Skip to main content
NCBI home page
ACS Omega logoLink to ACS Omega
. 2022 Jun 27;7(27):23213–23222. doi: 10.1021/acsomega.2c01068

Facile Sonochemical Synthesis of Flexible Fe-Based Metal–Organic Frameworks and Their Efficient Removal of Organic Contaminants from Aqueous Solutions

Ji Hwan Lee †, Yongjun Ahn †, Seung-Yeop Kwak †,‡,§,*
PMCID: PMC9280777  PMID: 35847297

Abstract

graphic file with name ao2c01068_0009.jpg

An iron-based metal–organic framework, MIL-53(Fe), was synthesized via the simple sonochemical method, which is a facial and fast strategy, and their adsorption performance for organic contaminants removal from aqueous solutions was studied. The crystal structure and morphology analysis indicate that the sonochemical synthesis of MIL-53(Fe) particles was faster than the solvothermal preparation method, showing high crystallinity with a downsized hexagonal bipyramid shape. Furthermore, the prepared MIL-53(Fe) exhibited enhanced adsorption capability for the organic dyes compared to metal–organic framework prepared via the solvothermal method and showed excellent maximum adsorption capability for the methyl orange removal from aqueous solutions. Based on the superior adsorption properties and facile synthesis, MIL-53(Fe) prepared by ultrasound irradiation has a potential application for an efficient, economic, and ecofriendly wastewater purification process.

1. Introduction

Recently, the discharge of textile wastewater effluent containing dyes and endocrine-disrupting chemicals (EDCs) has become a social and environmental issue because such chemicals are detrimental to the environment and living organisms.1 For instance, dyes such as methyl orange (MO) and methylene blue (MB) are challenging to chemically degrade and are potentially carcinogenic in nature. MO is a widely used anionic dye in textiles, printing, papers, and food.2 MB is mostly used in cationic dyes for wood, silk, and cotton.3 EDCs may cause developmental and reproductive disorders in humans and wildlife, through their endocrine-disrupting effects.4,5 Especially, bisphenol A (BPA) is one of the highest production and consumption volume chemicals in the world; however, it is a known EDC that is acutely toxic to the aquatic organisms in the 1000–10,000 mg L–1 range for both fresh water and marine species.6 Owing to their toxicities, the removal of MO, MB, and BPA from wastewater is considered vital for environmental sustainability in the field of water treatment.

Adsorption methods have been widely used to remove organic contaminants from aqueous environments because of the simplicity of the equipment and their ease of operation.7−10 Metal–organic frameworks (MOFs) have been investigated as promising adsorbents of hazardous contaminants in water because of the well-defined pore structure of MOFs.11 MOFs are porous crystalline hybrids consisting of metal ions connected by organic linkers that exhibit the advantages of both inorganic and organic porous solids. They have drawn interest because of the ease of tunability of their morphology, pore structure, and chemical properties via changes in the connectivity of the metal ions and the nature of organic linkers.12

Among the various demonstrated MOFs, the MIL-53 family has the advantages of high chemical stability and wide chemical versatility.13 Specifically, MIL-53(Fe), that is, iron-containing MIL-53, is known to have the advantage of biocompatibility and low cost of production.14 MIL-53(Fe) has an insufficient surface area because the presence of guest molecules only opens its pores. Fascinatingly, it can be swelled and used to capture guest molecules from aqueous solutions because of its flexible structure.15 Horcajada et al. reported that MIL-53(Fe) could be swelled and used to deliver drug molecules with the size of ca. 5 nm.16 There are some issues with the preparation method of MIL-53(Fe). The majority of MIL-53(Fe) has been synthesized via solvothermal methods that involve long reaction times and high reaction temperatures, which may result in low productivity.17−19 Furthermore, toxic mineralizing agents, such as hydrofluoric acid, are widely used to synthesize MIL-53(Fe) creating issues with environmental pollutant effluents.15,20 Thus, developing a faster, greener, and cost-effective synthetic method for MIL-53(Fe) with enhanced adsorption performance is required.

To prepare an economical and ecofriendly MIL-53(Fe), sonochemical synthesis may be among the best candidates as a synthesis method. The acoustic cavitation resulting from ultrasound (UTS) irradiation facilitates accelerated reactions and the homogeneous nucleation of MIL-53(Fe), derived from the generation of high temperatures (> 4,700 °C), pressures (> 2000 atm), and rate of temperature change (> 1011 °C s–1) because of the violent collapse of cavitation bubbles.21 From an economical and environmental perspective, UTS irradiation is also advantageous because it could be utilized to facilely synthesize MOFs without using toxic mineralizing agents.22 In addition, downsizing of MOFs often provides enhanced physical and chemical properties because of their controllable diffusion kinetics and morphologies.23 Localized high temperature and pressure by UTS irradiation promote enhanced crystallization kinetics, controlled shape, and phase selectivity.24 The size of MOFs can be reduced via UTS irradiation with improved nucleation. It is reported that the flexibility of the MOF increased by the reduction of the particle size.25 We expected that MIL-53(Fe) prepared via UTS irradiation will show enhanced adsorption performance for organic pollutants in an aqueous solution.

This study focused on the sonochemical synthesis of MIL-53(Fe) and its application in adsorption for dyes and EDCs from aqueous solutions. We successfully obtained dodecahedral MIL-53(Fe) by UTS irradiation, facilitating fast production. In addition, the adsorption efficiency of synthesized MIL-53(Fe) was investigated. To the best of our knowledge, sonochemically synthesized MIL-53(Fe) shows superior adsorption performance for the MO removal in an aqueous solution than previously reported adsorbents.

2. Materials and Methods

2.1. Materials

Terephthalic acid (98%), iron(III) chloride hexahydrate (98%), MO (85%), MB (97%), BPA (99%), cetyltrimethylammonium bromide (CTAB, 99%), pluronic F-127 (BioReagent), and dimethylformamide (DMF, 99.8%) were obtained from Sigma Aldrich.

2.2. Preparation of MIL-53(Fe)

The MIL-53(Fe)_UTS was prepared following a modified method of a previously described procedure.12 Terephthalic acid (6 mmol) was dissolved in 30 mL of DMF. Thereafter, an equivalent amount of iron(III) chloride hexahydrate (6 mmol) was dissolved in the terephthalic acid/DMF solution. The solution was then transferred to a reactor (reactor volume: 50 mL) that was equipped with an ultrasonic generator probe (VCX 750, Sonics & Materials, Inc.). This experiment was performed at 33% of maximum power for 2 h without temperature control (final temperature: ca. 70 °C). The product, denoted as MIL-53(Fe)_UTS-1, was filtered and washed three times with DMF and ethanol. Finally, the product was vacuum-dried at 100 °C overnight. When the amount of terephthalic acid was changed to 3 mmol, the prepared sample was referred to as MIL-53(Fe)_UTS-2. To compare the adsorptive properties, the MIL-53(Fe) series was solvothermally synthesized (150 °C, various reaction times) under identical reactant concentrations; in this case, the samples are referred to as MIL-53(Fe)_solvo-1-t and MIL-53(Fe)_solvo-2-t.

2.3. Characterization

The X-ray diffraction (XRD) pattern was recorded with a New D8 Advance X-ray diffractometer (Bruker, USA) using Cu Kα radiation. Fourier-transform infrared (FT-IR) spectra were acquired on a Nicolet iS10 IR spectrophotometer (Thermo Fisher Scientific, USA) with the sample in potassium bromide pellets. Thermogravimetric analysis (TGA) was conducted using a Q500 system (TA Instruments, USA) at a scan rate of 5 °C min–1 under an air atmosphere. The nitrogen adsorption–desorption isotherm was obtained using a 3Flex surface characterization analyzer (Micromeritics, USA) at −196 °C. The sample was vacuum-dried at 100 °C overnight prior to analysis. Field-emission scanning electron microscopy (FE-SEM) photographs were obtained on a SUPRA 55VP field-emission scanning electron microscope (Zeiss, Germany). Zeta potential was evaluated using a Z-1000 electrophoretic light scattering spectrophotometer (ELS, Otsuka Electronics, Japan).

2.4. Batch Adsorption Experiments

MIL-53(Fe) (5 mg) was added to an MO, MB, and BPA solution (20 mL) at a specific pH (usually 5.6) and then stirred at 30 °C for different durations. The concentrations of MO, MB, and BPA were determined using an ultraviolet–visible spectrophotometer at wavelengths of 464, 665, and 276 nm, respectively. The adsorption capacity was obtained according to the following equation:

2.4. 1

where qe (mg g–1) is the equilibrium adsorption capacity of MIL-53(Fe), Ci (mg L–1) is the initial concentrations of contaminants, Ce (mg L–1) is the equilibrium concentrations of contaminants, V (mL) is the volume of the solution, and M (mg) is the weight of MIL-53(Fe).

The adsorption kinetic models to explain the adsorption kinetics of MO, MB, and BPA on the MIL-53(Fe)_UTS include the pseudo-first-order (PFO) and pseudo-second-order (PSO) models. These two kinetic equations are as follows:

2.4. 2
2.4. 3

where qt (mg g–1) is the adsorption capacity of MIL-53(Fe) at time t, and k1 (min–1) and k2 (g mg–1 min–1) are the PFO rate constant and the PSO rate constant, respectively.

The adsorption isotherm models to explain the adsorption isotherms of MO, MB, and BPA on the MIL-53(Fe)_UTS include the Freundlich and Langmuir isotherm models. These two isotherm equations are as follows:

2.4. 4
2.4. 5

where KF ((mg g–1) (L mg–1)n) is the Freundlich constant, n (unitless) is the heterogeneity factor, KL (L mg–1) is the Langmuir constant, and qL (mg g–1) is the maximum adsorption capacity of MIL-53(Fe)_UTS. The procedure followed to evaluate the adsorption kinetics and isotherm is described in detail in the Supporting Information.

2.5. Simultaneous Adsorption Experiments

The selective adsorption performance of MIL-53(Fe) toward target contaminants was evaluated by dispersing 5 mg of the adsorbents into 20 mL of the aqueous solutions at a specific pH (5.6), with a concentration of 25 mg L–1 MO, 25 mg L–1 MB, 25 mg L–1 BPA, 25 mg L–1 F127, and 25 mg L–1 CTAB.

The effect of other contaminants on the adsorption of MO, MB, and BPA on MIL-53(Fe) was determined using eq 6:

2.5. 6

where Rq,i (unitless) is the ratio of adsorption capacities for the contaminant "i" at equilibrium; qm,i and qs,i (mg g–1) are the adsorption capacities for the contaminant i in the multicomponent system and the single-component system for the same initial concentration, respectively.

3. Results and Discussion

3.1. Optimal Conditions To Prepare MIL 53(Fe)

As shown in Figure 1, despite the absence of mineralizing agents in the synthesis process, the pattern of MIL-53(Fe)_UTS exhibits high intensities, indicating the high crystallinity of the sample regardless of the change in the molar ratio. The XRD pattern of MIL-53(Fe)_UTS showed the strong diffraction peaks (200), (110), and (1 1 −1), which was consistent with those of previously reported MIL-53(Fe).12,21 For MIL-53(Fe)_solvo, all the samples exhibit a crystalline diffraction pattern except for MIL-53(Fe)_solvo-1_16h. Only MIL-53(Fe)_solvo-1_24h showed a similar pattern to MIL-53(Fe)_UTS. The XRD patterns for MIL-53(Fe) can differ depending on pore opening because MIL-53(Fe) exhibits a breathing behavior. We consider that MIL-53(Fe)_UTS and MIL-53(Fe)_solvo-1_24h include an open pore structure; however, other MIL-53(Fe)_solvo samples exhibit a close pore structure.16 According to the Debye–Scherrer equation, broad and weak peaks in the XRD pattern for MIL-53(Fe)_solvo indicate that the crystallite size of MIL-53(Fe)_solvo samples are smaller than those of MIL-53(Fe)_UTS. These results suggest that UTS irradiation can accelerate the nucleation and growth of MIL-53(Fe) despite a much shorter reaction time compared to the solvothermal method.

Figure 1.

Figure 1

Open in a new tab

XRD patterns for (a) MIL-53(Fe)_UTS, (b) MIL-53(Fe)_solvo-1, and (c) MIL-53(Fe)_solvo-2, and the pink bars were stimulated based on the corresponding CheckCIF file of MIL-53(Fe).26

The adsorption capacities of the MIL-53(Fe)_UTS were measured to verify the optimal preparation condition for adsorption ability. The adsorption measurement was conducted for 840 min in a solution with initial MO, MB, and BPA concentrations of 200, 200, and 100 mg L–1, respectively. MIL-53(Fe)_UTS-2 exhibited higher adsorption capacities for MO, MB, and BPA (494.2, 221.9, and 160.1 mg g–1, respectively) than MIL-53(Fe)_UTS-1 (Figure 2). Based on these results, MIL-53(Fe)_UTS-2 and MIL-53(Fe)_solvo-1_24h were employed in further analyses to document their structural properties and adsorption behavior.

Figure 2.

Figure 2

Open in a new tab

Adsorption capacities for MIL-53(Fe)_UTS.

3.2. Comparison of MIL-53(Fe)_UTS and MIL-53(Fe)_solvo

Figure 3a shows that all FT-IR spectra contain IR bands that are characteristic of the MIL-53(Fe) structure. The characteristic band at ∼1685 cm–1 corresponds to the C=O stretching vibration of terephthalic acid, and the band at ∼750 cm–1 indicates the C–H bending vibration of the benzene ring. The IR bands at 3450, 2940, 1597, 1393, and 540 cm–1 are associated with the O–H stretching vibration, aromatic C–H stretching vibration, asymmetric and symmetric COO– stretching vibrations of terephthalate, and Fe–O stretching vibration, respectively. These bands suggest that the iron ions were linked to the terephthalate molecules in MIL-53(Fe)_UTS as well as MIL-53(Fe)_solvo.27

Figure 3.

Figure 3

Open in a new tab

(a) FT-IR spectra, (b) TGA curves, (c) N2 adsorption–desorption isotherms, (d) HK pore size distributions (for micropores), and (e) BJH pore size distributions (for mesopores and macropores) of MIL-53(Fe)_UTS and MIL-53(Fe)_solvo.

The TGA curves of MIL-53(Fe) indicated that the first weight loss below 250 °C resulted from the evaporation of the solvent from the framework (Figure 3b). The second weight loss, which occurred between 250 and 500 °C, was associated with the decomposition of MIL-53(Fe), resulting in an iron oxide-carbon composite.28 When the temperature reached 500 °C, this phase transformed to a pure iron oxide phase, and above 500 °C, the weight of the material was relatively stable.

N2 adsorption–desorption isotherms (Figure 3c) were measured to obtain specific surface areas and pore size distributions (Table 1, Figure 3d,e of MIL-53(Fe). The adsorptive behaviors of all MIL-53(Fe)s might be the combination of Type I and Type II with H3 hysteresis, suggesting the existence of micropores, mesopores, and macropores in their structure.29Table 1 indicates that the increase in the pore size might have resulted from the defect generation caused by UTS irradiation, although an inverse relationship is noted for the specific surface area by pore extension.30,31 The meso- and macropore sizes, acquired using the Barrett–Joyner–Halenda (BJH) method, were significantly different between samples, while the micropore size, determined using the Horvath–Kawazoe (HK) method, was almost similar. The increase in the pore size can be attributed to the absence of an organic linker between each ferric ion.

Table 1. Specific Surface Area and Average Pore Size of MIL-53(Fe).

sample specific surface area (m2 g–1) HK pore size (nm) BJH pore size (nm)
MIL-53(Fe)_UTS 5.01 1.01 32.91
MIL-53(Fe)_solvo 7.81 0.95 5.45
Open in a new tab

As shown in Figure 4, MIL-53(Fe)_solvo exhibited a clear hexagonal bipyramid morphology with a larger size (0.6–2.6 μm) because of the slow nucleation and sufficient growth occurring during the long reaction time (24 h). However, MIL-53(Fe)_UTS showed a slightly ambiguous morphology with a smaller size (0.4–1.8 μm) because of faster nucleation and insufficient growth during a shorter reaction time (2 h), which corresponds with previous results.21

Figure 4.

Figure 4

Open in a new tab

FESEM photographs and size distribution for MIL-53(Fe)_UTS and MIL-53(Fe)_solvo.

The adsorption capacities of MIL-53(Fe)_UTS and MIL-53(Fe)_solvo were compared through normalization by the specific surface area to identify the intrinsic affinity of MIL-53(Fe) toward organic contaminants. Adsorption was measured for 840 min in a solution with initial MO, MB, and BPA concentrations of 200, 200, and 100 mg L–1, respectively. The MIL-53(Fe)_UTS had much higher MO, MB, and BPA adsorption capacities (98.6, 44.3, and 32.0 mg m–2, respectively) than MIL-53(Fe)_solvo (Figure 5). It is hypothesized that the enhanced adsorptive properties of MIL-53(Fe)_UTS appear to be due to the reduced size of particles generated by UTS irradiation with the increased flexibility of frameworks.

Figure 5.

Figure 5

Open in a new tab

Normalized adsorption capacities for MIL-53(Fe)_UTS and MIL-53(Fe)_solvo.

3.3. Adsorption Behaviors of MIL-53(Fe)_UTS in the Single-Component System

Figure 6a displays the relationship between the adsorption of MIL-53(Fe)_UTS for MO, MB, and BPA at C0 (200, 200, and 100 mg L–1, respectively) and a time period from 0 to 840 min. The MO, MB, and BPA adsorption increased rapidly and attained equilibrium after 10 min. The initial rapid adsorption was attributed to an instantaneous adsorption process arising from abundant vacant adsorption surface sites.32 The adsorption kinetics of MO, MB, and BPA on MIL-53(Fe) _UTS were analyzed with PFO and PSO kinetic models. Table 2 indicates that a PSO kinetic model can fit MO, MB, and BPA adsorption. The adsorption kinetics of MIL-53(Fe) _UTS slowed in order from BPA to MB to MO according to their PSO rate constants and initial adsorption rates (h = k2 × qe2). This could be attributed to properties (e.g., mass transfer rate and diffusivity) resulting from the molecular size and molar mass.33 The molecular sizes and molar masses of MB (1.41 × 0.60 × 0.38 nm3 and 319.9 g mol–1) and MO (1.48 × 0.60 × 0.45 nm3 and 327.3 g mol–1) are higher than those of BPA (1.24 × 0.54 × 0.44 nm3 and 228.3 g mol–1), which could result in slower adsorption of MB and MO because molecules with a large molecular size and high molar mass seldom diffuse through the boundary layer near the adsorbent.6,34

Figure 6.

Figure 6

Open in a new tab

(a) Adsorption kinetics and (b) adsorption isotherms of MIL-53(Fe)_UTS for MO, MB, and BPA.

Table 2. Adsorption Kinetic Parameters for MIL-53(Fe)_UTS.

adsorbate pseudo-first-order kinetic
 pseudo-second-order kinetic
  qe k1 R2 qe k2 h R2
MO 483.5 0.0884 0.9951 510.5 0.0003 78.2 0.9957
MB 194.3 0.1906 0.9560 199.7 0.0023 91.7 0.9629
BPA 150.8 0.2743 0.9929 152.7 0.0071 165.6 0.9951
Open in a new tab

Figure 6b displays the relationship between the adsorption of MIL-53(Fe)_UTS for MO, MB, and BPA for 840 min and at various C0 (1000, 200, and 200 mg L–1, respectively). The adsorption capacities of MIL-53(Fe)_UTS for MO, MB, and BPA increased rapidly at lower initial concentrations and then continued to increase gradually at higher initial concentrations. This phenomenon was attributed to a limited number of adsorption sites on the adsorbent.35 The adsorption behavior analysis of MIL-53(Fe)_UTS was conducted by employing the Freundlich and Langmuir isotherm models. The resulting correlation coefficients indicated that the Freundlich model approximated the adsorption of MO on MIL-53(Fe)_UTS and the Langmuir model approximated the adsorption of MB and BPA (Table 3). Therefore, the most appropriate fitting for each sample is plotted. The type of adsorption for MO can be predicted according to the Freundlich constant n, which describes whether the adsorption process is favorable (0 < 1/n < 1) or not.36 The n values for the adsorption of MO by MIL-53(Fe)_UTS showed that the adsorption was favorable. Furthermore, the Freundlich model illustrated that MO was adsorbed onto MIL-53(Fe)_UTS to form a multilayer, suggesting that several adsorption interactions existed between MIL-53(Fe)_UTS and MO.37 The zeta potential of MIL-53(Fe)_UTS was evaluated to explain why MIL-53(Fe)_UTS exhibited a superior MO adsorption capacity (> 1,200 mg g–1). Figure S1 shows that the MIL-53(Fe)_UTS had a surface charge of approximately 20.75 mV at a pH value of 5.6, which implied that there were electrostatic attractions between positively charged MIL-53(Fe)_UTS and negatively charged MO molecules. This positive surface charge was higher than that of MIL-53(Fe)_solvo (approximately 0 mV at a pH value of 5.6), as shown in Figure S2. Therefore, several MO adsorption mechanisms were proposed: (1) π–π interaction between the MO benzene ring and organic linkers within MIL-53(Fe); (2) electrostatic attraction between MIL-53(Fe) and MO anions.38,39

Table 3. Adsorption Isotherm Parameters for MIL-53(Fe)_UTS.

adsorbate Freundlich isotherm
 Langmuir isotherm
  KF n R2 qL KL R2
MO 137.7 3.0 0.9551 1,485.3 0.0064 0.8700
MB 34.1 2.6 0.9592 240.9 0.0522 0.9758
BPA 26.1 2.5 0.8970 222.4 0.0537 0.9928
Open in a new tab

In the case of MB and BPA, the type of adsorption can be categorized using the equilibrium parameter RL, which is defined as follows:5

3.3. 7

The adsorption process can be categorized using the RL value as unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1), or irreversible (RL = 0). The RL values showed that MIL-53(Fe)_UTS favorably adsorbed MB (0.1608–0.7540) and BPA (0.0931–0.7487).

The Langmuir model indicated that MB and BPA formed monolayers on MIL-53(Fe)_UTS.40 The maximum adsorption capacities for MB and BPA were estimated using the Langmuir model to be 240.9 mg g–1 (0.8 mmol g–1) and 222.4 mg g–1 (1.0 mmol g–1), respectively. The different adsorption performances for each molecule could be explained in terms of different interactions between MOF surfaces and adsorbed molecules. BPA molecules are easily adsorbed with π–π interactions onto the surface of MIL-53(Fe)_UTS, while the adsorption of MB was hindered by electrostatic repulsion between MB cations and positively charged MIL-53(Fe)_UTS. Adsorption mechanisms of MIL-53(Fe)_UTS were proposed (Figure 7).

Figure 7.

Figure 7

Open in a new tab

Scheme for the adsorption of MIL-53(Fe)_UTS for MO, MB, and BPA.

The maximum adsorption capacities, rate constants, and synthetic conditions of MIL-53(Fe)_UTS were compared with those in previous reports using various adsorbents to confirm the potential of MIL-53(Fe)_UTS as an adsorbent toward dyes and EDCs.2,41−52 As shown in Table 4, the maximum adsorption capacity of MIL-53(Fe)_UTS for MO was significantly higher than those of other previously studied adsorbents. Regarding the removal of MB, only MIL-100(Fe) and the alkali-activated multiwalled carbon nanotube (MWCNT) exhibited higher adsorption capacity than MIL-53(Fe)_UTS. However, its adsorption rate and synthetic conditions were slower, toxic, and tedious.43,52 For the removal of BPA, most adsorbents exhibited higher adsorption capacity than MIL-53(Fe)_UTS. However, the synthetic conditions of these adsorbents included toxic metal ions such as chromium, hazardous agents such as hydrofluoric acid, high reaction temperatures, and long reaction times.41,42,49−51 MIL-53(Fe)_UTS had the advantages of short reaction times (2 h), mild reaction temperature (< 100 °C), and no usage of toxic and hazardous agents in the synthesis procedure. UTS irradiation can solve these as-forementioned problems of conventional MOF preparation. Considering the concerns involved with DMF, minimizing usage or no usage of DMF as the solvent is required for further research using UTS irradiation because DMF is also a recognized carcinogen, harmful to the environment and easily causes secondary pollution.53,54

Table 4. Comparison of the Maximum Adsorption Capacities (mg g–1)/Rate Constants (g mg–1 min–1) and Synthetic Conditions of Various Adsorbents.

adsorbent MO MB BPA synthetic/experimental pH conditions ref
mesostructured MIL-53(Al)     465/0.0007 F127, DMF, 130 °C for 2 d/pH 6.5 (41)
MIL-101(Cr)     253/0.0139 HF, NH4F, DMF, 220 °C for 8 h/pH 5.6 (42)
MIL-100(Fe) 1045/0.0002 736/0.0001   HF, HNO3, 150 °C for 4 d/pH 5.0 (43)
MOF-235(Fe) 477/0.0009 187/0.0002   DMF, 80 °C for 1 d/pH 5.6 (44)
Ce(III)-doped UiO-66(Zr) 640/0.0184 145/0.0207   DMF, 120 °C for 1 d/pH 7.0 (45)
mesostructured MIL-101(Cr) 208/0.0030 22/0.0490   DMF, CTAB, NaAc, 220 °C for 8 h/n.a. (2)
PED-MIL-101(Cr) 194/0.0030     HF, NH4F, 220 °C for 8 h, additional steps for functionalization/pH 5.6 (46)
commercial MIL-53(Al) 177/0.0570     n.a./pH 6.0 (47)
HKUST-1/GO   183.5/n.a.   120 °C for 12 h, Hummer method for GO preparation/n.a. (48)
MIL-53(Cr)     421.0/0.0019 175 °C for 7 h, microwave irradiation/pH 6.3 (49)
MIL-101(Cr)- (OH)3     97/n.a. HF, NH4F, DMF, 220 °C for 8 h, additional steps for functionalization/pH 7.0 (50)
argan nut shell-microporous-carbon     1408/0.0040 1. heating from RT to 500 °C (5 °C min–1) and maintaining for 1 h (51)
        2. after cooling, heating from RT to 800 °C (10 °C min–1) and maintaining for 2 h/pH 6.5  
alkali-activated MWCNT 149/0.0020 400/0.0007   1. preparing MWCNT by catalytic chemical vapor deposition method (52)
        2. after mixing with KOH, heating to 750 °C for 1 h/pH 7.0  
MIL-53(Fe)_UTS 1485/0.0003 241/0.0023 222/0.0071 DMF, ultrasonic irradiation, 2 h/pH 5.6 this study
Open in a new tab

To gain a deeper understanding of the structure and the pH effect of the MIL-53(Fe)_UTS in aqueous solutions, the MIL-53(Fe)_UTS was soaked in deionized water (pH 4, 5.6, and 10) for 65 h. All XRD patterns were identical, indicating that the MIL-53(Fe)_UTS was stable in the pH range of 4–10. New Bragg maxima appeared in the XRD pattern compared to the as-synthesized MIL-53(Fe)_UTS, showing a partial structural transformation of the MIL-53(Fe)_UTS in the aqueous solution (Figure S3). In general, as the synthesis of the MIL-53(Fe) proceeds in DMF, and the as-synthesized MIL-53(Fe) retains DMF molecules in its pore structure (MIL-53(Fe)[DMF] form). If sufficient solvent removal or exchange of the as-synthesized MIL-53(Fe) does not occur, the MIL-53(Fe) still retains DMF molecules.12,21,26 On the contrary, if sufficient solvent exchange occurs (exchange times >12 h), the MIL-53(Fe) can retain H2O molecules instead of DMF molecules (MIL-53(Fe)[H2O] form).15,55−57 Based on the XRD results and the presence or absence of solvent exchange in the process, we can conclude that the MIL-53(Fe)_UTS retained DMF molecules (MIL-53(Fe)[DMF] form) and that the MIL-53(Fe)_UTS_H2O retained H2O molecules (MIL-53(Fe)[H2O] form) in their pore structures. Several studies have reported on the structure of the MIL-53(Fe)_solvo obtained via XRD analyses. However, to the best of the authors’ knowledge, none of the previous studies have focused on the structure of the MIL-53(Fe)_UTS using XRD analyses. Therefore, we first indexed the XRD results and then extracted the lattice parameters of the MIL-53(Fe)_UTS using TREOR90 (Tables S1 and S2). The lattice parameters of the MIL-53(Fe)_UTS_H2O were estimated to be lower than those of the MIL-53(Fe)_UTS, which was in accordance with the results reported by Horcajada et al.16 and Loiseau et al.58 The −OH–O hydrogen bonds with the terminal H2O molecules on the iron octahedrons or the oxygen atoms of the bridging carboxylate groups might be attributed to the lattice contraction of the MIL-53(Fe)_UTS. The subnanometer lattice parameter of the MIL-53(Fe)_UTS-H2O can hinder the diffusion of large-sized organic molecules, imposing size selectivity for subnanometer-sized organic contaminants.

The pH effect evaluation on the adsorption (initial concentration of 100 mg L–1) and surface charge was also carried out. As shown in Figure S4, the adsorption of MO, MB, and BPA depends on the pH value of the aqueous solution. At acidic conditions, a high electrostatic attraction exists between the positively charged surface of the MIL-53(Fe)_UTS and the anionic dye MO. As the pH of the system increases, the number of positively charged sites decreases, lowering the adsorption of anionic dye because of decreased electrostatic attraction. However, the adsorption of the cationic dye showed the opposite trend with increasing pH. The adsorption of neutral EDCs was observed to be almost constant in the pH range of 4–10.

3.4. Simultaneous Adsorption of MIL-53(Fe)_UTS in the Multicomponent System

In the textile industry, surfactants are used to improve the binding between dyes and fabric.59 Therefore, it is required to evaluate the simultaneous adsorption of MIL-53(Fe)_UTS in multicomponent systems. We select CTAB as an ionic model surfactant and F127 as a nonionic model surfactant. Table 5 lists the results of the simultaneous adsorption of MO, MB, and BPA on MIL-53(Fe)_UTS. The types of simultaneous adsorption can be categorized as synergism (Rq > 1), antagonism (Rq < 1), and noninteraction (Rq = 1) according to the literature.60

Table 5. Ratios of Adsorption Capacities of MIL-53(Fe)_UTS.

adsorbent Rq,MO Rq,MB Rq,BPA
MIL-53(Fe)_UTS 0.95 0.45 0.46
Open in a new tab

MIL-53(Fe)_UTS exhibits an Rq,MO of 0.95, indicating that the MO adsorption capacity of MIL-53(Fe)_UTS remains nearly unaffected by the presence of MB, BPA, and coexisting organic substances such as F127 and CTAB in multicomponent systems. This phenomenon is in agreement with the adsorption behaviors of MIL-53(Fe)_UTS in a single-component system because the interactions of MIL-53(Fe) with MO were stronger than those with MB and BPA. Moreover, this phenomenon illustrates that coexisting organic substances cannot enter the pore and competitively interact with active sites in MIL-53(Fe)_UTS because F127 and CTAB have high molecular weights of 12,600 and 364.5 g mol–1, respectively.

Considering the sufficient adsorptive property and greener preparation method of MIL-53(Fe)_UTS, it could be regarded as an economical, ecofriendly, and efficient adsorbent for the treatment of wastewater.

4. Conclusions

In this study, we experimentally confirmed that the sonochemical synthesis of the flexible MIL-53(Fe) MOF is faster than the conventional solvothermal method, and the size of the MIL-53(Fe) particles prepared via UTS irradiation was reduced. Furthermore, the prepared MIL-53(Fe)_UTS particles exhibited enhanced adsorption performance for organic pigments compared to MIL_53(Fe) in aqueous solutions. These results suggested that the particle size of the flexile MOF influences the adsorption capacity toward organic compounds. Anionic MO was more efficiently adsorbed by MIL-53(Fe)_UTS than BPA and MB molecules because of the assistance of π–π interactions and electrostatic attraction. Fortunately, the maximum adsorption capacity of MIL-53(Fe)_UTS for MO was significantly higher than those of other previously reported adsorbents. MIL-53(Fe)_UTS had advantages over other MOF-based adsorbents in that it had high adsorption capacities and could be synthesized using facile and cost-effective methods without the use of toxic chemicals during synthesis. Flexible MIL-53(Fe)_UTS could be considered as an efficient, economical, and ecofriendly adsorbent for the purification of contaminated water on an industrial scale.

Acknowledgments

This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.2c01068.

  • Zeta potential of MIL-53(Fe)_UTS at pH 5.6 (Figure S1); zeta potential of MIL-53(Fe)_solvo at pH 5.6 (Figure S2); XRD patterns of MIL-53(Fe)_UTS_H2O (Figure S3); pH effect on zeta potential (a) and adsorption capacity (b) of MIL-53(Fe)_UTS (Figure S4); results of pattern indexing for MIL-53(Fe)_UTS and MIL-53(Fe)_UTS-H2O (Table S1); and lattice parameters of MIL-53(Fe)_UTS and MIL-53(Fe)_UTS-H2O (Table S2) (PDF)

The authors declare no competing financial interest.

Supplementary Material

ao2c01068_si_001.pdf (280.8KB, pdf)

References

  1. Zhou Y. B.; Hu Y. H.; Huang W. W.; Cheng G.; Cui C. Z.; Lu J. A novel amphoteric β-cyclodextrin-based adsorbent for simultaneous removal of cationic/anionic dyes and bisphenol A. Chem. Eng. J. 2018, 341, 47–57. 10.1016/j.cej.2018.01.155. [DOI] [Google Scholar]
  2. Shen T.; Luo J.; Zhang S.; Luo X. Hierarchically mesostructured MIL-101 metal–organic frameworks with different mineralizing agents for adsorptive removal of methyl orange and methylene blue from aqueous solution. J. Environ. Chem. Eng. 2015, 3, 1372–1383. 10.1016/j.jece.2014.12.006. [DOI] [Google Scholar]
  3. Ma Y.-X.; Shao W.-J.; Sun W.; Kou Y.-L.; Li X.; Yang H.-P. One-step fabrication of β-cyclodextrin modified magnetic graphene oxide nanohybrids for adsorption of Pb(II), Cu(II) and methylene blue in aqueous solutions. Appl. Surf. Sci. 2018, 459, 544–553. 10.1016/j.apsusc.2018.08.025. [DOI] [Google Scholar]
  4. Lee J. H.; Kwak S.-Y. Rapid adsorption of bisphenol A from wastewater by β-cyclodextrin-functionalized mesoporous magnetic clusters. Appl. Surf. Sci. 2019, 467–468, 178–184. 10.1016/j.apsusc.2018.10.054. [DOI] [Google Scholar]
  5. Huang W. W.; Hu Y. H.; Li Y. Y.; Zhou Y. B.; Niu D. C.; Lei Z. F.; Zhang Z. Y. Citric acid-crosslinked β-cyclodextrin for simultaneous removal of bisphenol A, methylene blue and copper: the roles of cavity and surface functional groups. J. Taiwan Inst. Chem. E 2018, 82, 189–197. 10.1016/j.jtice.2017.11.021. [DOI] [Google Scholar]
  6. Bhatnagar A.; Anastopoulos I. Adsorptive removal of bisphenol A (BPA) from aqueous solution: a review. Chemosphere 2017, 168, 885–902. 10.1016/j.chemosphere.2016.10.121. [DOI] [PubMed] [Google Scholar]
  7. Wu Q.; Feng C.; Wang C.; Wang Z. A facile one-pot solvothermal method to produce superparamagnetic graphene–Fe3O4 nanocomposite and its application in the removal of dye from aqueous solution. Colloids Surf., B 2013, 101, 210–214. 10.1016/j.colsurfb.2012.05.036. [DOI] [PubMed] [Google Scholar]
  8. Wang J.; Ji S.; Ma R.; Wu Q.; Wang C.; Qiang J.; Wang Z. Synthesis of magnetic Fe3O4 modified graphene nanocomposite and its application on the adsorption of some dyes from aqueous solution. Sep. Sci. Technol. 2014, 49, 861–867. 10.1080/01496395.2013.862721. [DOI] [Google Scholar]
  9. Gong Y.; Liu G.; Wang Q.; Zhu A.; Liu P.; Wu Q. Synthesis of a novel mesoporous Fe3O4@SiO2/CTAB-SiO2 composite material and its application in the efficient removal of bisphenol A from water. Colloid Polym. Sci. 2021, 299, 807–822. 10.1007/s00396-020-04801-6. [DOI] [Google Scholar]
  10. Jiao C.; Wang Y.; Li M.; Wu Q.; Wang C.; Wang Z. Synthesis of magnetic nanoporous carbon from metal-organic framework for the fast removal of organic dye from aqueous solution. J. Magn. Magn. Mater. 2016, 407, 24–30. 10.1016/j.jmmm.2016.01.031. [DOI] [Google Scholar]
  11. Hasan Z.; Jhung S. H. Removal of hazardous organics from water using metal-organic frameworks (MOFs): plausible mechanisms for selective adsorptions. J. Hazard. Mater. 2015, 283, 329–339. 10.1016/j.jhazmat.2014.09.046. [DOI] [PubMed] [Google Scholar]
  12. Gordon J.; Kazemian H.; Rohani S. MIL-53(Fe), MIL-101, and SBA-15 porous materials: potential platforms for drug delivery. Mater. Sci. Eng. C 2015, 47, 172–179. 10.1016/j.msec.2014.11.046. [DOI] [PubMed] [Google Scholar]
  13. Naeimi S.; Faghihian H. Application of novel metal organic framework, MIL-53(Fe) and its magnetic hybrid: for removal of pharmaceutical pollutant, doxycycline from aqueous solutions. Environ. Toxicol. Pharmacol. 2017, 53, 121–132. 10.1016/j.etap.2017.05.007. [DOI] [PubMed] [Google Scholar]
  14. Bernini M. C.; Fairen-Jimenez D.; Pasinetti M.; Ramirez-Pastor A. J.; Snurr R. Q. Screening of bio-compatible metal–organic frameworks as potential drug carriers using Monte Carlo simulations. J. Mater. Chem. B 2014, 2, 766–774. 10.1039/c3tb21328e. [DOI] [PubMed] [Google Scholar]
  15. Yılmaz E.; Sert E.; Atalay F. S. Synthesis, characterization of a metal organic framework: MIL-53 (Fe) and adsorption mechanisms of methyl red onto MIL-53 (Fe). J. Taiwan Inst. Chem. E 2016, 65, 323–330. [Google Scholar]
  16. Horcajada P.; Serre C.; Maurin G.; Ramsahye N. A.; Balas F.; Vallet-Regí M.; Sebban M.; Taulelle F.; Férey G. Flexible porous metal-organic frameworks for a controlled drug delivery. J. Am. Chem. Soc. 2008, 130, 6774–6780. 10.1021/ja710973k. [DOI] [PubMed] [Google Scholar]
  17. Gao Y.; Kang R.; Xia J.; Yu G.; Deng S. Understanding the adsorption of sulfonamide antibiotics on MIL-53s: Metal dependence of breathing effect and adsorptive performance in aqueous solution. J. Colloid Interface Sci. 2019, 535, 159–168. 10.1016/j.jcis.2018.09.090. [DOI] [PubMed] [Google Scholar]
  18. Pu M.; Guan Z.; Ma Y.; Wan J.; Wang Y.; Brusseau M. L.; Chi H. Synthesis of iron-based metal-organic framework MIL-53 as an efficient catalyst to activate persulfate for the degradation of Orange G in aqueous solution. Appl. Catal., A 2018, 549, 82–92. 10.1016/j.apcata.2017.09.021. [DOI] [PMC free article] [PubMed] [Google Scholar]
  19. Xiong W.; Zeng G.; Yang Z.; Zhou Y.; Zhang C.; Cheng M.; Liu Y.; Hu L.; Wan J.; Zhou C.; Xu R.; Li X. Adsorption of tetracycline antibiotics from aqueous solutions on nanocomposite multi-walled carbon nanotube functionalized MIL-53(Fe) as new adsorbent. Sci. Total Environ. 2018, 627, 235–244. 10.1016/j.scitotenv.2018.01.249. [DOI] [PubMed] [Google Scholar]
  20. Llewellyn P. L.; Horcajada P.; Maurin G.; Devic T.; Rosenbach N.; Bourrelly S.; Serre C.; Vincent D.; Loera-Serna S.; Filinchuk Y.; Ferey G. Complex adsorption of short linear alkanes in the flexible metal-organic-framework MIL-53(Fe). J. Am. Chem. Soc. 2009, 131, 13002–13008. 10.1021/ja902740r. [DOI] [PubMed] [Google Scholar]
  21. Gordon J.; Kazemian H.; Rohani S. Rapid and efficient crystallization of MIL-53(Fe) by ultrasound and microwave irradiation. Microporous Mesoporous Mater. 2012, 162, 36–43. 10.1016/j.micromeso.2012.06.009. [DOI] [Google Scholar]
  22. Stock N.; Biswas S. Synthesis of metal-organic frameworks (MOFs): Routes to various MOF topologies, morphologies, and composites. Chem. Rev. 2012, 112, 933–969. 10.1021/cr200304e. [DOI] [PubMed] [Google Scholar]
  23. Usman K. A. S.; Maina J. W.; Seyedin S.; Conato M. T.; Payawan L. M. Jr.; Dumee L. F.; Razal J. M. Downsizing metal–organic frameworks by bottom-up and top-down methods. NPG Asia Mater. 2020, 12, 58. 10.1038/s41427-020-00240-5. [DOI] [Google Scholar]
  24. Khan N. A.; Jhung S. H. Synthesis of metal-organic frameworks (MOFs) with microwave or ultrasound: Rapid reaction, phase-selectivity, and size reduction. Coord. Chem. Rev. 2015, 285, 11–23. 10.1016/j.ccr.2014.10.008. [DOI] [Google Scholar]
  25. Tiba A. A.; Tivanski A. V.; MacGillivray L. R. Size-dependent mechanical properties of a metal–organic framework: increase in flexibility of ZIF 8 by crystal downsizing. Nano Lett. 2019, 19, 6140–6143. 10.1021/acs.nanolett.9b02125. [DOI] [PubMed] [Google Scholar]
  26. Jia J.; Xu F.; Long Z.; Hou X.; Sepaniak M. J. Metal-organic framework MIL-53(Fe) for highly selective and ultrasensitive direct sensing of MeHg+. Chem. Commun. 2013, 49, 4670–4672. 10.1039/c3cc40821c. [DOI] [PubMed] [Google Scholar]
  27. Abdpour S.; Kowsari E.; Moghaddam M. R. A. Synthesis of MIL-100(Fe)@MIL-53(Fe) as a novel hybrid photocatalyst and evaluation photocatalytic and photoelectrochemical performance under visible light irradiation. J. Solid State Chem. 2018, 262, 172–180. 10.1016/j.jssc.2018.03.018. [DOI] [Google Scholar]
  28. Banerjee A.; Gokhale R.; Bhatnagar S.; Jog J.; Bhardwaj M.; Lefez B.; Hannoyer B.; Ogale S. MOF derived porous carbon–Fe3O4 nanocomposite as a high performance, recyclable environmental superadsorbent. J. Mater. Chem. 2012, 22, 19694–19699. 10.1039/c2jm33798c. [DOI] [Google Scholar]
  29. Qi L.; Tang X.; Wang Z.; Peng X. Pore characterization of different types of coal from coal and gas outburst disaster sites using low temperature nitrogen adsorption approach. Int. J. Min. Sci. Technol. 2017, 27, 371–377. 10.1016/j.ijmst.2017.01.005. [DOI] [Google Scholar]
  30. Valenzano L.; Civalleri B.; Chavan S.; Bordiga S.; Nilsen M. H.; Jakobsen S.; Lillerud K. P.; Lamberti C. Disclosing the complex structure of UiO-66 metal organic framework: a synergic combination of experiment and theory. Chem. Mater. 2011, 23, 1700–1718. 10.1021/cm1022882. [DOI] [Google Scholar]
  31. Chong S.; Thiele G.; Kim J. Excavating hidden adsorption sites in metal-organic frameworks using rational defect engineering. Nat. Commun. 2017, 8, 1539–1548. 10.1038/s41467-017-01478-4. [DOI] [PMC free article] [PubMed] [Google Scholar]
  32. Al-Muhtaseb A. A. H.; Ibrahim K. A.; Albadarin A. B.; Ali-khashman O.; Walker G. M.; Ahmad M. N. M. Remediation of phenol-contaminated water by adsorption using poly(methyl methacrylate) (PMMA). Chem. Eng. J. 2011, 168, 691–699. 10.1016/j.cej.2011.01.057. [DOI] [Google Scholar]
  33. Shuhong Y.; Meiping Z.; Hong Y.; Han W.; Shan X.; Yan L.; Jihui W. Biosorption of Cu2+, Pb2+ and Cr2+ by a novel exopolysaccharide from Arthrobacter ps-5. Carbohydr. Polym. 2014, 101, 50–56. 10.1016/j.carbpol.2013.09.021. [DOI] [PubMed] [Google Scholar]
  34. Li T.-T.; Liu Y.-M.; Wang T.; Wu Y.-L.; He Y.-L.; Yang R.; Zheng S.-R. Regulation of the surface area and surface charge property of MOFs by multivariate strategy: synthesis, characterization, selective dye adsorption and separation. Microporous Mesoporous Mater. 2018, 272, 101–108. 10.1016/j.micromeso.2018.06.023. [DOI] [Google Scholar]
  35. Ai L.; Zhang C.; Liao F.; Wang Y.; Li M.; Meng L.; Jiang J. Removal of methylene blue from aqueous solution with magnetite loaded multi-wall carbon nanotube: kinetic, isotherm and mechanism analysis. J. Hazard. Mater. 2011, 198, 282–290. 10.1016/j.jhazmat.2011.10.041. [DOI] [PubMed] [Google Scholar]
  36. Li Y.; Liang Y.-Q.; Mao X.-M.; Li H. Efficient removal of Cu(II) from an aqueous solution using a novel chitosan assisted EDTA-intercalated hydrotalcite-like compound composite: Preparation, characterization, and adsorption mechanism. Chem. Eng. J. 2022, 438, 135531 10.1016/j.cej.2022.135531. [DOI] [Google Scholar]
  37. Freundlich H. Concerning adsorption in solutions. Z. Phys. Chem., Stoechiom. Verwandtschaftsl. 1906, 57, 385–470. [Google Scholar]
  38. Vu T. A.; Le G. H.; Dao C. D.; Dang L. Q.; Nguyen K. T.; Nguyen Q. K.; Dang P. T.; Tran H. T. K.; Duong Q. T.; Nguyen T. V.; Lee G. D. Arsenic removal from aqueous solutions by adsorption using novel MIL-53(Fe) as a highly efficient adsorbent. RSC Adv. 2015, 5, 5261–5268. 10.1039/C4RA12326C. [DOI] [Google Scholar]
  39. Huo S.-H.; Yan X.-P. Metal–organic framework MIL-100(Fe) for the adsorption of malachite green from aqueous solution. J. Mater. Chem. 2012, 22, 7449–7455. 10.1039/c2jm16513a. [DOI] [Google Scholar]
  40. Langmuir I. The constitution and fundamental properties of solids and liquids Part I Solids. J. Am. Chem. Soc. 1916, 38, 2221–2295. 10.1021/ja02268a002. [DOI] [Google Scholar]
  41. Zhou M.; Wu Y. N.; Qiao J.; Zhang J.; McDonald A.; Li G.; Li F. The removal of bisphenol A from aqueous solutions by MIL-53(Al) and mesostructured MIL-53(Al). J. Colloid Interface Sci. 2013, 405, 157–163. 10.1016/j.jcis.2013.05.024. [DOI] [PubMed] [Google Scholar]
  42. Qin F.-X.; Jia S.-Y.; Liu Y.; Li H.-Y.; Wu S.-H. Adsorptive removal of bisphenol A from aqueous solution using metal-organic frameworks. Desalin. Water Treat. 2014, 54, 93–102. 10.1080/19443994.2014.883331. [DOI] [Google Scholar]
  43. Tong M.; Liu D.; Yang Q.; Devautour-Vinot S.; Maurin G.; Zhong C. Influence of framework metal ions on the dye capture behavior of MIL-100 (Fe, Cr) MOF type solids. J. Mater. Chem. A 2013, 1, 8534–8537. 10.1039/c3ta11807j. [DOI] [Google Scholar]
  44. Haque E.; Jun J. W.; Jhung S. H. Adsorptive removal of methyl orange and methylene blue from aqueous solution with a metal-organic framework material, iron terephthalate (MOF-235). J. Hazard. Mater. 2011, 185, 507–511. 10.1016/j.jhazmat.2010.09.035. [DOI] [PubMed] [Google Scholar]
  45. Yang J. M.; Ying R. J.; Han C. X.; Hu Q. T.; Xu H. M.; Li J. H.; Wang Q.; Zhang W. Adsorptive removal of organic dyes from aqueous solution by a Zr-based metal-organic framework: effects of Ce(III) doping. Dalton Trans. 2018, 47, 3913–3920. 10.1039/c8dt00217g. [DOI] [PubMed] [Google Scholar]
  46. Haque E.; Lee J. E.; Jang I. T.; Hwang T. K.; Chang J.-S.; Jegal J.; Jhung S. H. Adsorptive removal of methyl orange from aqueous solution with metal-organic frameworks, porous chromium-benzenedicarboxylates. J. Hazard. Mater. 2010, 181, 535–542. 10.1016/j.jhazmat.2010.05.047. [DOI] [PubMed] [Google Scholar]
  47. Sharabati M. A.; Sabouni R. Selective removal of dual dyes from aqueous solutions using a metal organic framework (MIL-53(Al)). Polyhedron 2020, 190, 114762 10.1016/j.poly.2020.114762. [DOI] [Google Scholar]
  48. Li L.; Liu X. L.; Geng H. Y.; Hu B.; Song G. W.; Xu Z. S. A MOF/graphite oxide hybrid (MOF: HKUST-1) material for the adsorption of methylene blue from aqueous solution. J. Mater. Chem. A 2013, 1, 10292–10299. 10.1039/c3ta11478c. [DOI] [Google Scholar]
  49. Park E. Y.; Hasan Z.; Khan N. A.; Jhung S. H. Adsorptive removal of bisphenol-A from water with a metal-organic framework, a porous chromium-benzenedicarboxylate. J. Nanosci. Nanotechnol. 2013, 13, 2789–2794. 10.1166/jnn.2013.7411. [DOI] [PubMed] [Google Scholar]
  50. Song J. Y.; Jhung S. H. Adsorption of pharmaceuticals and personal care products over metal-organic frameworks functionalized with hydroxyl groups: Quantitative analyses of H-bonding in adsorption. Chem. Eng. J. 2017, 322, 366–374. 10.1016/j.cej.2017.04.036. [DOI] [Google Scholar]
  51. Zbair M.; Ainassaari K.; El Assal Z.; Ojala S.; El Ouahedy N.; Keiski R. L.; Bensitel M.; Brahmi R. Steam activation of waste biomass: highly microporous carbon, optimization of bisphenol A, and diuron adsorption by response surface methodology. Environ. Sci. Pollut. Res. 2018, 25, 35657–35671. 10.1007/s11356-018-3455-3. [DOI] [PMC free article] [PubMed] [Google Scholar]
  52. Ma J.; Yu F.; Zhou L.; Jin L.; Yang M.; Luan J.; Tang Y.; Fan H.; Yuan Z.; Chen J. Enhanced adsorptive removal of methyl orange and methylene blue from aqueous solution by alkali-activated multiwalled carbon nanotubes. ACS Appl. Mater. Interfaces 2012, 4, 5749–5760. 10.1021/am301053m. [DOI] [PubMed] [Google Scholar]
  53. Lin K.-Y. A.; Chang H.-A.; Hsu C.-J. Iron-based metal organic framework, MIL-88A, as a heterogeneous persulfate catalyst for decolorization of Rhodamine B in water. RSC Adv. 2015, 5, 32520–32530. 10.1039/C5RA01447F. [DOI] [Google Scholar]
  54. Wang J.; Wan J.; Ma Y.; Wang Y.; Pu M.; Guan Z. Metal–organic frameworks MIL-88A with suitable synthesis conditions and optimal dosage for effective catalytic degradation of Orange G through persulfate activation. RSC Adv. 2016, 6, 112502–112511. 10.1039/C6RA24429G. [DOI] [Google Scholar]
  55. Huang D. D.; Li S.; Wu Y. P.; Wei J. H.; Yi J. W.; Ma H. M.; Zhang Q. C.; Liu Y. L.; Li D. S. In situ synthesis of a Fe3S4/MIL-53(Fe) hybrid catalyst for an efficient electrocatalytic hydrogen evolution reaction. Chem. Commun. 2019, 55, 4570–4573. 10.1039/c9cc01433k. [DOI] [PubMed] [Google Scholar]
  56. Chen H.; Liu Y.; Cai T.; Dong W.; Tang L.; Xia X.; Wang L.; Li T. Boosting photocatalytic performance in mixed-valence MIL-53(Fe) by changing Fe(II)/Fe(III) ratio. ACS Appl. Mater. Interfaces 2019, 11, 28791–28800. 10.1021/acsami.9b05829. [DOI] [PubMed] [Google Scholar]
  57. Liu S.; Huo Q.; Chen R.; Chen P.; Li Y.; Han Y. Synthesis and characterization of an iron nitride constructed by a novel template of metal organic framework. J. Spectrosc. 2015, 2015, 362103 10.1155/2015/362103. [DOI] [Google Scholar]
  58. Loiseau T.; Serre C.; Huguenard C.; Fink G.; Taulelle F.; Henry M.; Bataille T.; Ferey G. A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration. Chem. – Eur. J. 2004, 10, 1373–1382. 10.1002/chem.200305413. [DOI] [PubMed] [Google Scholar]
  59. Yaseen D. A.; Scholz M. Textile dye wastewater characteristics and constituents of synthetic effluents: a critical review. Int. J. Environ. Sci. Technol. 2019, 16, 1193–1226. 10.1007/s13762-018-2130-z. [DOI] [Google Scholar]
  60. Lee J. H.; Kwak S.-Y. Branched polyethylenimine-polyethylene glycol-β-cyclodextrin polymers for efficient removal of bisphenol A and copper from wastewater. J. Appl. Polym. Sci. 2020, 137, 48475. 10.1002/app.48475. [DOI] [Google Scholar]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

ao2c01068_si_001.pdf (280.8KB, pdf)

Articles from ACS Omega are provided here courtesy of American Chemical Society

RESOURCES