Highlights

 DNSA modified CS for the first time and acting as bridge between MB dye and MnFe2O4

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 Excellent thermal stability achieved upon coating with MnFe2O4  Hybrid DNSA@CS@MnFe2O4 exhibited adsorption and potent photodegradation towards MB under visible light with the aid of H2O2

 Hot filtration test proved the heterogeneity of reaction and good recyclability was

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attained with DNSA@CS@ MnFe2O4

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Abstract

High efficient 3,5-Dinitrosalicylic acid/ Chitosan/MnFe2O4 (DNSA@CS@MnFe2O4) nano photocatalyst

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was prepared to enrich both adsorption and photodecomposition under visible light. This paper focused

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on the importance of DNSA@CS as an excellent connector between methylene blue (MB) and MnFe2O4 for accelerating photodegradation with the encouragement of photo-Fenton catalytic reagent hydrogen

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peroxide (H2O2). The optimum conditions were: contact time, 30 min, H2O2 concentration, 0.16 M, pH factor 9 and dosage 0.06 g/l at R.T, allowing excellent catalytic achievements 98.9% degree of

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decolorization in 30 min. More interestingly, the hybrid DNSA@CS@MnFe2O4 mechanism explained on the basis of coexistence of Mn2+/Mn3+ and Fe3+/Fe2+ redox couples during the reaction. The photocatalytic decolorization experimentally affirmed the suitability of DNSA@CS@MnFe2O4 obeying

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Langmuir-Hinshelwood model. Also, the nano-catalytic system was stable even after five runs. The prepared nanostructured catalyst provides simple fabrication to promote deep understand criteria for the mechanistic role of MnFe2O4 catalyst for degradation of MB molecules.

Keywords: MnFe2O4, Chitosan, Photo-Fenton, Adsorption, Photodegradation 2

1. Introduction Water polluted with dyes is a catastrophic effect on the surrounded environment. At this moment, the textile finishing and dyeing industries contribute more than 20% of the total water pollution (Konstantinou & Albanis, 2004). These dyes as example derived from petroleum intermediate and coal tar products with annually production 7 ×105 metric tons in the industry and about 280L of natural water

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is being consumed for dying every kg of cloth (Alharbi & El-Sheshtawy, 2017; Bensalah, Alfaro, & Martínez-Huitle, 2009; Shoueir, Sarhan, Atta, & Akl, 2016) High COD, high intensity of color, stability to oxidizing agents and inhibition of photosynthesis reactivity is apart from the hazard effect of organic dyes. Moreover, many dyes are prepared from carcinogens such as aromatic compounds and benzidine (Baughman & Perenich, 1988; Kant, 2012; Prado, Bolzon, Pedroso, Moura, & Costa, 2008).

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Currently, treatment of such obvious and challenging effluents by different technologies is necessary to minimize their potential impacts on the environment, including physical, chemical, and even

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biological adsorption processes are not sufficient (Alnuaimi, Rauf, & Ashraf, 2007; Bensalah et al., 2009;

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Houas, Bakir, Ksibi, & Elaloui, 1999; Lin & Peng, 1996; Shoueir et al., 2016; Singh & Arora, 2011).

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Nowadays, advance oxidation processes (AOPs) are becoming more and more important technologies for water treatment, especially for hardly biodegradable contaminants (Jiao et al., 2018). Among the AOPs,

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the classical Fenton-like catalyst is widely used, due to the two main catalysts H2O2 and Fe2+/Fe3+ enhance the organic degradation potency. Nevertheless, Fenton homogeneous catalysis has some

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drawbacks. For example, efficient Fenton-system at low pH (2-3.7), so strong acids required to adjust the pH of the wanted wastewater containing high levels of iron to reach (Chen et al., 2011). Therefore, these

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disadvantages limit its widespread application. As common, the heterogeneous approach is green and highly efficient. Several and different catalysts such as palladium nanocatalyst blended with natural bio-

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polymers as chitosan and cellulose composite was fabricated by different routes (N. Y. Baran, Baran, & Menteş, 2018; T. Baran & Menteş, 2016; T. Baran, Sargin, Kaya, & Menteş, 2016). In general, heterogeneous photocatalysis implying great potential such as simplest, dirt-cheap, green and free

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renewable treatment process. Consequently, oxidize mineralization of the water contaminants matrix into popular CO2, H2O and mineral acids by initiation of the highly oxidizing hydroxyl radicals (•OH) groups (Herrera, Kiwi, Lopez, & Nadtochenko, 1999). Within the exploration of efficient visible-light-driven photocatalysts, convenient magnetic cubic spinel nano ferrites MnFe2O4 is the most proper one. Good biocompatibility, high adsorption rate, and 3

excellent optical property rather than CuFe2O4, NiFe2O4 and CoFe2O4 nanomaterials as reported (Goyal, Bansal, & Singhal, 2014; Yao et al., 2014). MnFe2O4 based hybrids are a vital solution towards the visible light, good responsive nano photocatalyst for detoxification of textile dyes with a narrow band gap of (2.0 ± 0.5eV) (Li, Hou, Zhao, & Wang, 2011). Moreover, the coated MnFe2O4 nanomaterials were used to decompose Red X-3B, MB, Congo red under microwave-assisted synthesis from different

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dye systems. The particular aggregation of the MnFe2O4 declines their catalytic rate (Fang, Xiao, Yang, He, & Sun, 2015; Yang et al., 2014). As a result, it is important to develop heterogeneous Fenton system involving bimetal oxide catalyst to avoid precipitation of Fe3+ ions and to expand the acceptable pH range and controlling the size particles for enhanced catalytic efficiency.

Chitosan (CS), is a pioneer amongst polysaccharides, composed of N-acetyl glucosamine, has fully advantages, like nontoxic, high chemical stability, biodegradable and the presence of bearing amino

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and hydroxyl groups as active sites (Gmurek, Foszpańczyk, Olak-Kucharczyk, Gryglik, & Ledakowicz,

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2017). However, individual CS cannot be widely applied due to lack of mechanical, heat stability and

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solubility under acidic condition (pH 4±0.5). So, enhancing functionality required an appropriate

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chemical modification to enhance and enforce functionality. To our knowledge, there is no previous work on the modification of CS by 3,5-dinitrosalcylic acid (DNSA). Therefore, the combination of DNSA@CS hopeful in size reduction to prolong its stability, achieve good stabilization of the

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photocatalyst with the assistant of H2O2 and prevent its agglomeration through squadron the

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photocatalyst in the polymer matrix to obtain bifunctional material, i.e., adsorbent and photocatalyst (Cui, An, Liu, Hu, & Liang, 2014). This returned to the ability of DNSA to provide best chemical

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synthons for construction of chemical bonded structural motifs (Cui et al., 2014). Zhaoyang Liu et al. synthesized chitosan/TiO2/Fe3O4; microspheres and possess highly adsorptive, self-regenerative and

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reusable properties (Z. Liu, Bai, & Sun, 2011). Ling Xiao et al. Fabricated Cu2O/chitosan-Fe3O4 had efficient photo-decolorization of brilliant red X-3B under visible-light source (Farzana & Meenakshi, 2015). Sankaran Meenakshi et al. reported ZnO impregnated chitosan beads for photocatalytic removal

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of Methylene blue (MB) and Rhodamine B dyes using visible light irradiations (Cao, Xiao, Chen, & Cao, 2015). However, un controlled size and magnetic features of MnFe2O4 make recovery and reusability of photocatalyst difficult during the course of water remediation (Priya et al., 2016). Herein, our group developed a novel approach to introducing powerful microwave synthesis of green DNSA@CS@MnFe2O4 hybrid nanocatalyst for photodegradation/adsorption activity against MB 4

molecule under visible light source in the presence of H2O2. Different factors were studied to attain the optimal conditions and the influence of stability and reusability. Besides, DNSA@CS, MnFe2O4, and DNSA@CS@MnFe2O4 have carried out a comparative study on dye detoxification at similar experimental conditions. The magnified DNSA@CS@MnFe2O4 separated smoothly by an external

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magnet and reused many times. Experimental

2.1. Materials

Chitosan (CS) powder low molecular wt. 50,000-190,000 Da and 3,5- dinitrosalicylic acid (DNSA), Manganese (II) sulfate monohydrate (MnSO4. H2O, 99%), and Iron (III) chloride hexahydrate

(FeCl3.6H2O, 98%) were provided from Aldrich Chemicals, USA. Methylene blue (MB) (cationic dye,

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Mw = 319.85 g/mol) was prepared by dissolving definite weight in double distilled water (DDI). Other

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common reagents like glacial acetic acid, dimethylformamide (DMF), formaldehyde, sodium hydroxide,

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were used as an analytical chemical grade.

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2.2. Synthesis of 3,5-dinitro salicylic acid-modified chitosan (DNSA@CS) A collective mixture including 7 ml CS solution and 1.23 g DNSA stirred for 25 min, followed by adding 10 mL of DMF and 8.11 ml formaldehyde. The reactants mixture allowed to heat at 90 oC for 20

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min into a Teflon-lined STRT SYNTH microwave oven (WX-4000). The aggregated pure yellow

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powder was soaked with a mixture of hot water and ethanol to get rid of odor and unreacted chemicals and the fine powder of DNSA@CS dried under vacuum at 65 oC for 12 h.

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2.3. Preparation of DNSA@CS@MnFe2O4 A stoichiometric material of hydrated MnSO4.H2O and FeCl3.6H2O were dissolved in 40 ml DDI to

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obtain a lucent solution, then 1M NaOH in 10 ml solution was dropped into the mixture to obtain coprecipitates as a precursor. Subsequently, the formed dark brown suspension added to 0.20 g of as-

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prepared DNSA@CS, then transferred again to a microwave oven for 50 min at 110 oC until rarely black coarse powder obtained. After completion, the net product was filtered, rinsed with mixed pure water and alcohol mixture to remove any residues. The precipitate was dried at 60oC overnight. Following the above-mentioned procedures, Individual MnFe2O4 was prepared to compare between with DNSA@CS and DNSA@CS@MnFe2O4. Simple schematic representation is shown in scheme 1a.

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1. (a) Postulated synthesis of hybrid DNSA@CS@MnFe2O4 nanocatalyst, (b)

Measurements

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3.

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ed activation mechanism of MB degradation onto DNSA@CS@MnFe2O4.

To detect the nanostructure of the synthesized materials HR-TEM, JEOL from Japan was used and

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operating at 200 keV. SEM, Sirion from FEI was used to recognize the surface morphology. SEM equipped with the pendent EDX detector (S-3400 N II, Hitachi, Japan). The samples covered with carbon tier to remove their further undesirable charging. DLS technique (Malvern Instruments Ltd, UK) used to measure the hydrodynamic sizes of the new DNSA@CS. To identify the chemical structures iS5-FTIR spectra (Model no. AUP1200343) spectrophotometer was used and adjusted in the range of 4000-500 cm-1 with a resolution of 1cm-1. TGA analysis (SDT Q600 V20.5 Build 15) instrument at 20 kV, was 6

used to study the thermal stability. The phase structure studied using XRD patterns, which recorded on Philips X Pert diffractometer in the 2θ range of 0-80° with a scan rate of 2° min-1. The specific surface area of the samples was determined by N2 sorption at 77 K using Brunauer–Emmett–Teller (BET) surface analyzer ((11-2370) Gemini, Micrometrics, USA) at 77.30°C. Before operation running, the samples were degassed at 110°C for 3h under P/Po = 0.99402 to remove any surface contaminants.

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Atomic force microscopy (AFM) WITec, Japan was used for surface roughness morphology. Vibrating Sample Magnetometer (VSM) (155 PAR) was used to measure the magnetic properties, the applied field dependence of magnetization takes the range of -20,000 Oe to 20,000 Oe at R.T. The remaining amount of manganese and iron in filtrate was detected by Inductive coupled plasma atomic emission spectrometry (ICP-AES) (Optima 5300DV, Perkin Elmer Type). UV-Vis double beam

spectrophotometer (Shimadzu UV-1208 model) was used to record absorbance of synthesized

Photocatalytic degradation and adsorption experiments.

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4.

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DNSA@CS, MnFe2O4 and hybrid DNSA@CS@MnFe2O4 and their photocatalytic efficiency.

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4.1. Light source.

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The photocatalyst solution illuminated by Heber Visible (Annular Type) Photo reactor equipped with 500 W tungsten halogen lamp (1050 lm). The illumination light source carefully localized on the solution during treatment to prevent light dispersion. Moreover, the intensity of light measured regularly

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by lux meter, to ensure the best scattering of light onto the photocatalyst. An aliquot of the prepared

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samples at known irradiation time interval was taken out and analyzed at a λmax= 664 nm for cationic M.B dye.

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4.2. Photodegradation Experiments.

Typically, 40 mg of the synthesized preliminary photocatalyst added to 10 ml of basic M.B dye

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solution (10 mg. l-1) irradiated under the effect of visible light at R.T. Then, adding 0.08 M of H2O2. 3 ml was taken off after intervals of time irradiation to extend the degree of decolorization (%). Removing of all the catalyst by external magnetic separation carefully after centrifugation is required. Before

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irradiation, the mixture stirring in the dark state in batch technique for at least 150 min to ensure adsorption saturation. After saturation, about 3 ml of the suspension collected, separated and the absorbance of the supernatant detected spectrophotometrically. In a batch degradation experiments, the extent of dyes removal in terms of percentage degradation calculated as follow:

𝐷𝑒𝑔𝑟𝑎𝑑𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 (%) = (

𝐶0 −𝐶𝑡 𝐶0

) × 100

(1) 7

Where, Co is the initial dye concentration (mg. l-1) and Ct is the dye concentration (mg. l-1) after time t (min). 3. Results and discussion 3.1.

Physicochemical evaluation of the nanoparticles

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3.1.1. Photocatalyst morphological studies The morphology of the prepared nanoparticles was characterized by using TEM and SEM as shown in Fig. 1 (a-f). The TEM image of MnFe2O4 clearly shows that the attached assembly particulates have some cubic uniform structure (yellow circles) having a mean diameter of 200 nm as presented in Fig 1a. Furthermore, relative SEM analysis shows surface heterogeneity with large pits, pores, and scree like structure Fig. 1b. Fig 1c, shows that the DNSA modified CS particles are smaller with a diameter of

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about 50 nm into a rope-like configuration, which agrees with particle size distribution analyzed from

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DLS. Similarly, the precursor DNSA@CS show extremely good monodisperse in the form of spherical structure shape as shown in Fig 1d. Upon formation of DNSA@CS@MnFe2O4, the morphology is

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completely different as presented in Fig1e. As expected, MnFe2O4 dispersed, aggregated and stacked

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with DNSA@CS as a soft coral shape which affirms the closeness of MnFe2O4 over DNSA@CS (Fig 1f). (Farzana & Meenakshi, 2013). In addition, the existence of many pleats on the surface of

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DNSA@CS@MnFe2O4, which viable for adsorption and discolor dye molecules and this may be due to

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successfully surface modification process. Moreover, the CS chains as a biopolymer are capable of bridge between two particles (Barbosa-Barros, García-Jimeno, & Estelrich, 2014; Fan et al., 2017). Fig 1g shows the EDX spectra of the DNSA@CS@MnFe2O4 affirming existence of FeK and MnK in the

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elemental combination of hybrid which agree with the diagram obtained from XRD patterns.

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The FT-IR spectrum of CS, DNSA@CS, DNSA@CS@MnFe2O4 hybrid and MnFe2O4 are shown in the Fig. 2a. For bare chitosan (Fig 2a), the absorbance of β-1-4 glycosidic linkage tunnel in the dominant peak at 1089 cm−1. The spectra at 1323 cm−1 assigned to carbon-nitrogen bond amino groups axial deformation (T. Baran, Menteş, & Arslan, 2015). Bands at 2928, 1640 and 1590 cm−1 belongs to the –CH backbone stretching vibration mode, amide I band (carbonyl ν (C=O)) and amide II (amine ν (NH2)

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tensions) (Azarudeen, Riswan Ahamed, Thirumarimurugan, Prabu, & Jeyakumar, 2016; M Hamed

Misbah, Espanol, Quintanilla, Ginebra, & Rodríguez-Cabello, 2016; Mohamed Hamed Misbah et al., 2017). While, in case of DNSA@CS (Fig. 2b), an explicit characteristic peak appeared such as a feeble peak at 3090 cm−1 merged with the former band assigned to the stretching modes of -CH in the aromatic ring structure (Sebastian et al., 2015). The presence of a manifested band at 1559 cm−1, which attributed to stretching mode of –NO2 group in the position 3 and 5 in DNSA structure (Ahamed, Jeyakumar, &

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Burkanudeen, 2013), indicating the modification of CS by DNSA. The small intensity peak at 1644 cm-1

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overlapping the amide band in CS structure, due to deformation vibration of –NH group proven a facile combination of DNSA and bare CS. Besides, the deformation of both the asymmetric –CH2 band at 1499

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cm−1 and symmetric –CH2 at 1347 cm-1 becomes dominant, revealing the true enhancement of -CH bond

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(Riswan Ahamed, Azarudeen, Prabu, & Burkanudeen, 2015). The characteristic intense peak of MnFe2O4 located at 567 cm-1 due to the metal element - oxygen stretching vibration and still in the DNSA@CS

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with small shift and intense peak to be 559 cm-1 indicating the presence of strong electrostatic attraction

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force (Kafshgari, Ghorbani, & Azizi, 2017). The intrinsic vibration of octahedral and tetrahedral coordination M+2 and Fe+3 ions in the spinal responsible for that shift (Wang et al., 2015). Therefore, it

fabricated.

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can be concluded that the modification of CS by DNSA in the presence of MnFe2O4 successfully

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TGA thermograms of the synthesized nanomaterials were assessed using TGA as in Fig 2b and Fig S1 TGA profile. In CS, the essential thermal degradation process at 213.99 oC due to both dehydration and depolymerization of the organic fragments in the saccharide and aromatic ring for DNSA@CS (Ma

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et al., 2017). In case of DNSA@CS, main decomposition temperature takes place before 200 oC (199.69 o

C), lower than that of the degradation stage of original CS, revealing that DNSA@CS less thermally

stable than CS. This decrease may be accounted for by the substitution of some free -NH2 groups with DNSA ring structure which destruction of backbone and lowering the crystallinity of CS (T. Baran & Menteş, 2016). For MnFe2O4 and DNSA@CS@MnFe2O4, it is clear that the weight loss over the temperature range from 50 oC - 850 oC not exceed ~ 3.22% and 33.51% respectively, which may be 10

believed to the formation of corresponding spinal phase (Shafiu, Topkaya, Baykal, & Toprak, 2013). Moreover, the thermal stability of DNSA@CS highly enhanced owing to the greater interaction between DNSA@CS and MnFe2O4, which restricts the thermal motion of DNSA@CS chain in the composite. XRD patterns of pure CS, DNSA@CS, MnFe2O4, and DNSA@CS@MnF2O4 hybrid are shown in

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Fig. 2c. The data shows that the addition of DNSA to CS does not change the spinal structure of the CS and the characteristic diffraction peaks appeared at 2θ = 9.8o,19.7o, 37.47o, 44.0o, 64.34o, and 77.54o remains constant. On the other hand, the addition of DNSA to CS broadened the crystalline peaks of CS at 19.7o due to insertion of DNSA, consequently, the peak intensity reduced and this returned to the steric hindrance effect (Abdelwahab & Helaly, 2017). Similarly, MnFe2O4 has well-crystallized peaks at 2θ = 29.66 o, 34.88 o. 42.70 o, 56.44 o, and 61.92 o. However, we have found that adding DNSA@CS to the pure

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MnFe2O4 not change observed in the phase crystallinity of MnFe2O4, signifying that the dominance of the MnFe2O4 as a coating material and the synthesis did not destroy the features of organic DNSA@CS

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(Farzana & Meenakshi, 2015).

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Fig. 2d. Shows the magnetization hysteresis loops at 25 oC obtained by VSM technique and the

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obtained values of saturation magnetization (Ms), retentivity (Mr) and coercivity (Hci) are given in Table 1. Both MnFe2O4 and DNSA@CS@MnF2O4 nanoparticles exhibit a superparamagnetic behavior.

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The Ms value of magnified MnFe2O4 was reduced from 85.98 to 29.95 emu/g upon adding CS@DNSA, which ascribed to the basic diamagnetic features of organic materials such as CS and DNSA surrounding

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MnFe2O4, (Stoia, Muntean, Păcurariu, & Mihali, 2017). The neglected Ms and Mr for macromolecule DNSA@CS attributed to non-magnetic islands separating the magnetic domains, thereby decrease the

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values of Mc and Mr MnFe2O4 value (Almasian, Chizarifard, & Najafi, 2017; Topkaya, Kurtan, Baykal, & Toprak, 2013). Also, it can be seen the coercive force (Hci) which measure magnetocrystalline

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anisotropy getting more intense with MnFe2O4, due to the crystal size becomes smaller, which enlarge the area of the surface-to-volume ratio (Rivas et al., 2013). Similar results have been reported in the

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literature for the MnFe2O4 coated polyvinylpyrrolidone (Kazan et al., 2016; Shafiu et al., 2013).

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Fig. 2. (a) FT-IR spectra of CS, DNSA@CS, DNSA@CS@MnFe2O4, and MnFe2O4 from up to down; (b) TGA profiles in argon atmosphere; (c) XRD patterns of bare CS, DNSA@CS, MnFe2O4 and DNSA@CS, MnFe2O4; and (d) Magnetic hysteresis (M-H) loops for the same materials.

Magnetic Properties

Surface Characteristics Total pore

Surface

Pore

Pore radius

Average pore

Ms

Mr

Hci

volume

area

volume

Dv(r)

radius

(emu/g)

(emu/g)

(g)

(cc/g)

(m2/g)

(cc/g)

1.045

0.006

98.36

3.18

153.04

0.33

18.45 A0

MnFe2O4

85.98

2.92

122.28

2.35

69.42

0.74

9.27 A0

DNSA@CS@

29.95

8.59

484.02

4.95

219.36

2.43

11.45 0

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Sample coded

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DNSA@CS

MnFe2O4 Table 1. VSM measurements and surface characteristics of DNSA@CS; MnFe2O4; and hybrid DNSA@CS@ MnFe2O4 nanocatalyst.

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2.4 nm 6.4 nm 1.56 nm

Table 1, shows the surface characteristics of materials. The data measured by BET observed that significant differences between the surface areas. In DNSA@CS@MnF2O4 hybrid formulation maximum porosity and surface area were detected due to wrapping MnFe2O4 into chemically modified CS scaffold. The BET increased from 153.04 to 219.36 m2/g due to electronic property, chemical stability can serve as an ideal coating matrix for growing nanoparticles and offer sufficient reactive sites. The increased pore

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volume determined from the desorption isotherm were 0.33, 0.74 and 2.43 cc/g for DNSA@CS,

MnFe2O4, and DNSA@CS@MnF2O4, respectively. This returned to the closeness stack between MnFe2O4 and DNSA@CS particles (S.-T. Liu, Zhang, Yan, Ye, & Chen, 2014).

Fig. 3, shows the 3DAFM topography of the prepared materials. The average surface roughness calculated from the roughness profile of the 3DAFM images of DNSA@CS, MnFe2O4, and

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DNSA@CS@MnF2O4 are 52.29, 41.67, and 63.45 nm, respectively. These values are consistent with size measured from TEM images indicating that the DNSA@CS surface had become rough after coating

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with a hard layer from MnFe2O4. This behavior returned to clear deposition of a MnFe2O4 forming layer

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on the surface of DNSA@CS. Moreover, the increment in surface roughness is responsible for attaining

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adsorption saturation as stated in the literature (Kumar et al., 2014).

Fig. 3. The 3DAFM topography module of (a) DNSA@CS; (b) MnFe2O4; and hybrid DNSA@CS@MnFe2O4 nanocatalyst.

3.2. Adsorption capacity evaluation Fig. S2 shows the UV–vis spectra of M.B dye suspension in contact with DNSA@CS, MnFe2O4, and DNSA@CS@MnF2O4 nanocatalyst in the dark. Generally, cationic M.B has strong absorption band 13

centered at 664 nm and another little absorption shoulder band nearly at about 615 nm. With increasing contact time, all the peak intensity is shifted downward or all nanocatalyst, especially for a hybrid DNSA@CS@MnF2O4 the change is most remarkable (60 min). The enhancement is attributed to the big differences in total surface properties as well as the presence of nitro, amino, hydroxyl and MnFe2O4 which acted as important active sites (Gupta et al., 2017). The adsorption capacities (qe) of the prepared

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nanocatalyst were determined by the following formula: (𝐶0 −𝐶𝑒 )𝑉𝑙

𝑞𝑒 (𝑚𝑔/𝑔) =

(2)

𝑀𝑔

Where qe is the quantity of M.B adsorbed, C0 and Ce are initial and saturation concentration (mg/l), respectively, (V) is the volume of M.B solution and (M) is the mass of DNSA@CS, MnFe2O4, and

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DNSA@CS@MnFe2O4 nanocatalyst. Pseudo-first-order and pseudo-second-order kinetic models are of the most important parameters to evaluate the interaction between the M.B molecule and nanocatalyst

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surfaces. Lagergren-first-order model, pseudo-second-order model, and intra-particle mass transfer

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diffusion model were applied to investigate the kinetics of adsorption. The empirical formula of these

log(𝑞𝑒 − 𝑞𝑡 ) = 𝑙𝑜𝑔𝑞𝑒 − 1 𝑘2 𝑞𝑒2

+

2.303

𝑡

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𝑞𝑡

=

𝑘1

𝑞𝑡

(5)

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𝑞𝑡 = 𝑘𝑝 𝑡 0.5 + 𝐶

(3) (4)

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𝑡

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models represented as follow (M. A. El-Kemary et al., 2017).

Where qe and qt (mg/g) are the amounts of M.B adsorbed onto nanocatalyst at equilibrium and at time t, respectively; k1 is a constant rate of the pseudo-first-order (min−1) of the adsorption process and k2 is

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the pseudo-second-order rate constant (g·mg-1·min-1) of adsorption. The k2 and correlation coefficient R2 was evaluated by plotting the t/qt versus t.

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As shown in Fig. S3 and Table 2, only DNSA@CS obeyed pseudo-second-order rate owing to higher

R2 which closer to unity (0.91) and the qcal significantly agree with the qexp value. Therefore, the adsorption rate of DNSA@CS toward MB was probably controlled by the chemical adsorption process by sharing or electrons change between the two adsorbent /adsorbate surfaces (Fan et al., 2017; Kafshgari et al., 2017; Shoueir et al., 2016; Zhao, Tao, Xiao, & Su, 2017). In case of MnFe2O4 and DNSA@CS@MnFe2O4, the qe for MnFe2O4 was 46.1 mg/g is relatively close to the experimental qe 48.1 14

mg/g with a high R2 0.95 rather than second order and qe for the corresponding DNSA@CS@MnFe2O4 was 112.6mg/g while the experimental qe was 97.6 mg/g with R2 0.96, confirming that the adsorption of MB onto the magnified adsorbents only are better represented by Lagergren- pseudo- first-order kinetics.

Pseudo-second-order

Sample coded

K1 (min-1)

R12

DNSA@CS

4.6×10 -3

0.79

14.2

2.04×10-3

MnFe2O4

1.7×10 -3

0.95

48.1

0.18×10-3

DNSA@CS @ MnFe2O4

0.02×10 -3 0.96

112.6

0.02×10-3

K2 (gmg−1min−1)

R22

q cal.

0.91

q exp.

30.3

0.88 0.95

29.15

47.3

46.3

163.8

97.6

L-H Kinetics

C

R2

5.7

0.10 0.07

Kid

0.61

Rate constant (min-1)

R2

0.94

0.012

0.919

2.9

0.95

0.057

0.975

0.6

0.99

0.093

0.982

N

U

q cal (mg/g)

Intra-particle diffusion

SC RI PT

Pseudo-first-order

Table 2. Kinetic parameters for MB adsorption on dark and parameters of L-H model under visible light

A

The rate constants of intraparticle diffusion, kid and C mainly determine the rate-determining step in

M

the adsorption process. If the value of C is quite zero the adsorption process takes place by surface adsorption and the intraparticle diffusion. The value of C ultimately higher than zero so the intraparticle

D

diffusion was not the rate-determining step for DNSA@CS during adsorption of MB and bulk mass transfer is the predominant one. On contrary, values of C for MnFe2O4 is 2.9 (mg. g-1) and DNSA@CS@

TE

MnFe2O4 is very low 0.6 (mg. g-1) indicates that the adsorption process governed by intraparticle diffusion (Habiba, Islam, Siddique, Afifi, & Ang, 2016). Fig. 4, shows the degree of decolorization (%)

EP

of MB against time (min). The estimated decolorization (%) of MB removal for all nanocatalyst exhibited gradual decolorization rate 29.15% within 135min, 46.38% within 60min and 80.65% within

CC

enough 60 min respectively. Initially, the adsorption enhances the collision between MB and oxidizing species in the surface as time increased till maximum surface area clog up. In the last stages of

A

adsorption, a small diffusion control adsorption of MB into the internal pores. Consequently, the adsorption process became slower.

15

60

40

20 DNSA@CS@MnFe2O4 MnFe2O4

0

DNSA@CS 0

20

40

60

80

100

120

140

U

Time (min)

SC RI PT

Decolorization (%)

80

N

Fig.4. Decolorization (%) against time for DNSA@CS, MnFe2O4, and DNSA@CS@MnFe2O4 without visible light source.

A

3.3. Photocatalytic performance

The photocatalytic degradation of MB was investigated in the presence of hydroxyl radical (•OH)

M

active species using 0.08 M H2O2 scavenger in this experiment. From Fig. 5, it could be seen that the intensity of adsorption peaks diminished gradually as the degradation time increased and blue-shifted

D

MB undergoes complete degradation at 80, 40, and 30 min after light irradiation of DNSA@CS,

TE

MnFe2O4, and DNSA@CS@MnFe2O2 respectively. Indicating the potency of H2O2 on the photocatalytic degradation. These results revealed that the azo bonds and the aromatic rings of MB molecule were

EP

destroyed under visible light irradiation in the presence of the of the photocatalyst. Our trends are

A

CC

completely consistent with the results obtained by Zhu et al. (Zhu et al., 2014).

16

SC RI PT U N A M D TE

Fig. 5. UV–vis spectra of M.B dye suspension in contact with (a) DNSA@CS, (b) MnFe2O4, and (c)

EP

DNSA@CS@MnFe2O4 nanocatalyst under visible light irradiation.

The standard formula by Langmuir–Hinshelwood (L–H) model was analyzed to comprehend the

CC

photodegradation kinetics of the heterogeneously catalyzed reaction. The simplified formula of this model to the apparent pseudo-first-order expressed as follow: 𝐶

A

ln( ) = −𝑘𝑎𝑝𝑝 t

(6)

𝐶0

Where kapp is the apparent pseudo-first-order constant (min-1). Typical plots of ln(C/Co) against time are linear with slope equal to kapp. From Fig. 6 a, b and Table 2 it can be seen that the photocatalytic potency of DNSA@CS@MnFe2O4 with kapp value of 0.093 min-1 is higher than DNSA@CS and pure MnFe2O4 systems and all nanocatalyst obeyed Langmuir-Hinshelwood model. This data goes well with the obvious 17

crystalline phase of MnFe2O4 in XRD. The presence of DNSA@CS coated MnFe2O4 helped faster degradation. Also, larger surface area (219.36 m2/g) and little particle size generate surface active sites. As a result, the existence of (•OH) on the site increased which leads to a production more (•OH) radicals, the major oxidant necessary for improving the photocatalytic towards photodegradation.

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Based on the results in Fig.6c, the relation between photodegradation and contact time prove that the maximum degradation obtained with DNSA@CS@MnFe2O4 after 30 min reaches 94.44%. While 80 min (91.01%) and 40 min (73.9%) for DNSA@CS and MnFe2O4 respectively, is sufficient to attain saturation time and degradation. The results confirming that the nanocatalyst DNSA@CS@MnFe2O4 combination system, significantly accelerates the degradation of MB under visible light 0.9 3.5

(a)

0.8

-ln (C/Co)

0.3

M

0.4 MnFe2O4

0.2 0.1 10

20

50

40

30

60

70

100

DNSA@CS

1.0 0.5

0

10

20

30

40

50

60

Time (min)

DNSA@CS@MnFe2O4

(c)

EP

90

1.5

0.0

80

TE

Time (min)

D

DNSA@CS@MnFe2O4

0.0

80 70

CC

MnFe2O4

60 50 40

A

Photodegradation (%)

MnFe2O4

2.0

A

0.5

N

2.5

0.6 C/Co

U

3.0

DNSA@CS

0.7

(b)

DNSA@CS@MnFe2O4

DNSA@CS

30 20 10

0

10

20

30

40

50

60

70

80

90

Time (min)

Fig. 6. (a) Time course degradation curves, (b) Linear plot of the Langmuir–Hinshelwood model, and (c) photodegradation (%) vs time (min) under visible light irradiation.

18

70

80

90

3.4. Degradation of MB by DNSA@CS@MnFe2O4 hybrid nanocatalyst under different conditions 3.4.1. Influence of pH factor Owing to less sensitivity of DNSA@CS and pure MnFe2O4 towards photocatalytic degradation rather than hybrid DNSA@CS@MnFe2O4. So, this combined system only was used to illustrate the rest

SC RI PT

parameters. The controlled pH had a strong effect on DNSA@CS@MnFe2O4 nanocatalyst as decolorizer as in Fig. 7a. Generally, in acidic medium (pH 3.0), the degradation rate increased gradually up to 42.2% then the degradation efficiency level off. The hydroxyl, amino, nitro and carboxylic moieties of DNSA@CS carrier were protonated under acidic conditions as the following reaction stated: R-XH+ where X may be -OH, -NO2, -NH2, and -COOH

(7)

U

R-X + H+

Presence of MnFe2O4 as the coating material is presumably (+ve) charged in acidic media which unable

N

to provide more -OH groups to generate (•OH) radicals on the surface. Moreover, the nature of MB

A

cationic dye in acidic range doing electrostatic repulsion between MB and nanocatalyst. For these

M

reasons the degradation efficiency decreased. On contrary, at higher pH ( ̴ 9.0) the degradation ability reaches 98.35%. In alkaline solution, promote higher levels of -OH- groups to yield (•OH) radicals

D

attacked and destroy the target MB. Under pH> 9.5, the surface became (+ve) charged favoring the removal of MB molecule. But, the instability of H2O2 scavenger in alkaline solution led to the formation

TE

of ferric hydroxide complexes and reduce (•OH) radicals. Also, Mn2+ ion participate in the chain reaction, forming (HO2•/O2•-). Another considered reason, the reactivity of a high valence iron species

EP

Fe3+ less than (•OH) radicals and this might be formed in pure alkaline medium (He, Ji, Wang, & Zhang,

CC

2017; Luo et al., 2010). The following equations support the meaning: 2H2O2

2H2O + O2

(8)

Fe3+ + •OH + OH-

(9)

Mn2+ + •OH

Mn3+

(10)

Mn3+ + H2O2

MnO2+

(11)

MnO2+ + H+

Mn2+ + HO2•/O2•-

(12)

A

Fe3+ + H2O2

19

Fe3+ + HO2•/O2•-

Fe2+ + O2 + H+

(13)

3.4.2. Influence of H2O2 concentration Fig. 7b. Shows the effect of extra H2O2 concentration (0.02, 0.04, 0.08 and 0.16 M) on the photodegradation of MB. The photodegradation efficiency directly proportional to the concentration of

SC RI PT

H2O2. At low concentration of H2O2, the MB degradation decreased to the lowest rate 74.8% because of there is no sufficient amount of •OH radicals produced anymore. At H2O2 higher concentration (0.16 M) faster reaction proceed due to rapid generation of potent •OH radicals. 3.4.3. Influence of nanocatalyst dosage

Fig. 7c. represented the effect of nanocatalyst dosage (0.02, 0.04, 0.08 and 0.1g/l) on the degradation

U

of MB by DNSA@CS@MnFe2O4. When the nanocatalyst amount increased from 0.02 to 0.04g/l; the

N

decolorization increased from 93.4 to optimal 98.9%. This powerful efficiency mainly was because of the availability of more active sites, leads to the production of active radical species on the surface of nano

A

photocatalyst (Abdelwahab & Helaly, 2017; He et al., 2017; Rasoulifard, Dorraji, Amani-Ghadim, &

M

Keshavarz-Babaeinezhad, 2016). The efficiency decreased upon increasing the dosage exactly at 0.08 and 0.1g/l, this may be attributed to blocking and excessive scattering of incident light as catalyst amount

D

increased (M. El-Kemary, Abdel-Moneam, Madkour, & El-Mehasseb, 2011).

TE

3.4.4. Stability and reusability of DNSA@CS@MnFe2O4 Economically, the stability of any photocatalyst is a desirable trait for practical applications. The

EP

nanocatalyst was isolated using an external magnet, washed and dried before use at 80 oC to attain sapless. Thus, the stability experiment was conducted for five runs under using optimum conditions

CC

(contact time, 30 min, H2O2 concentration, 0.16 M, pH factor 9 and dosage 0.06 g/l) for 1hr. Fig. 7d shows the first two recycling runs were performed without any loss of catalytic ability. Beginning from

A

the third run till fifth run plateau, the degree of decolorization reduced to 91.7,84.3 and 83.1%, respectively. Ferrites exhibited paramagnetic character and easily recoverable from catalytic system even after five runs (He et al., 2017; Lou et al., 2017). This expects that DNSA@CS@MnFe2O4 able to eliminate various of pollutants disrupters in wastewater. On the other hand, the modified nanocatalyst was recovered and studied by EDX and SEM (Figure 7e), which shows that chemical structure, size, and morphology of the nanocatalyst remains unchanged, more indicating their excellent stability.

20

3.4.5. Hot filtration test In order to confirm that the reaction is heterogeneous, a hot filtration test was performed in the model reaction. The model reaction was carried out for 7 min in the presence of magnetic nanocatalyst. At this stage, the degradation of MB was 62.2%. The catalyst was then removed and the filtered reaction

SC RI PT

mixture was then stirred for another 2 h under the same condition. Fig 7f reveal that there is no corresponding increase of product yield was observed, suggesting that no homogeneous catalyst was involved. In addition, metal leaching in the catalyst was determined and ICP-AES analysis of the clear filtrate indicated that the Mn and Fe contents were 0.03 and 0.2 ppm, respectively. This very slight loss of Mn and Fe species in the filtrate is an outstanding data and indicates potent interact of the bimetallic element species with DNSA@CS and affirm the heterogeneous nature of DNSA@CS@MnFe2O4 during

U

photo treatment. However, no significant improvement in the degradation percentage of MB was observed after separation of catalyst from the reaction mixture. These results proved that the

N

DNSA@CS@MnFe2O4 hybrid nanocatalyst was stable under the reaction conditions and apparently

M

(a)

100

pH 3 pH 7 pH 9

0.8

20

5

10

15

20

C/C0

0.0

25

30

35

Time (min)

5

10

15

20

Time (min)

A

0

CC

0

0.4

0.2

EP

40

0.02 M 0.04 M 0.08 M 0.16 M

0.6

TE

60

(b)

1.0

D

80

Decolorization (%)

A

there was no leaching of the metal content from the magnetic nanostructure.

21

25

30

(c)

1.0

0.02 g/l 0.04 g/l 0.08 g/l 0.1 g/l

0.8

SC RI PT

0.4

0.2

0.0 5

10

15

20

25

30

EP

TE

D

M

A

N

U

Time (min)

CC

Fig. 7. (a) Effect of pH on DNSA@CS@MnFe2O4; (b) Normalized changes in MB photodegradation for the addition of extra H2O2 concentration as a function of time; (c) influence of various nanocatalyst dosage; (d) Effect of recyclability on photodegradation and relative decolorization degree (%); (e) EDX and SEM stability after subjected to irradiation; and (f) hot filtration test

A

C/C0

0.6

3.4.6. Exploration of the Catalytic Mechanism The mechanism of photocatalytic performance for the prepared DNSA@CS@MnFe2O4 nano

photocatalyst was presented in Scheme 1b. The remarkable synergistic enhancement of MnFe2O4 and the modified CS is the significant role in photoreactivity. DNAS@CS acting as a bridge between the MnFe2O4 coater and the respective MB molecule. From EDX data the intensity of Fe3+ larger than Mn2+ 22

so during photo treatment Fe3+ reduced to Fe2+ which accelerates the Fe3+/ Fe2+ cycle to produce primary catalytic •OH radical helping decomposition of MB molecules (Guo, Zhang, Guo, & Jimmy, 2013). The interaction between most stable oxidation state Mn2+ /MnFe2O4 surface and H2O2 also participate in the chain reaction to produce surface-shielded •OH radical which essential for a remarkable increase in

SC RI PT

the catalytic activity (Ai, Gao, Zhang, He, & Yin, 2013). As a result, the performance of MnFe2O4 is superior rather than individually MnO and Fe2O3 (Peng et al., 2016). Eqn. (14) and eqn. (15) and the same case with Fe2+ species on the nanocatalyst surface takes place eqn. (16) and eqn. (17): Mn3+ - OH- + •OH

Mn2+ - OH- + H2O2

(14)

Mn2+ - OH- + •OOH + H+

Mn3+- OH- + H2O2

Fe3+ - OH- + •OH + OHFe2+ - OH- + •OOH + H+

(17)

N

Fe3+ - OH- + H2O2

(16)

U

Fe2+ - OH- + H2O2

(15)

A

Besides, the synergetic effects of the reducing couples Mn2+/Mn3+ and Fe3+/Fe2+ cycles (eqn. (1-4), the reaction is thermodynamically favored, which cyclically benefits from redox cycles given significant

M

catalytic efficiency through repeated internal electron transfer (Divyapriya, Nambi, & Senthilnathan, 2016; He et al., 2017). Accordingly, the different functionality located hybrid DNSA@CS@MnFe2O4

D

adsorbed MB molecules and promote the electron transport during the catalytic reaction. Also, H2O2

TE

catalyzed to produce a large amount of •OH radicals due to MnFe2O4 anchored on the surface of DNSA@CS which facilitate the degradation of cationic MB structure into CO2, H2O, and minerals.

EP

Therefore, the coupling contribution of both DNSA@CS and MnFe2O4 nanocatalyst improves the decomposition of MB molecules.

1.

CC

3.4.7. The preparation advantages of DNSA@CS@MnFe2O4, rather than reported literature Microwave-assisted hydrothermal able to fabricate DNSA@CS@MnFe2O4 in a very short time at

A

relatively low temperature and pressure. Consequently, save both times consuming and energy which effects on adsorption/photodegradation performances rather than other reported materials during literature survey (Areerob, Cho, Jang, & Oh, 2018; Fan et al., 2017; Mahmoodi, 2015; Meng et al., 2015) 2.

Magnetic isolation is convenient for all sides, however, new DNSA@CS exhibited diamagnetic domain. While DNSA@CS@MnFe2O4 have powerful magnetization 29.95 Mg (emu/g) comparing 23

with reported magnified CS materials with further modification (Abdelwahab & Ghoneim, 2018; Gautam et al., 2017; Verma, Singh, Ram, Shah, & Kotnala, 2011) 3.

Coating MnFe2O4 with a biocomponent like DNSA@CS permits sequestration of MB molecules, improves biocompatibility and allow ease attachment of targeting moieties (Habiba et al., 2016;

SC RI PT

Xiao, Liang, Chen, & Wang, 2013). Thus, a DNSA@CS@MnFe2O4 promising adsorbent for adsorption and photodegradation in terms of its excellent achievement in magnetization and

adsorption decomposition capacity compared with various materials reported in the literature. Conclusions

In summary, a novel modified CS with DNSA are synthesized for the first time to enlarge the specific surface area and then coupled with MnFe2O4 to produce DNSA@CS@MnFe2O4 nanocatalyst. FTIR

U

prove that strong electrostatic attraction force between MnFe2O4 and DNSA@CS matrix. Anchoring of

N

MnFe2O4 enhances thermal stability to be not more than 4% due to spinal phase nature. The crystal phase of individual pure CS, DNSA@CS, MnFe2O4, and combined and DNSA@CS@MnF2O4 was confirmed

A

by XRD analysis and exhibited successful fabrication of the hybrid nanocomposite. For adsorption of

M

MB, the magnified DNSA@CS@MnF2O4 was better represented by Lagergren- pseudo- first-order kinetics. However, photodegradation kinetics of the heterogeneously catalyzed reaction showed that the

D

hybrid nanocomposite obeyed Lagergren-first-order model. In particular excellent catalytic achievements

TE

98.9% degree of decolorization was obtained under visible light irradiation and within 30 min in the support of H2O2 at R.T. Importantly, the degradation efficiency nearly stopped after removal of catalyst and no leaching detected of the catalytic system. This paper not only offers a green and new approach for

EP

the synthesis of novel modified CS by DNSA, but also participate understanding the redox mechanism of

CC

manganese ferrite by using heterogeneous photo-Fenton catalyst system. ASSOCIATED CONTENT Supplementary data (available in data in brief file)

A

Fig S1, Tangent curves of TGA profile Fig S2, UV–vis spectra of M.B dye suspension in contact with nanomaterials Fig S3, Kinetics of Lagergren first-order, pseudo- second-order and intraparticle diffusion models for nanomaterials towards adsorption of M.B

Notes: The authors declare no competing financial interest. 24

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