Bio-based magnetic metal-organic framework nanocomposite: Ultrasound-assisted synthesis and pollutant (heavy metal and dye) removal from aqueous media

Applied Surface Science 480 (2019) 288–299

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Bio-based magnetic metal-organic framework nanocomposite: Ultrasoundassisted synthesis and pollutant (heavy metal and dye) removal from aqueous media

T

Niyaz Mohammad Mahmoodia, , Mohsen Taghizadeha, Ali Taghizadeha, Jafar Abdia, ⁎ Bagher Hayatib, , Ali Akbar Shekarchic ⁎

a b c

Department of Environmental Research, Institute for Color Science and Technology, Tehran, Iran Department of Environmental Health, Khalkhal University of Medical Sciences, Khalkhal, Iran Department of Pathology and Anatomy, Ardabil University of Medical Sciences, Ardabil, Iran

ARTICLE INFO

ABSTRACT

Keywords: Magnetic metal-organic frameworks ZIF-67 Biocomposite Copper ion capture Dye adsorption

In the recent decade, Metal-Organic Frameworks (MOFs) and their most popular subclasses (zeolitic imidazolate frameworks (ZIFs)) are widely studied for removing contaminants from the effluent. Herein, the magnetic bionanocomposite (eggshell membrane-zeolitic imidazolate framework) was synthesized using a facile, efficient, and green ultrasound-assisted method. Zeolitic imidazolate frameworks-67 (ZIF-67) crystals were stabilized on the surface of magnetic eggshell membrane (Fe3O4@ESM) support to prepare the ZIF-67@ Fe3O4@ESM composite as a novel adsorbent with the high surface area (1263.9 m2/g). Several analyses such as XRD, FTIR, SEM/ EDS/Mapping, VSM, and BET were used to confirm the characterization and structural changes of ZIF-67 crystals before and after the composition process. Thereafter, copper cation (Cu2+) capture and dye (Basic Red 18: BR18) adsorption process were designed and thoroughly studied using the prepared adsorbents. It was found that the adsorption rate and removal percentage of the ZIF-67@Fe3O4@ESM composite are faster and higher than that of the pure ZIF-67 for both types of contaminants. Moreover, the magnetic feature of the composite adsorbent caused to a facile separation from liquid media. The results showed that the Langmuir adsorption isotherm well explained the obtained equilibrium data with a maximum adsorption capacity of 344.82 and 250.81 mg/g for Cu2+ and BR18, respectively. Kinetic studies showed that the pseudo-second order model was capable to fit the experimental data of the simultaneous removal of heavy metal ion and dye molecule.

1. Introduction Today's modern world, water pollution is an important serious environmental problem, so water and wastewater treatment became the most global genuine concern. Water as a significant material on the earth is directly related to the surviving of any living life [1–3]. Since industrial revolution at 18th century, considerable increase of industrial activities and appearance of various industries including leather, paper cosmetics, tanning, plastics, rubber, food processing, printing and dye manufacturing that purged their unwanted byproducts in rivers, lakes, and seas made water pollution as the severe global problem [4–6]. Thus, nowadays the water treatment became so important issue. Dyes, as the used organic materials in various industries, are one of the concerning pollutants in water resources [7–10]. These

⁎

contaminants before releasing in our ecosystem must be deleted from industrial wastewater [11,12]. Recently, many of them have forbidden in some countries because of causing allergic and other side effects. Animal models show the effects of environmental pollutants on several diseases such as breast cancer which is the prevalent cancer among women [13–16]. However, several useful and practical applications of some dyes in different ways were recorded such as anti-corrosion, food colorant, pH indicator, water-cooling for looks and medicine appliance, etc. [17,18]. So far, various physical, chemical, and biological methods have been applied for trapping and separation of dyes molecules from wastewaters supplies. Adsorption, photocatalysis, enzymatic oxidation, membrane filtration, electrochemical process, and chemical coagulation are the most common methods. Due to the economic feasibility, high efficiency, and facile operation process without remaining any

Corresponding authors. E-mail addresses: [email protected], [email protected] (N.M. Mahmoodi), [email protected] (B. Hayati).

https://doi.org/10.1016/j.apsusc.2019.02.211 Received 6 November 2018; Received in revised form 20 February 2019; Accepted 24 February 2019 Available online 26 February 2019 0169-4332/ © 2019 Elsevier B.V. All rights reserved.

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subproduct or byproduct, adsorption is considered as an attractive technology in most research items and involved in separation, purification, detoxification, and metabolism of medicinal drug process [19–25]. Construction of metal cations and structure-building organic “linker” units causes well-ordered 3D hybrid organic-inorganic polymers called metal-organic frameworks (MOFs) [26,27]. The diversity of structures and large surface area of MOFs made them great adsorbent and also lead to wide usage of them in many applications such as drug delivery, water purification, air treatment, and soil pollution removal [28–32]. Zeolitic imidazolate frameworks (ZIFs) as the most significant topologies for porous materials are sub-member of MOFs, which have various valuable characteristics including thermal stability, high porosity, and chemical hardness [29,33–38]. In order to get more efficiency in these materials, various composites of them on different supported beds have been investigated until now. Activated carbon (AC), carbon nanotubes (CNT), graphene oxide (GO), biomaterials and different types of natural and synthesized polymer beads, membranes and nanofibers were the most popular ZIFs supported materials that recent papers presented (Table 1) [39–53]. Lately, due to eco-friendly and commercial matters, use of bio-waste was notable in industrial and laboratory scales. The eggshell membrane (ESM) as a natural biopolymer that obtained from the inner side of the eggshell is a bio-waste material that could play an efficient role as a support bed. Table 2 showed that ESM was utilized for many applications such as sensors, battery, cell culture, capacitors, catalyst, and adsorption [54–67]. Nowadays, chemical processes and reactions were helped by a highenergy chemical approach called sonochemistry [68]. A few points of interest are associated with the sonochemical process including the utilization of green and eco-friendly solvents, the decline of energy usage for chemical transformations, and the introduction of the other or renewable feedstocks [68,69]. The novelty of the idea for this research, came from the usage of the eggshell membrane (ESM), a natural, eco-friendly, biocompatible, and cost-efficient polymer, for the first time as a nucleation agent to grow ever better and better of the MOFs crystals. Also, the applied sonochemical-assisted method was accelerated the formation process of ZIF67 crystals. The synthesis of materials in this work were aided by ultrasound waves, which were improved the local turbulence/liquid microcirculation and increased the mass transport rate. So, the required time for green (organic solvent-free) synthesis of ZIF-67 was well-

Table 2 A literature review about ESM application.

Solvent

Application

Year

Ref.

ZIF-67

DW MetOH MetOH – –

2015 2017 2015 2017 2016

[39] [40] [29] [41] [30]

2016 2008 2018 2018 2018

[42] [43] [44] [45] [46]

– –

– MG dye removal Cr(VI) adsorption Ethane/ethylene separation Propylene/propane separation Phenol CO2 capture Congo red removal Pb(II) and Cu(II) RB, MO, and MB dye removal Biodiesel production Methane/ethylene

2018 2016

[47] [48]

DW DW MetOH DW MetOH

Sulfur cells Benzotriazole removal CV and MG dye removal MG dye removal MO and MB dye removal

2018 2016 2018 2016 2018

[49] [50] [51] [52] [53]

ZIF-8/ZIF-67 ZIF-67/lipase ZIF-67/water-ethylene glycol Graphene/ZIF-67 Magnetic graphene/ZIF-67 RGO/ZIF-67 aerogel Magnetic rGO/ZIF-67 Fe2O3/ZIF-67

DW – – DMF DW

Application

Year

Ref.

ESM

DR80 and AB25 dye removal Heavy metal ions elimination Pb(II) and bovine serum albumin Arsenate and speciation of inorganic arsenic Cr(VI) adsorption MB dye removal Hg(II) adsorption Oxygen reduction reaction and supercapacitor Supercapacitors Cr(VI) removal Pb(II) and bovine serum albumin Serum triglyceride detection Biosensor (urinary oxalate) Biosensor Heavy metal ion removal Heavy metal and dye adsorption

2006 1994 2011

[54] [55] [56]

2013

[57]

2007 2012 2010 2017

[58] [59] [60] [61]

2012 2011 2011

[62] [63] [56]

2010 2008 2012 2013

[64] [65] [66] [67] This work

Thiol-functionalized ESM FeCo/biocarbon derived ESM Carbonized ESM Polyethyleneiminated ESM Carbonized ESM ESM/lipase Chemical-activated ESM/lipase ESM/urease Ammonium thioglycolate ESM ZIF-67@Fe3O4@ESM

improved from 6 h to 3 h in comparison to stirring method which was applied in original report [49]. The ESM for the first time was magnetized using a low-temperature and water-based co-precipitation method in order to boost the adsorption performance and make the separation process better and faster. Well-growth of ZIF-67 crystals on the surface of Fe3O4@ESM was fully analyzed using different techniques such as FTIR, XRD, SEM/EDS/Mapping, VSM, and BET analysis. In addition, heavy metal adsorption and dye removal studies were investigated using ZIF-67@Fe3O4@ESM as a magnetic composite. 2. Experimental 2.1. Materials and apparatus Basic Red 18 (BR18) was purchased from Ciba Company, Switzerland. The salts including Cu(NO3)2.3H2O, Co(NO3)2.6H2O, FeCl2, FeCl3, NaOH and 2-methylimidazole were purchased from Merck, Germany. The synthesis of materials was performed using an ultrasonic bath (Parsonic 15 s, Pars Nahand Engineering, Iran) operated at frequency of 30 kHz and power of 200 W. In order to have a better investigation of the surface functional groups of the synthesized materials, FTIR analysis was done by Perkin-Elmer spectrophotometer (Spectrum One) using potassium bromide (KBr) pellet method. Scanning electron microscopy (SEM) was used for observation of the morphological structure of the prepared materials and energy-dispersive X-ray spectroscopy (EDXS) was employed to elemental analysis and detection of the individual elements via X-rays emitted from the materials. SEM/EDXS analyses were done using LEO 1455VP electron microscope. XRD analysis was done using X'pert Pro MPD (115 PANalytical) to reorganize the crystal structure of materials. BrunauerEmmett-Teller (BET) surface area analysis was performed to determine the specific surface area and porosity of the synthesized materials by BELSORP-mini II through N2 adsorption/desorption at 77 K. The magnetic properties of samples were determined via a vibrating sample magnetometer analysis (VSM, Sharif University of Technology, Iran). The determination of the BR18 and Cu2+ concentration in the aqueous phase was performed by double beam UV–Vis spectrophotometer (Perkin Elmer, Lambda 25, USA) and atomic absorption spectrometer (AAS, Hitachi Z-2000, Japan), respectively.

Table 1 The published papers related to ZIF-67. Material

Material

289

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2.2. Schematic of synthetic route for materials

1000 mL of deionized water to reach the heavy metal ion stock solutions containing certain concentrations (10, 15, and 20 mg/L). The binary mixture of heavy metal ion and BR18 was provided by adding a certain amount of BR18 to the Cu2+ stock solution. The prepared adsorbents of Fe3O4@ESM, ZIF-67, and ZIF-67@Fe3O4@ESM were utilized to study dye adsorption behavior and heavy metal ion elimination from a single mode and binary mixture of Cu2+ and BR18 as an industrial wastewater model. The adsorption percentage and capacity were calculated by adding various amounts of adsorbents (0.004–0.008 g) into the different concentrations of pH-adjusted solution followed by agitation in room temperature to detect the optimum condition. At the end of the adsorption process, the solids were completely separated from aliquots taken in the regular interval using a magnetic field. Then, the remaining concentrations of BR18 dye and Cu2+ cation were determined using a UV–Vis spectrophotometer and AAS, respectively, based on calibration curves. The amount of adsorbed Cu2+ and BR18 and removal percentage at equilibrium point were estimated by the following equations:

The utilized ESM in this research was obtained similar to the previous published paper [54]. Briefly, the collected eggshells were submerged in a diluted acetic acid solution and after dissolving the mineral shell, the remained membrane (ESM) was rinsed with distilled water repeatedly, and dried at 313 K for 48 h. The well-dried ESM was milled and sieved to the particle size of ≤0.125 mm. An environmentally friendly low-temperature co-precipitation method was applied to the synthesis of Fe3O4 nanoparticles (Fe3O4 NPs). A certain ratio of Fe2+ and Fe3+ (1:2) was completely mixed with 5 g of ESM for 15 min. NaOH solution (3 M) was added to the mixture drop wisely until pH reached 11 and the green color of mixture turned to dark brown. After that, the mixture was kept stirring at 353 K. The whole process was carried out under N2 atmosphere. At last, the remained materials were separated using a magnetic field and the precipitated solids were washed three times with deionized water and dried at 353 K for 1 h. Synthesis of ZIF-67 on Fe3O4@ESM was performed based on the literature with sonochemical modification [49]. 0.75 g of cobalt nitrate hexahydrate was dissolved in 50 mL of double distilled water and sonicated for 1 h. Then, the final solution was mixed with 0.035 g of Fe3O4@ESM on a magnetic stirrer for 1 h more. Afterward, the concentrated 2-methylimidazole solution (8.5 g/30 mL) was added to the former solution drop wisely under sonication condition for 3 h. Finally, the synthesized ZIF-67@Fe3O4@ESM was separated from dark purple solution using an external magnet and before being dried at vacuum oven at 353 K for 12 h, rinsed several times by a mixture of methanol, ethanol, and distilled water. The schematic of synthetic route for materials was presented at Fig. 1.

q e = [(C i R% = [(Ci

Ce) × V]/m Ce) × 100]/Ci

(1) (2)

3. Results and discussion 3.1. Characterization of materials The FTIR spectra of the materials were obtained to confirm the composition and functional groups. As shown in Fig. 2, the FTIR spectrum of ESM shows the bands positions at 3433, 2970, 1638, 1087, 794, and 625 cm−1. The observed band at 3433 cm−1 is related to the eOH and eNH groups. The peaks at 2970, 1638, and 1087 cm−1 could be ascribed to stretching of eCH2 units, amide group and CeO bond in the eggshell membrane, respectively [70]. The specific absorption bands of Fe3O4 can be observed at 588, 889, and 1088 cm−1. The strong peak at 588 cm−1 is assigned to the vibration of the FeeO functional

2.3. Batch adsorption process The synthetic wastewater was prepared in our lab via the following way: the set of various amounts of Cu(NO3)2.3H2O was dissolved in

Fig. 1. Schematic of the green synthesis of materials. 290

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Fig. 2. FTIR spectra of the synthesized samples.

group which authenticates the magnetite property of the Fe3O4 nanoparticles [71]. Furthermore, two other peaks at 3400 and 1621 cm−1 are related to the vibrations of the hydroxyl group (OeH) bond due to the ambient moisture [72,73]. The absorption peaks emerged from 450 to 1550 cm−1 correspond to the characteristic bands of the imidazole ring. The bands in the region of 1350–1550 cm−1 are related to the stretching vibration mode of the entire imidazole ring. Also, the various bands between 950 and 1350 cm−1 are allocated to the in-plane bending vibration of the ring; whereas the observed bands at 450–800 cm−1 could be ascribed to the out-of-plane bending vibration. Moreover, the absorption band at 1579 cm−1 is related to the stretching vibration of CeN bond in H-MIM, and the stretching mode of CeH bond can be recognized at 2923 and 3133 cm−1, which assigned to the aliphatic chain and aromatic ring of H-MIM, respectively [69,74,75]. It is obvious that all of the ZIF-67 peaks well-appeared in the spectrum of the ZIF-67@Fe3O4@ESM composite. This affirms the accuracy of the composite structure and the success of growing ZIF-67 crystals on the Fe3O4@ESM. The purity and crystalline structures of the prepared samples were determined by X-ray diffraction analysis. As illustrated in Fig. 3, the XRD pattern of the synthesized Fe3O4 nanoparticles shows specific diffraction peaks which located at 2θ values of 30.33°, 35.69°, 43.32°, 53.72°, 57.28°, and 62.87° with relating to diffraction planes of 220, 311, 400, 422, 511, and 440. This pattern accord with the cubic structure of magnetite-based on JCPDS card No. 19-0629 [76]. After combining of magnetic nanoparticles with ESM, the characteristic peaks of Fe3O4 can be clearly observed in the XRD pattern of Fe3O4@ ESM. Typically, the XRD pattern of the chicken eggshell membrane has weak and wide diffraction peaks which emerge around 2θ = 24° and 43°, implying the low crystallinity and amorphous nature of ESM [77]. Therefore, these peaks did not appear in the XRD pattern of Fe3O4@ ESM due to the intense peaks of Fe3O4 particles. Also, there are some extra unknown peaks in the composition of Fe3O4@ESM, which could be ascribed to the remaining calcium compounds (such as CaO, Ca (OH)2 and Ca(CO)3) of eggshell onto ESM. The XRD patterns of ZIF-67 conforms to the other reported samples in the literature [78]. The diffraction peaks of crystalline ZIF-67 with the SOD-type phase at 2θ values of 7.37°, 10.40°, 12.73°, 14.69°, 16.45°, 18.03°, 22.12°, 24.49°, and 26.65° are relating to the diffraction planes of 011, 002, 112, 022, 013, 222, 114, 233 and 134 [53]. Furthermore, it is obvious that the characteristics peaks of ZIF-67 well-appeared in the XRD pattern of the ZIF-

Fig. 3. XRD patterns of the prepared materials.

67@Fe3O4@ESM composite. This affirms the accuracy of the composite structure and the success of growing ZIF-67 crystals on the Fe3O4@ ESM. The morphological observation of materials in each step was studied by SEM analysis. The nanoscale spherical shape of Fe3O4 particles was clearly depicted from Fig. 4a. Overall, ESM porous film is made up from highly interwoven cross-linked protein fibers (Fig. 4b) [79,80]. As can be seen from Fig. 4c, the surface morphology of Fe3O4 nanoparticles loaded on ESM indicates a macroporous network structure associated by the aggregation of very fine magnetite nanocrystals [81]. The microscopic structure of the cobalt-based zeolitic imidazolate framework is also presented. The Fig. 4d illustrates a numerous uniform and welldefined facets of ZIF-67. Also, to facilitate the observation of the smeared surface of well-defined truncated rhombic dodecahedrons shape of ZIF-67, a single crystal of it in larger magnification was selected and studied [27,82]. Clearly, Fig. 4e reveals the particles average size is in range of 2 μm or even more. Finally, in order to view more insights into the morphological structure of the composite (ZIF-67@ 291

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Fig. 4. SEM images of the samples (a) Fe3O4, (b) ESM, (c) Fe3O4@ESM, (d) and (e) ZIF-67, and (f) ZIF-67@Fe3O4@ESM.

Fe3O4@ESM), SEM image was taken. With the addition of Fe3O4@ESM, the nucleation agent size of ZIF-67 crystals decrease, but the polyhedral shape of ZIF-67 particles does not considerably affect. Actually, the composite shows a regular form compared to naked ZIF-67 (Fig. 4f). Meanwhile, the successful synthesis of ZIF-67 on the surface of Fe3O4@ ESM can be confirmed by the XRD analysis (Fig. 3). Moreover, the elemental analysis was performed and the results illustrated that the final compound of the synthesized ZIF-67@Fe3O4@ESM included the related pieces, which was in great agreement with the formation of MOF composite. As Fig. 5a, presents, the weight percentages and the amount of each element in MOF composite structure can be determined

by EDS spectrum. Also, the elemental mapping provides the visual overview from density of elements (Fig. 5b). One of the most important features of adsorbents is the capability of facile separation from the liquid media. Therefore, the VSM analysis was performed to confirm the superparamagnetic properties of the synthesized materials. As can be seen from Fig. 6, both magnetic samples of Fe3O4 and ZIF-67@Fe3O4@ESM illustrate the superparamagnetic property with saturation magnetization values of 26.5 and 8.3 emu/g, respectively. It is obvious that the magnetization of the ZIF-67@Fe3O4@ESM composite is lower than that of Fe3O4. Nevertheless, this adsorbent still exhibits enough magnetization, which 292

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Fig. 6. Magnetic curves for the synthesized materials. Table 3 BET analysis data of the materials. Sample

SBET (m2/g)

ESM [54] Fe3O4@ESM ZIF-67 ZIF-67@Fe3O4@ESM

2.21 25.96 1403.7 1211.3

Fig. 7. Nitrogen adsorption isotherms for the materials at 77 K.

adsorption process, was also reported. The details of the BET analysis were listed in Table 3. As can be seen from Table 3, the successful synthesis of ZIF-67 leads to increase in value of BET surface area of ESM. This amount for ZIF-67@Fe3O4@ESM is very close to the synthesized ZIF-67 value. Fig. 7 shows the adsorption behavior of the prepared materials. According to the IUPAC category for porous materials, ZIF-67 and ZIF-67@Fe3O4@ESM match with the typical type I isotherms, indicating that the microporous structure is the most dominant configuration of pores.

Fig. 5. The EDS spectrum (a) and elemental mapping (b) of the synthesized ZIF67@Fe3O4@ESM.

guarantees the capability of magnetic separation. In this work, at the end of the adsorption procedure, the magnetic composite adsorbent was separated quickly by an external magnet from the wastewater solution, which indicated its magnetic nature. In this study, the BET surface area as a very important factor in

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Fig. 8. Cu2+ adsorption ability of the materials.

3.2. Pollutant removal process Nowadays, due to industrial activities, heavy metal cations are commonly found in natural and wastewater [83]. In this research, an industrial wastewater polluted by Cu2+ was modeled. For this purpose, series of the various conditions of adsorption process (adsorbent dose = 0.004–0.008 g, solution pH = 4, 5, and 6, mixing time up to 150 min, and heavy metal ion concentration = 10, 15, and 20 mg/L) were considered and studied in details. The obtained results were plotted according to the adsorption capacity and pollutant removal percentage. The process of unrivaled adsorbent selection was carried out by testing the Cu2+ trapping strength of the materials as diverse as Fe3O4@ESM, ZIF-67, and ZIF-67@Fe3O4@ESM. The governing conditions on the experiment were fixed on pH = 5, the concentration of Cu2+ = 15 mg/L, and 0.006 g of each adsorbent. According to the Fig. 8, the ZIF-67@Fe3O4@ESM, by removing the heavy metal ion at the acceptable and higher value in comparison with the others, was selected as a superior adsorbent for the rest of study. The effect of operational conditions (adsorbent dose, mixing time, pH, and initial pollutant concentration) on the adsorption behavior of ZIF-67@Fe3O4@ESM was fully studied and interpretational graphs in present of adsorption capacity and removal percentage were indicated at Fig. 9. According to the data, the observed increase in adsorption amount of Cu2+ from 145.02 to 248.95 m2/g was due to the increase of ZIF-67@Fe3O4@ESM nanocomposite dosage from 0.004 g to 0.008 g. Of course, the adsorption progress is depended on the number of active sites which trap the pollutant molecules, increasing in the amount of adsorbent interrupts it and leads to the reverse results. So, 0.006 g was a candidate as optimum dose to further tests. The solution pH alterations can easily change the adsorption process results by manipulating in the adsorbent surface chemistry and the heavy metal ions chemical speciation [84]. Initially, the Cu2+ concentration (15 mg/L) and a ZIF-67@Fe3O4@ESM dose of 0.006 g/L were fixed at 298 K. Then, the pH alteration influence at various acidic range (4, 5, and 6) was evaluated (Fig. 9b). As the pH value increases, according to the decrease in H+ cation which is manipulating the surface functional groups of ZIF-67@Fe3O4@ESM, the saturated adsorption capacity of the adsorbent increases. Also, the effect of mixing time and Cu2+ concentration on heavy metal ion removal (%) was studied, when the solution pH was adjusted to 5 and ZIF-67@Fe3O4@ESM dosage was fixed to 0.006 g. As can be

Fig. 9. Operational conditions effect on adsorption process of copper ion (a) ZIF-67@Fe3O4@ESM dosage (b) Cu2+ solution pH (c) ion concentration and mixing time effect. 294

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for adsorption on the adsorbent active surface was observed. Truly, this phenomenon well explains the little decreases occurred in removal (%) and Cu2+ adsorption capacity. The mechanism of Cu2+ cation capture and BR18 dye adsorption on the ZIF-67@Fe3O4@ESM nanocomposite was fully studied and the related schematic was presented at Fig. 11. The physical and chemical features of the adsorbent are the main keys which control the adsorption process as well as mass transfer phenomenon [88]. The obtained data from the binary mixture of pollutants removal experiments can clearly describe the processes phenomena. In this study, according to the positive surface charge of ZIF-67 in acidic solution which was reported by Qingxiang Yang [53], the possible mechanism of Cu2+ capture by ZIF-67, can be explained by insertion of cations into the MOF structure. The other effective factor in physical adsorption is the π-π interaction. The aromatic rings in the structures of both MOF and BR18 dye molecules, can affect each other and lead to a strong non-covalent, non-polar/π-π attraction between adsorbate and adsorbent. According to the same surface charge of both adsorbate and adsorbent (BR18 molecules and ZIF-67@Fe3O4@ESM) and also the low variation in the adsorption capacity of Cu2+ cation (regarding to obtained data), it is conceived that the π-π attraction force plays a vital role in BR18 dye adsorption from binary pollutants mixture. 3.3. Isotherm and kinetic study The equilibrium adsorption isotherms as the monumental experimental equations obtained by scheming the solid-phase concentration versus liquid-phase concentration, could demonstrate multitude phenomena such as the adsorbent affinities, equilibrium data of adsorption, surface properties of adsorbent, adsorption properties and mechanism by tracking the adsorbent and adsorbate interaction behavioral trait [85–88]. So far, several adsorption isotherm theorems were available. In this study, several isotherms were studied, including the Temkin Langmuir, Freundlich, and Elovich. The isotherm constant parameters and curves were presented at Table S1 and Fig. S1, respectively. The monolayeric adsorbate sorption on the adsorbent uniform structure and multilayer adsorption on the heterogeneity of the sorbent surface with uniform energy distribution are the fundamentals of the Langmuir and Freundlich equilibrium isotherms theory, respectively [89]. The Dubinin–Radushkevich (D-R) theory, an empirical equation, is based on the multilayer sorption of adsorbates. The Temkin isotherm theorem explains the increasing coverage of sorbent active sites leads to the adsorption energy decrease [73]. In this study, due to the obtained results, for copper ion sorption and BR18 adsorption, the equilibrium isotherm was pursued the Langmuir model (Table 4). The speed of solute adsorption rate on the surface of adsorbent is a very notable feature in the aqueous effluent treatment process. Analysis of controlling mechanism of the sorptive process was tried by several common kinetic models. Adsorption as a multi-stage process is involving of mass transfer from liquid bulk to the adsorbent active sites, adsorption reaction on active spots, the intra-particle diffusion of adsorbates in the channels and the pores of adsorbent and so forth. This research was helped by the most common kinetic models including pseudo-first and pseudo-second order, intraparticle diffusion, and the Elovich models to investigate the rate of Cu2+ and dye removal uptake of ZIF-67@Fe3O4@ESM. The pseudo-first and pseudo-second order models were applied to examine the adsorption rate based on the equilibrium time data [84]. In 1898, for the first time, the Lagergren has proposed the pseudo-first order model [90–92]. The pseudo-second order kinetic model could anticipate the adsorption behavior throughout the adsorption range [75,93]. The intra-particle diffusion model is mostly applied in order to distinguish the pathway and mechanism as well as the driving force involved in the adsorption [94]. Finally, to accomplish the kinetic study, the Elovich model was also investigated. The kinetic model constants and curves were presented at Table S2 and Fig. S2,

Fig. 10. Pollutant removal from wastewater at pH = 5 and 0.006 g of Fe3O4/ ESM/ZIF-67 (a) BR18 dye (b) Cu2+ and BR18 mixture.

seen from revealed data, while the adsorbent dose stays unchanged and pollutant solution was concentrated, the possibility of pollutant molecule flux from solution bulk onto adsorbent active sites increases. Actually, a higher concentration gradient as the mass transfer driving force leads to more number of the Cu2+ ions collision with the active sites of the ZIF-67@Fe3O4@ESM surface. So, intense pollutant molecular adsorption which occurred at its low concentration causes the faster equilibrium for the adsorption process [85–87]. To do a further investigation of ZIF-67@Fe3O4@ESM contaminant removal ability, basic dye removal and coexisting pollutant (Cu2+ ion and dye (BR18) molecule) effect on the adsorption process were studied. This experiment ran at pH = 5, ZIF-67@Fe3O4@ESM = 0.006 g, and diverse concentration of BR18 at 298 K temperature. According to the obtained data from Fig. 10, high dye removal percentage (91.6%) was achieved while the concentration of dye solution was reached to 10 mg/L at single mode test. Fig. 10 indicates, the BR18 removal (%) was still high, albeit adding Cu2+ ion into the dye solution. In this binary mixture of heavy metal ion and basic dye (raising the amount of adsorbates), a competition between dye molecule and heavy metal ion 295

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Fig. 11. The governing mechanism on Cu2+ and BR18 removal by ZIF-67@Fe3O4@ESM.

ZIF-67@Fe3O4@ESM was decreased slightly after fifth cycles (93%) and still showed excellent and high stability. After that, a sharper reduction of efficiency (%) was observed in sixth run of regeneration process which could be attributed to imperfect desorption of contamination from microenvironment of adsorbent and occupation of active sites of adsorbent. The stability of adsorbents is important in purification process, large-scale application, and industrial uses. In this work, the stability of the well-ordered synthesized ZIF-67 crystals on magnetic eggshell membrane support was testified and reported. To investigate the stability of the ZIF-67 frameworks on Fe3O4@ESM support, several analyses such as XRD, SEM/EDS, and ICP were performed. According to the obtained results, the high similarity of the SEM image and XRD pattern between inexperienced sample and after use sample confirms the stability of the composite structure (Fig. S4). Actually, the ZIF-67@ Fe3O4@ESM showed high stability and maintained their original shape (SEM images), and remained without a significant change in crystallinity (XRD pattern). Therefore, such excellent reproducibility, reusability, and easy superstation procedure, are making ZIF-67@Fe3O4@ ESM as an ideal material for wastewater treatment. In addition, EDS analysis (at 15 kV) was performed to validate the negligible Co leaching from MOF's framework. Moreover, the ICP analysis was carried out to accurate study Co cation release from ZIF-67@Fe3O4@ESM skeleton. Almost, from a certain concentration of ZIF-67@Fe3O4@ESM (60 mg/

Table 4 The candidate equilibrium isotherm constants for Cu2+ and BR18 removal. Model

Parameter

Langmuir

qe =

qm KLCe (1 + KlCo )

qm (mg/g) KL R2

Sorbent Cu2+

BR18

344.82 9.66 0.993

250.81 4.44 0.984

respectively. Due to the obtained results, for Cu2+ sorption and BR18 adsorption, the kinetic model was followed pseudo-second order model (Table 5). 3.4. Stability and reusability of adsorbent The reusability of the adsorbents is a vital factor for real-world applications. In this research, the results of six times reproducing process were presented in Fig. S3 at the optimum point of operational parameters of the experiment (pH = 5, room temperature, Cu2+ concentration = 15 mg/L same adsorbent dosage = 0.006 g). After each run, the adsorbent was revived by dilute acid solution (5 mM HCl) and ultrasonic aid. Then, it was rinsed several times by doubly deionized water and dried at 353 K. According to Fig. S3, the efficiency (%) of the Table 5 The candidate kinetic model constants for Cu2+ and BR18 removal. Model

Parameters

Adsorbate Cu2+

Concentration (mg/L) Pseudo-second-order t qt

=

1

k2q 2e

+

t qe

(qe) k2 R2

Cal

BR18

10

15

20

10

15

20

208.33 0.0011 0.998

333.33 0.0003 0.980

357.14 0.0005 0.997

208.33 0.0001 0.966

277.77 0.0012 0.951

294.11 0.0001 0.962

296

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L), < 1% (0.41 mg/L) of Co cations were leached out from the ZIF-67 frameworks. According to the fact that 50 mg/L of ZIF-67 is equivalent to 36 mg/L of cobalt ions in the reaction solution [95], the magnitude of the released Co cations from composite structure is negligible and insignificant [96]. So, authors assert the prepared ZIF-67@Fe3O4@ESM bionanocomposite is a stable material in aqueous medium.

[10]

[11] [12]

4. Conclusion

[13]

In the present work, magnetic eggshell membrane (Fe3O4@ESM) was synthesized via a low-temperature co-precipitation method and considered as a MOF support bed. Zeolitic imidazolate framework-67 (ZIF-67) crystals as a high surface area (1403.7 m2/g) and large porous volume subclass of MOFs were successfully grown and stabilized on the surface of the Fe3O4@ESM to prepare the water-based ZIF-67@Fe3O4@ ESM composite using ultrasound-assisted approach. The synthesized samples were analyzed using XRD, FTIR, SEM/EDS/Mapping, VSM, and BET techniques. It was observed that the ZIF-67@Fe3O4@ESM composite has faster adsorption rate and better performance for the removal of BR18 dye and Cu2+ cation from wastewater in comparison with other prepared adsorbents, due to the high surface area. The results showed that the equilibrium data were best matched and explained by the Langmuir isotherm model with a maximum adsorption capacity of 344.82 and 250.81 mg/g for Cu2+ and BR18, respectively. Also, the kinetic studies showed that the adsorption process followed the pseudosecond order model. The advantages of this work can be summarized as the accelerated method to green synthesis of ZIF-67 crystals, the capability of simultaneous heavy metal and dye adsorption, low amount of adsorbent, fast adsorption rate and easy separation of adsorbent from pollutant solution.

[14] [15] [16] [17] [18] [19] [20] [21] [22]

[23]

Acknowledgement

[24]

This manuscript is extracted from Joint research project between Khalkhal University of Medical Sciences and Institute for Color Science and Technology. This research was funded by the Khalkhal University of Medical Sciences, Khalkhal, Iran.

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Appendix A. Supplementary data Supplementary data to this article can be found online at https:// doi.org/10.1016/j.apsusc.2019.02.211.

[27]

References

[28] [29]

[1] N.M. Mahmoodi, Binary catalyst system dye degradation using photocatalysis, Fibers and Polymers 15 (2), 273–280. [2] M. Ranjbar-Mohammadi, M. Arami, H. Bahrami, F. Mazaheri, N.M. Mahmoodi, Grafting of chitosan as a biopolymer onto wool fabric using anhydride bridge and its antibacterial property, Colloids Surf. B: Biointerfaces 76 (2010) 397–403. [3] N.M. Mahmoodi, M. Oveisi, A. Taghizadeh, M. Taghizadeh, Novel magnetic amine functionalized carbon nanotube/metal-organic framework nanocomposites: from green ultrasound-assisted synthesis to detailed selective pollutant removal modelling from binary systems, J. Hazard. Mater. 368 (2019) 746–759, https://doi.org/ 10.1016/j.jhazmat.2019.01.107. [4] N.M. Mahmoodi, Nickel ferrite nanoparticle: synthesis, modification by surfactant and dye removal ability, Water, Air, & Soil Pollution 224 (2013) 1419. [5] N.M. Mahmoodi, Synthesis of core–shell magnetic adsorbent nanoparticle and selectivity analysis for binary system dye removal, J. Ind. Eng. Chem. 20 (2014) 2050–2058. [6] N.M. Mahmoodi, N.Y. Limaee, M. Arami, S. Borhany, M. Mohammad-Taheri, Nanophotocatalysis using nanoparticles of titania: mineralization and finite element modelling of Solophenyl dye decolorization, J. Photochem. Photobiol. A Chem. 189 (2007) 1–6. [7] S. Davarpanah, N.M. Mahmoodi, M. Arami, H. Bahrami, F. Mazaheri, Environmentally friendly surface modification of silk fiber: chitosan grafting and dyeing, Appl. Surf. Sci. 255 (2009) 4171–4176. [8] C. Racles, M.F. Zaltariov, M. Iacob, M. Silion, M. Avadanei, A. Bargan, Siloxanebased metal–organic frameworks with remarkable catalytic activity in mild environmental photodegradation of azo dyes, Appl. Catal. B Environ. 205 (2017) 78–92, https://doi.org/10.1016/j.apcatb.2016.12.034. [9] B. Hayati, N.M. Mahmoodi, Modification of activated carbon by alkaline to remove

[30]

[31] [32]

[33]

[34] [35]

[36]

297

dyes from wastewater: mechanism, isotherm and kinetic, Desalin. Water Treat. 47 (2012) 322–333. N.M. Mahmoodi, M. Taghizadeh, A. Taghizadeh, Activated carbon/metal-organic framework composite as a bio-based novel green adsorbent: preparation and mathematical pollutant removal modeling, J. Mol. Liq. 277 (2019) 310–322, https://doi.org/10.1016/j.molliq.2018.12.050. B. Hayati, N.M. Mahmoodi, A. Maleki, Dendrimer–titania nanocomposite: synthesis and dye-removal capacity, Res. Chem. Intermed. 41 (2015) 3743–3757. N.M. Mahmoodi, M. Arabloo, J. Abdi, Laccase immobilized manganese ferrite nanoparticle: synthesis and LSSVM intelligent modeling of decolorization, Water Res. 67 (2014) 216–226. B. Hayati, M. Arami, A. Maleki, E. Pajootan, Thermodynamic properties of dye removal from colored textile wastewater by poly (propylene imine) dendrimer, Desalin. Water Treat. 56 (2015) 97–106. E. Farzaneh, H. Heydari, A.A. Shekarchi, A. Kamran, Breast and cervical cancerscreening uptake among females in Ardabil, Northwest Iran: a community-based study, OncoTargets Ther. 10 (2017) 985–992. M. Rahnamay, M. Mahdavi, A.A. Shekarchi, P. Zare, M.A.H. Feizi, Cytotoxic and apoptosis inducing effect of some pyrano [3, 2-c] pyridine derivatives against MCF7 breast cancer cells, Acta Biochim. Pol. 65 (2018) 397–402. F.P. De Sá, B.N. Cunha, L.M. Nunes, Effect of pH on the adsorption of sunset yellow FCF food dye into a layered double hydroxide (CaAl-LDH-NO3), Chem. Eng. J. 215–216 (2013) 122–127, https://doi.org/10.1016/j.cej.2012.11.024. K. Hunger, P. Mischke, W. Rieper, R. Raue, K. Kunde, A. Engel, Azo Dyes, in: Ullmann's Encycl. Ind. Chem., Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 2000. doi:https://doi.org/10.1002/14356007.a03_245. N.M. Mahmoodi, Dendrimer functionalized nanoarchitecture: synthesis and binary system dye removal, J. Taiwan Inst. Chem. Eng. 45 (2014) 2008–2020. N.M. Mahmoodi, Photodegradation of dyes using multiwalled carbon nanotube and ferrous ion, J. Environ. Eng. 139 (2013) 1368–1374. N.M. Mahmoodi, Photocatalytic degradation of textile dyes using ozonation and magnetic nickel ferrite nanoparticle, Prog. Color Colorants Coat. 9 (2016) 161–172. N.M. Mahmoodi, M. Arami, Numerical finite volume modeling of dye decolorization using immobilized titania nanophotocatalysis, Chem. Eng. J. 146 (2009) 189–193. N.M. Mahmoodi, M. Arami, N.Y. Limaee, K. Gharanjig, F. Nourmohammadian, Nanophotocatalysis using immobilized titanium dioxide nanoparticle: degradation and mineralization of water containing organic pollutant: case study of Butachlor, Mater. Res. Bull. 42 (2007) 797–806. N.M. Mahmoodi, Synthesis of amine-functionalized magnetic ferrite nanoparticle and its dye removal ability, J. Environ. Eng. 139 (2013) 1382–1390. M. Oveisi, M.A. Asli, N.M. Mahmoodi, Carbon nanotube based metal-organic framework nanocomposites: synthesis and their photocatalytic activity for decolorization of colored wastewater, Inorg. Chim. Acta 487 (2019) 169–176. N.M. Mahmoodi, J. Abdi, M. Taghizadeh, A. Taghizadeh, B. Hayati, A.A. Shekarchi, M. Vossoughi, Activated carbon/metal-organic framework nanocomposite: preparation and photocatalytic dye degradation mathematical modeling from wastewater by least squares support vector machine, J. Environ. Manag. 233 (2019) 660–672, https://doi.org/10.1016/j.jenvman.2018.12.026. J. Yang, F. Zhang, H. Lu, X. Hong, H. Jiang, Y. Wu, Y. Li, Hollow Zn/co ZIF particles Derived from Core-Shell ZIF-67@ZIF-8 as selective catalyst for the semi-hydrogenation of acetylene, Angew. Chem. Int. Ed. 54 (2015) 10889–10893, https://doi. org/10.1002/anie.201504242. Q. Shi, Z. Chen, Z. Song, J. Li, J. Dong, Synthesis of ZIF-8 and ZIF-67 by steamassisted conversion and an investigation of their Tribological behaviors, Angew. Chem. Int. Ed. 50 (2011) 672–675, https://doi.org/10.1002/anie.201004937. C. Wang, X. Liu, N. Keser Demir, J.P. Chen, K. Li, Applications of water stable metal–organic frameworks, Chem. Soc. Rev. 45 (2016) 5107–5134, https://doi.org/ 10.1039/C6CS00362A. X. Li, X. Gao, L. Ai, J. Jiang, Mechanistic insight into the interaction and adsorption of Cr(VI) with zeolitic imidazolate framework-67 microcrystals from aqueous solution, Chem. Eng. J. 274 (2015) 238–246, https://doi.org/10.1016/j.cej.2015.03. 127. P. Krokidas, M. Castier, S. Moncho, D.N. Sredojevic, E.N. Brothers, H.T. Kwon, H.K. Jeong, J.S. Lee, I.G. Economou, ZIF-67 Framework: A Promising New Candidate for Propylene/Propane Separation. Experimental Data and Molecular Simulations, J. Phys. Chem. C. 120 (2016) 8116–8124. doi:https://doi.org/10.1021/acs.jpcc. 6b00305. K.Y.A. Lin, C.H. Wu, Efficient adsorptive removal of toxic Amaranth dye from water using a Zeolitic Imidazolate framework, Water Environ. Res. 90 (2018) 1947–1955. N.M. Mahmoodi, M. Taghizadeh, A. Taghizadeh, Ultrasound-assisted green synthesis and application of recyclable nanoporous chromium-based metal-organic framework, Korean J. Chem. Eng. 36 (2019) 287–298, https://doi.org/10.1007/ s11814-018-0162-1. S. Li, S. Peng, L. Huang, X. Cui, A.M. Al-Enizi, G. Zheng, Carbon-coated Co 3+ −rich cobalt selenide Derived from ZIF-67 for efficient electrochemical water oxidation, ACS Appl. Mater. Interfaces 8 (2016) 20534–20539, https://doi.org/10.1021/ acsami.6b07986. E.X. Chen, H. Yang, J. Zhang, Zeolitic Imidazolate framework as formaldehyde gas sensor, Inorg. Chem. 53 (2014) 5411–5413. B. Ren, Y. Xu, L. Zhang, Z. Liu, Carbon-doped graphitic carbon nitride as environment-benign adsorbent for methylene blue adsorption: kinetics, isotherm and thermodynamics study, J. Taiwan Inst. Chem. Eng. 0 (2018) 1–7. doi:https://doi. org/10.1016/j.jtice.2018.03.041. R. Wagia, I. Strashnov, M.W. Anderson, M.P. Attfield, Insight and control of the crystal growth of Zeolitic Imidazolate framework ZIF-67 by atomic force

Applied Surface Science 480 (2019) 288–299

N.M. Mahmoodi, et al.

[37] [38]

[39]

[40] [41] [42]

[43]

[44]

[45] [46] [47]

[48]

[49]

[50] [51]

[52]

[53] [54] [55] [56]

[57]

[58]

[59] [60]

microscopy and mass spectrometry, Cryst. Growth Des. 18 (2018) 695–700, https:// doi.org/10.1021/acs.cgd.7b01058. Z.-X. Low, J. Yao, Q. Liu, M. He, Z. Wang, A.K. Suresh, J. Bellare, H. Wang, Crystal transformation in Zeolitic-Imidazolate framework, Cryst. Growth Des. 14 (2014) 6589–6598, https://doi.org/10.1021/cg501502r. D. Esken, S. Turner, O.I. Lebedev, G. Van Tendeloo, R.A. Fischer, Au@ZIFs: stabilization and encapsulation of cavity-size matching gold clusters inside functionalized zeolite imidazolate frameworks, ZIFs, Chem. Mater. 22 (2010) 6393–6401, https://doi.org/10.1021/cm102529c. C. Avci, J. Ariñez-Soriano, A. Carné-Sánchez, V. Guillerm, C. Carbonell, I. Imaz, D. Maspoch, Post-synthetic anisotropic wet-chemical etching of colloidal sodalite ZIF crystals, Angew. Chem. Int. Ed. 54 (2015) 14417–14421, https://doi.org/10. 1002/anie.201507588. K.Y.A. Lin, H.A. Chang, Ultra-high adsorption capacity of zeolitic imidazole framework-67 (ZIF-67) for removal of malachite green from water, Chemosphere. 139 (2015) 624–631, https://doi.org/10.1016/j.chemosphere.2015.01.041. P. Krokidas, M. Castier, I.G. Economou, Computational study of ZIF-8 and ZIF-67 performance for separation of gas mixtures, J. Phys. Chem. C 121 (2017) 17999–18011, https://doi.org/10.1021/acs.jpcc.7b05700. Y. Pan, Z. Li, Z. Zhang, X.S. Tong, H. Li, C.Z. Jia, B. Liu, C.Y. Sun, L.Y. Yang, G.J. Chen, D.Y. Ma, Adsorptive removal of phenol from aqueous solution with zeolitic imidazolate framework-67, J. Environ. Manag. 169 (2016) 167–173, https://doi.org/10.1016/j.jenvman.2015.12.030. S. Bauer, C. Serre, T. Devic, P. Horcajada, N. Stock, High-throughput assisted rationalization of the formation of metal organic frameworks in the Iron (III) aminoterephthalate solvothermal system, Inorg. Chem. 47 (2008) 7568–7576, https:// doi.org/10.1021/ic800538r. N.T. Thanh Tu, T.V. Thien, P.D. Du, V.T. Thanh Chau, T.X. Mau, D.Q. Khieu, Adsorptive removal of Congo red from aqueous solution using zeolitic imidazolate framework-67, J. Environ. Chem. Eng. 6 (2018) 2269–2280, https://doi.org/10. 1016/j.jece.2018.03.031. Y. Huang, X. Zeng, L. Guo, J. Lan, L. Zhang, D. Cao, Heavy metal ion removal of wastewater by zeolite-imidazolate frameworks, Sep. Purif. Technol. 194 (2018) 462–469, https://doi.org/10.1016/j.seppur.2017.11.068. Y. Li, K. Zhou, M. He, J. Yao, Synthesis of ZIF-8 and ZIF-67 using mixed-base and their dye adsorption, Microporous Mesoporous Mater. 234 (2016) 287–292, https://doi.org/10.1016/j.micromeso.2016.07.039. S. Rafiei, S. Tangestaninejad, P. Horcajada, M. Moghadam, V. Mirkhani, I. Mohammadpoor-Baltork, R. Kardanpour, F. Zadehahmadi, Efficient biodiesel production using a lipase@ZIF-67 nanobioreactor, Chem. Eng. J. 334 (2018) 1233–1241, https://doi.org/10.1016/j.cej.2017.10.094. Y. Pan, C. Jia, B. Liu, Z. Zhang, X. Tong, H. Li, Z. Li, R. Ssebadduka, C. Sun, L. Yang, G. Chen, Separation of methane/ethylene gas mixtures efficiently by using ZIF-67/ water-ethylene glycol slurry, Fluid Phase Equilib. 414 (2016) 14–22, https://doi. org/10.1016/j.fluid.2016.01.003. J.Y. Hong, Y. Jung, D.W. Park, S. Chung, S. Kim, Synthesis and electrochemical analysis of electrode prepared from zeolitic imidazolate framework (ZIF)-67/graphene composite for lithium sulfur cells, Electrochim. Acta 259 (2018) 1021–1029, https://doi.org/10.1016/j.electacta.2017.11.016. K.Y. Andrew Lin, W. Der Lee, Self-assembled magnetic graphene supported ZIF-67 as a recoverable and efficient adsorbent for benzotriazole, Chem. Eng. J. 284 (2016) 1017–1027, https://doi.org/10.1016/j.cej.2015.09.075. Q. Yang, R. Lu, S. Ren, C. Chen, Z. Chen, X. Yang, Three dimensional reduced graphene oxide/ZIF-67 aerogel: effective removal cationic and anionic dyes from water, Chem. Eng. J. 348 (2018) 202–211, https://doi.org/10.1016/j.cej.2018.04. 176. K.Y.A. Lin, W. Der Lee, Highly efficient removal of malachite green from water by a magnetic reduced graphene oxide/zeolitic imidazolate framework self-assembled nanocomposite, Appl. Surf. Sci. 361 (2016) 114–121, https://doi.org/10.1016/j. apsusc.2015.11.108. Q. Yang, S.S. Ren, Q. Zhao, R. Lu, C. Hang, Z. Chen, H. Zheng, Selective separation of methyl orange from water using magnetic ZIF-67 composites, Chem. Eng. J. 333 (2018) 49–57, https://doi.org/10.1016/j.cej.2017.09.099. M. Arami, N. Yousefi Limaee, N.M. Mahmoodi, Investigation on the adsorption capability of egg shell membrane towards model textile dyes, Chemosphere. 65 (2006) 1999–2008, https://doi.org/10.1016/j.chemosphere.2006.06.074. K. Suyama, Y. Fukazawa, Y. Umetsu, A new biomaterial, hen egg shell membrane, to eliminate heavy metal ion from their dilute waste solution, Appl. Biochem. Biotechnol. 45–46 (1994) 871–879, https://doi.org/10.1007/BF02941856. L. Lin, P. Yuan, Q. Wu, J. Xie, Transformed in situ fabrication of macroporous carbon network structures from egg membranes and its biomacromolecule adsorption, Polym. Compos. 32 (2011) 1062–1068, https://doi.org/10.1002/pc. 21123. M.L. Chen, C.B. Gu, T. Yang, Y. Sun, J.H. Wang, A green sorbent of esterified eggshell membrane for highly selective uptake of arsenate and speciation of inorganic arsenic, Talanta. 116 (2013) 688–694, https://doi.org/10.1016/j.talanta.2013.07. 061. A.-M. Zou, X.-W. Chen, M.-L. Chen, J.-H. Wang, Sequential injection reductive biosorption of Cr(vi) on the surface of egg-shell membrane and chromium speciation with detection by electrothermal atomic absorption spectrometry, J. Anal. At. Spectrom. 23 (2008) 412, https://doi.org/10.1039/b714535g. D.D. Salman, W.S. Ulaiwi, N.M. Tariq, Determination the optimal conditions of methylene blue adsorption by the chicken egg Shell membrane, Int. J. Poult. Sci. 11 (2012) 391–396, https://doi.org/10.3923/ijps.2012.391.396. X.Z. Cheng, C.J. Hu, K. Cheng, B.M. Wei, S.C. Hu, Removal of mercury from wastewater by adsorption using thiol-functionalized eggshell membrane, Adv. Mater.

[61]

[62]

[63] [64]

[65]

[66] [67] [68] [69]

[70]

[71] [72] [73]

[74]

[75]

[76]

[77] [78] [79]

[80] [81]

[82]

[83]

[84]

298

Res. 113–116 (2010) 22–26, https://doi.org/10.4028/www.scientific.net/AMR. 113-116.22. J. Tong, W. Wang, Q. Li, F. Liu, W. Ma, W. Li, B. Su, Z. Lei, L. Bo, Composite of FeCo alloy embedded in biocarbon derived from eggshell membrane with high performance for oxygen reduction reaction and supercapacitor, Electrochim. Acta 248 (2017) 388–396, https://doi.org/10.1016/j.electacta.2017.07.125. Z. Li, L. Zhang, B.S. Amirkhiz, X. Tan, Z. Xu, H. Wang, B.C. Olsen, C.M.B. Holt, D. Mitlin, Carbonized chicken eggshell membranes with 3D architectures as highperformance electrode materials for supercapacitors, Adv. Energy Mater. 2 (2012) 431–437, https://doi.org/10.1002/aenm.201100548. B. Liu, Y. Huang, Polyethyleneimine modified eggshell membrane as a novel biosorbent for adsorption and detoxification of Cr(VI) from water, J. Mater. Chem. 21 (2011) 17413–17418, https://doi.org/10.1039/c1jm12329g. J. Narang, M. Minakshi, C.S. Bhambi, Pundir, determination of serum triglyceride by enzyme electrode using covalently immobilized enzyme on egg shell membrane, Int. J. Biol. Macromol. 47 (2010) 691–695, https://doi.org/10.1016/j.ijbiomac. 2010.09.001. C.S. Pundir, M. Bhambi, N.S. Chauhan, Chemical activation of egg shell membrane for covalent immobilization of enzymes and its evaluation as inert support in urinary oxalate determination, Talanta. 77 (2009) 1688–1693, https://doi.org/10. 1016/j.talanta.2008.10.004. S.F. D'Souza, J. Kumar, S.K. Jha, B.S. Kubal, Immobilization of the urease on eggshell membrane and its application in biosensor, Mater. Sci. Eng. C 33 (2013) 850–854, https://doi.org/10.1016/j.msec.2012.11.010. S. Wang, M. Wei, Y. Huang, Biosorption of multifold toxic heavy metal ions from aqueous water, J. Agric. Food Chem. 61 (2013) 4988–4996, https://doi.org/10. 1021/jf4003939. I. Gonçalves, C. Silva, A. Cavaco-Paulo, Ultrasound enhanced laccase applications, Green Chem. 17 (2015) 1362–1374, https://doi.org/10.1039/c4gc02221a. J. Abdi, M. Vossoughi, N.M. Mahmoodi, I. Alemzadeh, Synthesis of amine-modified zeolitic imidazolate framework-8, ultrasound-assisted dye removal and modeling, Ultrason. Sonochem. 39 (2017) 550–564, https://doi.org/10.1016/J.ULTSONCH. 2017.04.030. H. Chen, J. Liu, X. Cheng, Y. Peng, Adsorption for the removal of malachite green by using eggshell membrane in environment water samples, Environ. Sci. Mater. Eng. 573–574 (2012) 63–67, https://doi.org/10.4028/www.scientific.net/AMR.573574.63. N.D. Kandpal, N. Sah, R. Loshali, R. Joshi, J. Prasad, Co-precipitation method of synthesis and characterization of iron oxide nanoparticles, J. Sci. Ind. Res. 73 (2014) 87–90, https://doi.org/10.1080/01614949808007106. S.G. Ullattil, P. Periyat, B. Naufal, M.A. Lazar, Self-doped ZnO microrods—high temperature stable oxygen deficient platforms for solar Photocatalysis, Ind. Eng. Chem. Res. 55 (2016) 6413–6421, https://doi.org/10.1021/acs.iecr.6b01030. N.M. Mahmoodi, M. Taghizadeh, A. Taghizadeh, Mesoporous activated carbons of low-cost agricultural bio-wastes with high adsorption capacity: preparation and artificial neural network modeling of dye removal from single and multicomponent (binary and ternary) systems, J. Mol. Liq. 269 (2018) 217–228, https://doi.org/10. 1016/j.molliq.2018.07.108. J. Abdi, N.M. Mahmoodi, M. Vossoughi, I. Alemzadeh, Synthesis of magnetic metalorganic framework nanocomposite (ZIF-8@SiO2@MnFe2O4) as a novel adsorbent for selective dye removal from multicomponent systems, Microporous Mesoporous Mater. 273 (2019) 177–188, https://doi.org/10.1016/j.micromeso.2018.06.040. J. Abdi, M. Vossoughi, N.M. Mahmoodi, I. Alemzadeh, Synthesis of metal-organic framework hybrid nanocomposites based on GO and CNT with high adsorption capacity for dye removal, Chem. Eng. J. 326 (2017). doi:https://doi.org/10.1016/j. cej.2017.06.054. Y. Chi, Q. Yuan, Y. Li, L. Zhao, N. Li, X. Li, W. Yan, Magnetically separable Fe3O4@ SiO2@TiO2-ag microspheres with well-designed nanostructure and enhanced photocatalytic activity, J. Hazard. Mater. 262 (2013) 404–411, https://doi.org/10. 1016/j.jhazmat.2013.08.077. X. Li, J. Liang, Z. Hou, Y. Zhu, Y. Qian, Recycling chicken eggshell membranes for high-capacity sodium battery anodes, RSC Adv. 4 (2014) 50950–50954, https:// doi.org/10.1039/C4RA07995G. Y. Li, K. Zhou, M. He, J. Yao, Synthesis of ZIF-8 and ZIF-67 using mixed-base and their dye adsorption, Microporous Mesoporous Mater. 234 (2016) 287–292, https://doi.org/10.1016/j.micromeso.2016.07.039. D. Yang, L. Qi, J. Ma, Eggshell membrane templating of hierarchically ordered macroporous networks composed of TiO2tubes, Adv. Mater. 14 (2002) 1543–1546, https://doi.org/10.1002/1521-4095(20021104)14:21<1543::AID-ADMA1543>3. 0.CO;2-B. S. Park, K.S. Choi, D. Lee, D. Kim, K.T. Lim, K.H. Lee, H. Seonwoo, J. Kim, Eggshell membrane: review and impact on engineering, Biosyst. Eng. 151 (2016) 446–463, https://doi.org/10.1016/j.biosystemseng.2016.10.014. J. Fan, D. Chen, N. Li, Q. Xu, H. Li, J. He, J. Lu, Adsorption and biodegradation of dye in wastewater with Fe3O4@MIL-100 (Fe) core–shell bio-nanocomposites, Chemosphere. 191 (2018) 315–323, https://doi.org/10.1016/j.chemosphere.2017. 10.042. M.R. Azhar, H.R. Abid, V. Periasamy, H. Sun, M.O. Tade, S. Wang, Adsorptive removal of antibiotic sulfonamide by UiO-66 and ZIF-67 for wastewater treatment, J. Colloid Interface Sci. 500 (2017) 88–95, https://doi.org/10.1016/j.jcis.2017.04. 001. E. Calì, J. Qi, O. Preedy, S. Chen, D. Boldrin, W.R. Branford, L. Vandeperre, M.P. Ryan, Functionalised magnetic nanoparticles for uranium adsorption with ultra-high capacity and selectivity, J. Mater. Chem. A 6 (2018) 3063–3073, https:// doi.org/10.1039/c7ta09240g. G. Zhou, J. Luo, C. Liu, L. Chu, J. Crittenden, Efficient heavy metal removal from

Applied Surface Science 480 (2019) 288–299

N.M. Mahmoodi, et al.

[85]

[86]

[87]

[88]

[89]

[90]

industrial melting effluent using fixed-bed process based on porous hydrogel adsorbents, Water Res. 131 (2018) 246–254, https://doi.org/10.1016/j.watres.2017. 12.067. N.M. Mahmoodi, S. Keshavarzi, M. Ghezelbash, Synthesis of nanoparticle and modelling of its photocatalytic dye degradation ability from colored wastewater, J. Environ. Chem. Eng. 5 (2017) 3684–3689, https://doi.org/10.1016/j.jece.2017.07. 010. G. Crini, P.-M. Badot, Application of chitosan, a natural aminopolysaccharide, for dye removal from aqueous solutions by adsorption processes using batch studies: a review of recent literature, Prog. Polym. Sci. 33 (2008) 399–447, https://doi.org/ 10.1016/j.progpolymsci.2007.11.001. M. Oveisi, M.A. Asli, N.M. Mahmoodi, MIL-Ti metal-organic frameworks (MOFs) nanomaterials as superior adsorbents: synthesis and ultrasound-aided dye adsorption from multicomponent wastewater systems, J. Hazard. Mater. 347 (2018) 123–140. L. Zhou, J., Wang, Y., Wang, J., Qiao, W., Long, D., Ling, Effective removal of hexavalent chromium from aqueous solutions by adsorption on mesoporous carbon microspheres, J. Colloid Interface Sci. 462 (2016) 200–207. https://www. sciencedirect.com/science/article/pii/S0021979715302472 (accessed September 14, 2018). F. Gimbert, N. Morin-Crini, F. Renault, P.M. Badot, G. Crini, Adsorption isotherm models for dye removal by cationized starch-based material in a single component system: error analysis, J. Hazard. Mater. 157 (2008) 34–46, https://doi.org/10. 1016/j.jhazmat.2007.12.072. A. Vargas, A. Cazetta, M. Kumita, T. Silva, V. Almeida, Adsorption of methylene

[91]

[92] [93] [94]

[95]

[96]

299

blue on activated carbon produced from flamboyant pods {(D}elonix regia): study of adsorption isotherms and kinetc models, Chem. Eng. J. 168 (2011) 722–730 https://www.sciencedirect.com/science/article/pii/S1385894711001112 , Accessed date: 24 August 2018. K. Vijayaraghavan, T. Padmesh, K. Palanivelu, M. Velan, Biosorption of nickel(II) ions onto Sargassum wightii: application of two-parameter and three-parameter isotherm models, J. Hazard. Mater. 133 (2006) 304–308, https://doi.org/10.1016/ j.jhazmat.2005.10.016. S. Lagergren, About the theory of so-called adsorption of soluble substance, Ci.Nii. Ac.Jp. 24 (1898) 1–39. doi:10.1023/B. Y. Ho, G. McKay, Pseudo-second order model for sorption processes, Process Biochem. 34 (1999) 451–465, https://doi.org/10.1016/S0032-9592(98)00112-5. H. Haroon, T. Ashfaq, S.M.H. Gardazi, T.A. Sherazi, M. Ali, N. Rashid, M. Bilal, Equilibrium kinetic and thermodynamic studies of Cr(VI) adsorption onto a novel adsorbent of Eucalyptus camaldulensis waste: batch and column reactors, Korean J. Chem. Eng. 33 (2016) 2898–2907, https://doi.org/10.1007/s11814-016-0160-0. R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa, M. O'Keeffe, O.M. Yaghi, High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO 2 Capture, Science (80-. ). 319 (2008) 939–943. doi:https://doi.org/10.1126/ science.1152516. K.-Y.A. Lin, H.-A. Chang, Zeolitic imidazole framework-67 (ZIF-67) as a heterogeneous catalyst to activate peroxymonosulfate for degradation of rhodamine B in water, J. Taiwan Inst. Chem. Eng. 53 (2015) 40–45, https://doi.org/10.1016/j. jtice.2015.02.027.