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Sustainable Synthesis of MOF-5@GO Nanocomposites for Efficient

Removal of Rhodamine B from Water
Gyanendra Kumar and Dhanraj T. Masram*
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ABSTRACT: Herein, a metal−organic framework (MOF-5) is

synthesized by a solvothermal process and graphene oxide (GO) is
prepared from the improved Hummer’s method. The synthesis of
MOF-5@GO nanocomposites is one-pot process via a grinding
method and employed for the removal of Rhodamine B (RhB)
Downloaded via 103.120.38.88 on May 14, 2021 at 06:15:45 (UTC).

dye. The removal efficiency of RhB is found to be 60.64% (151.62

mg·g−1) at 500 ppm. About 98.88% of RhB is removed within 5
min of contact time and increased up to 99.68% up to 10 min. The
removal rate of MOF-5@GO nanocomposites is much better than
that of pristine MOF-5. Equilibrium adsorption capacity is
determined by a series of different experimental conditions such
as pH, time, and concentration of dye solution. Although the
results also showed that dye removal on MOF-5@GO nano-
composites is well described by the Langmuir isotherm (R2 = 0.9703), the adsorption kinetics data reveals pseudo-second-order (R2
= 0.9908). The synthesized nanocomposite is efficient for removal of dye, cost-effective, and reusable. Additionally, stability and self-
degradation studies of pure RhB are reported in aqueous solution for up to 120 days at different pH values (pH 1−12).

1. INTRODUCTION zole (HBT),10 alumina oxides,11 Fe3O4@L-arginine,12 porous

Rhodamine B (RhB) is a well-known cationic fluorescent dye
that is widely used as a colorant in textiles, foodstuffs, scientific
research, and pharmaceutical industries.1 It is toxic and
harmful to human beings and animals, causes damage to
skin, eyes, and respiratory tract, and causes gene mutations.
Additionally, it is a well-known carcinogenic and neurotoxic
material toward animals and humans.2 Worldwide, more than
10,000 textile dyes are used commercially with their yearly
production exceeding ∼7 × 105 metric tons,3 out of which
about 2% (∼14 × 103 metric tons) of the annual dye
production is discharged as an effluent from manufacturing
units. Color is one of the clearest indicators of water pollution
caused by the discharge of dye as a waste, which is responsible
for the damage to water bodies, aesthetic pollution,
eutrophication, and perturbations in aquatic life.4,5 RhB exists
for a long time in a natural water body or aqueous medium. So,
it is necessary to remediate dye from the aqueous solution. The
remediation of dye from the aqueous medium is one of the
most challenging tasks. Among the several purification
techniques, adsorption process has been verified to be one of
the best and simplest techniques for eliminating pollutants
from water bodies. The advantages of the adsorption process
are its cost-effectiveness, accuracy, remarkable versatility,
simplicity in design, safety of operation, high efficiency, and
adsorbent reusability.6−8 There are many reports where a
variety of substrates are used for adsorption of dye from
wastewater such as Cu-MOF,9 modified 1-hydroxybenzotria-
© 2021 The Authors. Published by
American Chemical Society
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silica beads,13 carbon nanotubes14 (CNT), carbon-based
materials,15 and graphene oxide16 (GO); however, in these
cases, there is poor sorption capacities, multi-step synthesis,
and low sorption rates. Therefore, MOFs/GO-based nano-
composites are potential material for the adsorption of dye due
to easy modification of surface, low toxicity, and large surface
area. Consequently, there is an urgent need for these types of
nanocomposite materials that can adsorb toxic dye more
efficiently. The cationic dye (RhB) is known to be better
adsorbed on the graphene oxide via strong interactions from
negatively charged oxygenated functional groups.17,18 Already
available adsorbents are not only expensive but also difficult to
handle and redevelop after use. Meanwhile, metal−organic
frameworks (MOFs) are highly ordered crystalline coordina-
tion polymers and one of the most fascinating classes of
adsorbent,19 having the advantages of high surface area,
porosity, excellent absorbability, good catalytic activity, and
controlled modification synthesis.20 Additionally, MOFs are
promising candidates for a variety of applications such as dye
Received: January 9, 2021
Accepted: March 17, 2021
Published: March 30, 2021
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Figure 1. FTIR spectra of (a) (i) GO, (ii) MOF-5, (iii) MOF-5@GO, (iv) RhB, and (v) RhB-MOF-5@GO nanocomposites. XRD pattern of (b)
MOF-5 standard and (c) (i) graphite powder, (ii) GO, (iii) MOF-5, (iv) MOF-5@GO, and (v) RhB-MOF-5@GO nanocomposites. (d, e) FTIR
and XRD of as-synthesized nanocomposites and after water immersion for up to 7 days.
adsorption, energy storage, catalysis, and gas separation.21 In
the case of MOF-5, formerly described in 1999, it is made up
of ZnO4 units connected by a 1,4-benzenedicarboxylate linker
to form an amazing cubic network. The first series of MOF-5
reported in 2002 is cubic in shape.22 The increased catalytic
activity, conductivity, and surface area of MOFs needed to be
combined with other materials such as mesoporous silica/
MOF, mesoporous alumina/MOF, and MOF/graphene have
been reported for adsorption.23−29 Furthermore, carbon-based
materials including activated carbon, CNT, and GO have also
been incorporated with MOFs to improve the adsorptive
properties of composite materials.30 Owing to their remarkable
chemical and physical characteristics, MOFs/GO-based nano-
composite materials are in tremendous demand for adsorption
of dye.31,32 In the last 10 years, the excellent and exclusive
chemical, electrical, and mechanical characteristics of graphene
oxide have attracted remarkable interest.33 The process of
chemical modification of graphene and graphene oxide
includes covalent binding and non-covalent binding.34 The
structure of graphene is extremely stable, the bond between
each carbon atom is strong, and the connection between
carbon atoms via a covalent bond is strong. Graphene has a
simpler synthetic process and lower production cost as
compared to other carbon-based materials. GO is a two-
dimensional material with hexagonal shape and has well-
developed functional groups that contain oxygen moieties.
However, these oxygen-containing groups may increase
catalytic activity, increase stability, and are also according to
the requirements that need chemical modification.35 GO is
readily dispersed in water and some other polar solvents due to
its hydrophilic character, water stability, and solution
dispersibility.36 A series of MOF@GO composites of excellent
adsorption capacity has been recorded by the Bandosz
group.24,37 However, the possible interactions between GO
and MOF-5 composites enhance the hydrophobic stability of
the MOF-5 framework.38,39 MOF-5 also has the characteristic
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problem due to lack of stability in water. The development of
MOF-GO composites occurs through interactions between
oxygen groups of GO and the metallic centers of MOFs by
chemical bonding or electrostatic interaction.40,41 Therefore, to
resolve its shortcomings, the combination of MOF-5 with GO
is largely necessary. However, there are needs for MOF-5@GO
nanocomposites such as one-step synthesis, ambient reaction
conditions, potential for catalyst recovery, recyclability, and
efficient and successful adsorbents for RhB in the treatment of
wastewater. This is a simple and solvent-free synthetic process
to minimize environmental pollution. Herein, we report a one-
step synthesis of MOF-5@GO nanocomposites employed for
adsorption kinetic studies of RhB. Additionally, the effect of
MOF-5 and GO ratio (1:1, 1:2, and 2:1) with pH, contact
time, and concentration of RhB on the adsorption performance
is also studied. Moreover, adsorption kinetics and adsorption
isotherms are well described along with the plausible
mechanism of RhB adsorption onto MOF-5@GO nano-
composites. The stability and self-degradation studies of RhB
(up to 120 days) at different pH values (pH 1−12) are also
reported.
2. RESULTS AND DISCUSSION
2.1. FTIR and XRD Study. The FTIR and XRD spectra of
pristine GO, MOF-5, MOF-5@GO, and RhB-MOF-5@GO
nanocomposites are given in Figure 1. The FTIR spectrum of
GO exhibits strong characteristics bands at 3414, 1734, 1618,
1224, 1041, and 866 cm−1 (Figure 1a(i)). The typical peaks
found in GO are the hydroxyl group of −OH stretching
vibrations at 3414 cm−1, the carbonyl or carboxylic moiety of
CO stretching frequency at 1734 cm−1, the aromatic
stretching frequency of CC present at 1618 cm−1, and the
stretching vibration of C−O epoxy found at 1224 cm−1. The
C−O alkoxy stretching vibration appeared at 1041 cm−1, and
the epoxy or peroxide functional group occurred at 866 cm−1
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Figure 2. High-resolution XPS of (a) C1s of GO, (b) C1s of MOF-5, (c) O1s of GO, (d) O1s of MOF-5, and (e) Zn2p metal. (f) Survey XPS
spectra of (i) GO, (ii) MOF-5, and (iii) MOF-5@GO nanocomposites.
of GO.42 The pure MOF-5 shows two strong bands present at
1657 and 1599 cm−1 corresponding to the CO and C−O
stretching vibration of the aromatic ring of terephthalic acid.
The stretching frequency of C−H is found at 1387 cm−1,
although the characteristics peaks were found at 1200−600
cm−1 out-of-plane vibrations of an aromatic ring of terephthalic
acid of the MOF-5 framework.43 The absorption band appears
at 530 cm−1 can be assigned to the Zn−O stretching frequency
as shown in Figure 1a(ii). FTIR spectra of MOF-5@GO
nanocomposites show that the majority of peaks for GO and
MOF-5 are retained and there was no significant change. It was
also proven that GO did not affect the property of MOF-5, as
given in Figure 1a(iii). FTIR spectra of RhB are shown in
Figure 1a(iv), and the absorption band displayed at 1683 cm−1
can be assigned to the stretching frequency of CO. The
peaks at 2985 cm−1 indicated the stretching band of −CH. The
peaks at 1586 cm−1 were attributed to the stretching vibration
of the aromatic benzene ring of CC. The functional group of
RhB shows peaks at 1403 (−CH3), 1327 (CN), and 991
cm−1 for the C−H group. The RhB-adsorbed MOF-5@GO
nanocomposite is shown in Figure 1a(v).
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The adsorption band slightly shifted, and the obtained bands
are found at 2977, 1685, 1586, 1549, 1389, 1294, 932, and 757
cm−1, which may be hydrogen bonding and confirm the RhB
adsorbed on MOF-5@GO nanocomposites.44 The Zn−O
band is shifted and found to be 494 cm−1 due to interactions
with water, GO, and RhB. However, after being immersed in
water up to 5 days, the MOF-5@GO nanocomposite did not
lose its crystallinity. Additionally, some interactions from
oxygenated functional groups of graphene oxide with vacant
sites of the zinc cluster of MOF-5 maintain the crystallinity as
well as increase the conductivity of MOF-5 and enhanced the
adsorption properties, and this is consistent with a previous
study.45 Furthermore, the FTIR spectrum of MOF-5@GO
nanocomposites in water is observed up to the 7th day, which
is represented in Figure 1c. Subsequently, the interactions of
the −OH group of the water molecule from vacant sites of the
zinc cluster may create some disorderness of MOF-5 by
breaking of the Zn−O bond between the metal cluster and
organic linker.
The XRD pattern of graphite, GO, MOF-5, MOF-5@GO,
and RhB-MOF-5@GO nanocomposites is shown in Figure 1c.
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Figure 3. (a) (i) GO, (ii) MOF-5, (iii) RhB, and (iv) RhB-MOF-5@GO nanocomposites. (b) RL values.
Graphite shows a characteristic sharp peak at 2θ = 26.5°
attributed46 to ⟨002⟩ as shown in Figure 1c(i). Furthermore,
GO shows typical peaks in Figure 1c(ii) for planes ⟨001⟩ and
⟨100⟩ at 2θ = 10.3° and 46.3°, respectively. Pure MOF-5 has
shown crystalline peaks, which find 2θ values at 6.82, 9.65
13.65, 15.30, 20.59, 22.36, 24.71, 31.31, and 32.13 for crystal
planes ⟨200⟩, ⟨220⟩, ⟨400⟩, ⟨420⟩, ⟨531⟩, ⟨533⟩, ⟨551⟩, ⟨751⟩,
and ⟨911⟩, respectively, as depicted in Figure 1c(iii). The
MOF-5@GO shows diffraction peaks detected at 2θ at 10.12,
15.61, 18.55, 20.58, 25.95, 27.27, 28.39, 30.31, 31.12, 32.34,
34.06, and 43.80, and these peaks are slightly shifted as
compared to pure MOF-5 but do not distort the crystalline
nature after the combination of GO as shown in Figure 1c(iv).
The RhB-adsorbed MOF-5@GO nanocomposite shows
similar diffraction peaks for MOF-5@GO nanocomposites,
which is shown in Figure 1c(v). The adsorbed molecule RhB is
not crystalline, it is amorphous. Furthermore, XRD results
show that the crystalline nature of MOF-5@GO nano-
composites did not distort up to the 5th day of MOF-5@
GO nanocomposites47 as shown in Figure 1e. However, after 7
days, the crystallinity of MOF-5@GO nanocomposites was lost
and might be some distorted after being immersed in water
due to strong interactions from the free vacant d-orbital of the
zinc metal cluster,48,49 as given in Figure 1d.
2.2. X-ray Photoelectron Spectroscopy (XPS) Studies.
The synthesized GO, MOF-5, and MOF-5@GO nano-
composites were further studied via XPS to define the
chemical states of different aspects and the presence of
functional groups.50,51 The deconvoluted high-resolution XPS
C1s region spectra of GO and MOF-5 are displayed in Figure
2a,b, respectively. The C1s spectra of pristine GO have
characteristic peaks at binding energies of 282.80, 284.78,
285.81, and 287.16 eV, representing C−C, C−O, and OC
O, and CO respectively (Figure 2a). Similarly, the high-
resolution XPS of the C1s region spectra of MOF-5 (Figure
2b) have peaks with binding energies of 284.91, 286.0, and
288.86 eV, which can be attributed to C−C, CO, and O
CO, respectively. Figure 2c illustrates the XPS of O1s of GO
where peaks at binding energies of 529.55, 530.59, 531.34, and
531.62 eV represent OCO, CO, C−OH, and C−O−C,
respectively. Moreover, the deconvoluted O1s of MOF-5 as
shown in Figure 2d depicts peaks at binding energies of 529.91
and 531.49 eV representing OCO and CO, respec-
tively. Furthermore, peaks at binding energies of 1045.13 and
1022.07 are attributed to Zn2p1/2 and Zn2p3/2 as represented
in Figure 2e. The full spectra of GO, MOF-5, and MOF-5@
GO nanocomposites clearly showing the presence of carbon,
oxygen, and zinc metal are represented in Figure 2f.
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2.3. Thermogravimetric Analysis. GO, MOF-5, and
RhB-MOF-5@GO nanocomposites were characterized by
thermogravimetric analysis (TGA) and are shown in Figure
3. GO shows four weight loss results between 25 and 600 °C as
shown in Figure 3a(i). The first weight loss observed between
25 and 106 °C (17.07%) can be assigned to the removal of
physically adsorbed water. The second weight loss between
106 and 183 °C (9.39%) is attributed to the removal of labile
oxygen-containing functional groups. The third weight loss
between 183 and 220 °C (24.3%) indicates the decomposition
of stable oxygen functionalities. The fourth weight loss
between 220 and 600 °C (27.68%) is due to the full collapse
of GO.
There are four weight loss results of MOF-5 depicted in
Figure 3a(ii). The weight loss between 25 and 119 °C (2.67%)
is due to the removal of physically adsorbed water. The weight
loss between 119 and 215 °C (15.62%) is attributed to the
removal of N,N-dimethylformamide. The weight loss between
215 and 330 °C (13.1%) is due to the partial decomposition of
the MOF-5 frameworks. The weight loss between 330 and 524
°C (41.79%) is due to the collapse of the framework52 of
MOF-5 and constant up to 600 °C.
RhB shows three weight loss results between 176 and 600
°C and stability up to 176 °C. The first weight loss between
176 and 215 °C (4.07%) is attributed to the removal of water,
the second weight loss between 215 and 300 °C (8.89%) is
credited to the removal of the oxygen functionality group, and
the third weight loss between 300 and 600 °C (65.22%) is
attributed to aromatic containing groups as illustrated in Figure
3a(iii).
In the case of RhB-MOF-5@GO nanocomposites, there are
five weight loss results. The first weight loss between 25 and 99
°C (7.32%) indicates the loss of physically adsorbed water.
The second weight loss between 97 and 167 °C (4.07%)
indicates the loss of oxygen functionality of the surface of GO
sheet. The third weight loss between 167 and 215 °C (12.76%)
is due to the DMF molecule as well as the stable oxygen
functionality of GO and RhB functional groups, and the fourth
weight loss between 215 and 300 °C (18.28%) is attributed to
the partial decomposition of the MOF-5 frameworks, GO, and
RhB functional groups, while the fifth weight loss between 300
and 600 °C (23.57%) can be attributed to the full
decomposition of RhB-MOF-5@GO nanocomposites as
shown in Figure 3a(iv).
2.4. Surface Area Analysis. The N2 adsorption−
desorption isotherm of GO (Figure S2a), MOF-5 (Figure
S2b), and MOF-5@GO nanocomposites (Figure S2c) is
shown in the Supporting Information. The MOF-5@GO
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Figure 4. FESEM monograph of (a) GO, (b) MOF-5, and (c) RhB-MOF-5@GO. (d) HRTEM image of RhB-MOF-5@GO nanocomposites.
Figure 5. (a) Stability of RhB at pH 1−12. (b) Calibration plot of RhB.
nanocomposite of the surface area is found to be 135.37 m2
g−1, indicating the successful reaction with GO and MOF-5.
The surface area of the MOF-5 is 29.95 m2 g−1, which is
greater than that from the literature, which is given as 12.35 m2
g−1.53 This value is too low due to air exposure during the
treatment, and the perfect BET surface area of MOF-5 as
reported by the group of Yaghi54 reached up to 2900 m2 g−1.
The surface area of GO is found to be 9.45 m2 g−1. The specific
surface area of the synthesized nanocomposite material is
increased due to the combination of MOF-5 and GO. The
calculated results indicate that the average pore size of the
MOF-5@GO nanocomposite is found to be 0.014 nm. The
higher surface area and pore volume of MOF-5@GO
nanocomposites can afford extra possible sites for adsorption
reactions. The MOF-5@GO nanocomposite displays a type III
curve and H3 hysteresis loop, and this indicates that the MOF-
5@GO nanocomposite is shown as a mesoporous structure
with a relatively high surface area.
2.5. Morphological Characterization. The morphologies
of nanocomposite are studied by HRTEM and FESEM, and
illustrations of the pristine GO sheet, pure MOF-5, and RhB-
adsorbed MOF-5@GO nanocomposites are shown in Figure 4.
The FESEM image of GO shows that it is a typical sheet-like
randomly aggregated thin crumpled layer structure as shown in
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Figure 4a. The FESEM image of pure MOF-5 depicts a stacked
elongated hexagonal structure as shown in Figure 4b. However,
in the FESEM image in Figure 4c and HRTEM image in
Figure 4d of RhB-MOF-5@GO nanocomposites, MOF-5
formed an irregularly shaped structure of 50−200 nm instead
of an elongated hexagon, and this might be due to the facile
synthesis of the nanocomposite. Furthermore, energy-dis-
persive X-ray spectroscopy (EDS) of RhB-adsorbed MOF-
5@GO nanocomposites shows the elemental composition as
well as mapping of elements such as C, O, N, Cl, and Zn as
given in the Supporting Information, i.e., Figure S3a−g.
2.6. Influence of Process Variable on Adsorption.
2.6.1. Effect of pH on RhB. The absorbance spectra of the RhB
were recorded in an aqueous solution from the wavelength of
350−650 nm in a quartz cell having a path length of 1 cm with
λmax corresponding to RhB found at 554 nm. The absorbance
spectra of RhB show a pH-independent behavior at pH 4−12
and are shown in Figure 5a. There is no noticeable change that
occurs in this range. Thus, this confirms that RhB is more
stable and does not lose its chemical behavior between pH 4
and 12.
2.6.2. Calibration Plot of RhB. The stock solution of RhB
was prepared in double-distilled water. A series of solutions
with known concentrations (1−8 ppm) were prepared in a 25
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Figure 6. Removal of RhB at (a) 1:1, (b) 1:2, and (c) 2:1 ratios as a function of pH and (d) a function of time.

Figure 7. Percentage removal (a) effect of the initial concentration of RhB and (b) effect of Ni2+ and Cu2+ metal ions.

mL standard volumetric flask. The Lambert−Beer law is valid %removal of RhB

up to 6 ppm for RhB dye. RhB in aqueous solution shows a
pH-independent absorption behavior at a range of 4−12.
However, the calibration plot of RhB was prepared at pH 7,
and the correlation coefficient (R2) was found to be 0.996 and
is shown in Figure 5b. Hence, at pH 7, further estimation of
RhB has been carried out.
2.6.3. Batch Extraction Study and Removal of RhB. Using
the batch extraction process, the adsorption behavior of RhB
on MOF-5@GO nanocomposites was studied as a function of
pH, contact time, and initial concentration of the aqueous RhB
solution. Each experiment was done with 50 mg of the
nanocomposite at room temperature. The unabsorbed RhB
concentration present in the supernatant was calculated by
UV−Vis spectrophotometry. The percentage (%) removal of
RhB on the MOF-5@GO nanocomposite was determined
using eq 1:
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initial con. of RhB − final con. of RhB
= × 100
initial con. of RhB (1)
2.6.4. Removal of RhB as a Function of pH. In the
adsorption method, pH plays an important role in RhB. This
study was done at 50 mg of the nanocomposite in different
ratios of MOF-5 and GO and 25 mL of 20 ppm RhB at
different pH values like 2, 4, 5, 6, 8, and 12 at room
temperature as given in Figure 6. Adsorption of RhB on the
ratio of MOF-5 and GO such as 1:1, 1:2, and 2:1 is shown in
Figures 66b, and 6ca, , respectively. The highest removal of
RhB was observed on the ratio of 1:1 in comparison to 1:2 and
2:1. Henceforth, the 1:1 ratio is selected for further batch
study. The amount of RhB adsorbed on MOF-5@GO
nanocomposites was found in a higher acidic medium (at
pH 2) as compared to the basic medium and remained almost
constant from pH 6 to 8. So, consequently, pH 2 and 1:1 ratio
are chosen for further study.
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Table 1. Parameters of the Kinetic and Adsorption Isotherm
pseudo-first-order kinetics
K1 (min−1) qe (mg/g) R2
0.4470 9.6272 0.4025
Freundlich adsorption isotherm
1/n n Kf R2
0.5254 1.9033 9.4362 0.0861
2.6.5. Removal of RhB as a Function of Contact Time. In
the study, 50 mg of MOF-5@GO nanocomposites was used
for 25 mL of 20 ppm RhB for adsorption while maintaining the
pH at 2. Approximately 98.88% of RhB is removed within 5
min of contact time, which increased to 99.68% within 10 min,
and this may be due to the availability of more adsorption sites
due to a high surface area. However, adsorption remained
almost constant after 15 min as shown in Figure 6d. The
reason thereof, during the initial few minutes, is that the rate of
removal of RhB is very fast due to the concentration gradient
that formed at the start of the process between RhB and the
adsorbent surface. This effect is clarified by the presence of
vacant sites on the surface of MOF-5@GO nanocomposites
available for adsorption. Furthermore, due to the saturation of
adsorption sites or blockage of pore on MOF-5@GO
nanocomposites, the adsorption percent of RhB becomes
constant.
2.6.6. Effect of the Initial Concentration of RhB. The
removal of RhB by MOF-5@GO nanocomposites is also
affected by the initial amount of RhB present in the aqueous
solution. Therefore, the consequence of initial concentration
on the removal of RhB is investigated with 25 mL of RhB with
50 mg of MOF-5@GO nanocomposites at pH 2, and the
concentration of RhB that varies from 5 to 550 ppm is shown
in Figure 7a. The rate of removal of RhB by MOF-5@GO
nanocomposites increases up to 500 ppm; however, due to
saturation of available loading sites, no significant increment in
adsorption percentage of RhB is further observed.
The removal of RhB was found to be 60.64% (151.62 mg·
g−1) at 500 ppm; therefore, RhB adsorbed on MOF-5@GO
nanocomposites. Hence, to investigate the structure and
morphology of MOF-5@GO nanocomposite with appropriate
analytical techniques, it was prepared in large amount.
2.6.7. Effect of Metal Concentration on RhB. The effect of
metal ion concentration also played a crucial role in the
remediation of RhB. The effect of metal ions Ni2+ and Cu2+ at
different concentrations (5−100 ppm) on the removal of RhB
on MOF-5@GO nanocomposites has been studied. In the
presence of Cu2+, the percentage removal efficiency of RhB on
MOF-5@GO nanocomposites decreases with an increase in
the concentration of a metal ion, but in the case of Ni2+ ion,
the percentage removal of RhB on MOF-5@GO nano-
composites slightly decreases with increasing the concentration
of a metal ion in aqueous solution.55 In the presence of heavy
metals, the adsorption capacity of dyes onto the MOF-5@GO
surface decreases due to the preferential adsorption of these
metal ions onto the active site of the MOF-5@GO
nanocomposite shown in Figure 7b.
2.7. Description of Adsorption Kinetics and Iso-
therms. Chemical kinetics deals with the rate of reaction, as
well as its mechanism, which is given in the Supporting
Information. In the adsorption process, there are three types of
adsorption kinetics. Pseudo-first-order kinetics is defined by
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pseudo-second-order kinetics
K2 [g/mg·min)] qe (mg/g) R2
0.0367 26.7379 0.9908
Langmuir adsorption isotherm
qmax (mg/g) KL (dm3/mg) R2 RL
169.4915 0.0302 0.9703 0.1418
Lagergren in which the plot between log qe−qt against t gives a
straight line as shown in Figure S1a, pseudo-second-order
kinetics is described by Ho and McKay in which the plot
between t/qt against t gives a straight line (Figure S1b), and
the intraparticle diffusion (ID) model given by Weber and
Morris in which the plot between qt against gives a straight line
(Figure S1c) in which the correlation coefficient R2 is found to
be 0.7779. The experimental parameters of pseudo-first-order
and pseudo-second-order kinetics are listed in Table 1. From
the experimental parameter based on the correlation coefficient
value, it is observed that pseudo-second-order kinetics is best
fitted as compared to pseudo-first-order kinetics.
The adsorption capacity of MOF-5@GO nanocomposites
for RhB is also determined by the equilibrium adsorption
study. There are three types of adsorption isotherm. Langmuir
adsorption isotherm defines the development of the monolayer
surface of RhB quantitatively around the adsorbent in which
the plot between Ce/qe against Ce gives a straight line as shown
in Figure S1d, and it can also be defined in terms of a
dimensionless constant known as Hall separation factor (RL)
shown in Figure 3b, which is found to be 0.1418. Freundlich
adsorption isotherm explains the adsorption process in the
heterogeneous systems and the formation of multilayer
adsorption in which the plot between log qe against log Ce
gives a straight line as shown in Figure S1e. Temkin adsorption
isotherm explains the heat of adsorption of the entire molecule
in the adsorbent−adsorbate interaction in which the plot
between qe against Ce gives a straight line as shown in Figure
S1f.
Experimental parameters of the Langmuir and Freundlich
adsorption isotherm are listed in Table 1. From the
experimental parameter based on the correlation coefficient
value, it is observed that the Langmuir adsorption isotherm is
best fitted as compared to the Freundlich adsorption isotherm
in the adsorption of RhB on to the MOF-5@GO nano-
composite.
2.8. Natural Degradation of RhB Concerning pH. Self-
degradation studies of RhB were done to see the degradation
efficiency process naturally at different pH values (pH 1−12)
at a time duration of 1−120 days and are shown in Figure 8a−
l. In acidic conditions, at pH 1, 12.40% (Figure 8a), there is a
small degradation that takes place, but in pH 2, 35.87% (Figure
8b) degraded within 60 days and it remains constant up to 120
days. In pH 3, there is no degradation up to 60 days but
21.59% (Figure 8c) degradation within 90 days takes place and
it remains constant up to 120 days, but in the case of pH 4 and
pH 5, there is no degradation up to 90 and 30 days,
respectively, but in both cases, 30.25% (Figure 8d) and 21.72%
(Figure 8e) degraded up to 120 days. In the case of pH 6, there
are slight decreases after 30 days (Figure 8f). From pH 7 to pH
11, there is no degradation of RhB that was found up to 120
days (Figure 8g−k), but in the case of the strong basic medium
https://doi.org/10.1021/acsomega.1c00143
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Figure 8. Degradation of RhB for 1−120 days at various pH values: (a) pH 1, (b) pH 2, (c) pH 3, (d) pH 4, (e) pH 5, (f) pH 6, (g) pH 7, (h) pH
8, (i), pH 9, (j) pH 10, (k) pH 11, and (l) pH 12.

According to the available reports,56,57 the pH of the

at pH 12, slight degradation was found, which is 36.16% seawater, river, sewage, and lake water may exist from pH 6 to
(Figure 8l) from 15 to 120 days. pH 8, and from experimental data, it is evidenced that RhB
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Figure 9. (a) Removal efficiency of RhB on MOF-5@GO nanocomposites in different cycles. (b) SEM image of MOF-5@GO nanocomposites
after the fifth run.

does not undergo any degradation in this region. It can be cationic dye with highly efficient adsorbents MOF-5@GO
concluded that the RhB exists for a long time in an aqueous nanocomposites.
medium and it is imperative to remediate RhB.
2.9. Adsorption Mechanism of RhB on MOF-5@GO Table 2. Adsorption Capacity of RhB onto MOF-5@GO
Nanocomposites. The adsorption of RhB on the surface and Nanocomposites as Compared with Previous Studiesa
the cavity of MOF-5@GO nanocomposites can be due to
different factors such as electrostatic/ionic interactions, Qe conditions
adsorption adsorbate (mg/g) (°C) ref
hydrogen bonding, and π−π interactions.58−60 Keeping this
in mind, it can be proposed that electrostatic attraction takes CoOF RhB 72.15 20 °C 63
place between positively charged RhB molecules and RGO RhB 13.15 25 °C 64
negatively charged −OH groups of the surface of the MOF- sodium montmorillonite RhB 42.19 30 °C 65
5@GO nanocomposites. The MOF-5@GO nanocomposite CNSs RhB 01.95 25 °C 66
has great advantages, such as high surface area, variable pore MCM-22 RhB 01.05 30 °C 67
sizes, and different functionalities. Figure 1a(v) shows the Perlite RhB 08.72 30 °C 68
FTIR spectrum for the comparison of MOF-5@GO nano- Nano-NiO RhB 111.0 20 °C 69
composite before and after adsorption of RhB. The shifted MOF-5@GO RhB 151.5 RT PW
nanocomposite
peak position is because of the hydrogen bonding, π−π a
PW, present work; RT, room temperature.
interactions, and electrostatic attraction. The removal of dye is
usually based on the effect of size and the importance of ionic
selectivity. Lan et al. created a mesoporous MOF of about 38 Å 2.11. Cyclability. The recycling ability of MOF-5@GO
size-tunable cages and investigated that the size-exclusion nanocomposites is also established where it is renewed by
effect depends on the separation of large dye molecules.61 The centrifugation after the batch experiment followed by excessive
widely accepted theories accounting for the adsorption washing with ethanol and dried at 75 °C before further use in
mechanism of adsorbents are based on their ionic selectivity the next cycle. The recycling performance of regenerated
and size effect. It may also be possible that the cause is due to MOF-5@GO nanocomposites is shown in Figure 10a. An
the filling of pores occurring in the MOF-5 and GO, which is insignificant decrease in adsorption percentage is observed
the inhibition of the adsorption of RhB to that of the after the first three cycles, however remaining constant for the
synthesized MOF-5@GO nanocomposites. Including the high last two cycles.
pore volume also allows them to absorb a greater amount of This slight decrement in adsorption efficiency of nano-
RhB in an aqueous solution. The mechanism for the composites might be due to the movement of the RhB
adsorption of RhB on MOF-5@GO nanocomposites can be molecule toward the interior cavities of the MOF-5@GO
ionic interactions due to presence of unsaturated bonds (C nanocomposite and it could not be washed out easily. The
C, O−CO) in MOF-5, negatively charged GO surface, and SEM image of MOF-5@GO nanocomposites depicted in
positive charge of RhB.62 Furthermore, π−π interaction also Figure 10b after the fifth cycle also shows that there are no
plays as active binding sites for the adsorption of the RhB significant changes occurring in the morphology. These results
molecule with MOF-5@GO nanocomposites. Since RhB demonstrated quicker adsorption integrated with excellent
contains CC double bonds and π-electrons, this π-electron reversibility, thus making it a promising candidate for RhB
can easily interact with the π-electrons of benzene rings on the adsorption in real applications. Furthermore, as compared with
MOF-5 and GO surface via π−π interactions. Based on the previous studies, the MOF-5@GO nanocomposite displays the
above facts of interactions, RhB easily got adsorbed on the highest adsorption capacity, which is listed in Table 2.
surface of MOF-5@GO nanocomposites. A schematic
representing the proposed mechanism of RhB adsorption is 3. CONCLUSIONS
shown in Figure 9. We have successfully developed MOF-5@GO nanocomposites
2.10. Comparison Study. RhB removal capacities by the employed for the removal of toxic dye. Due to electrostatic
synthesized nanocomposites showing greater effectiveness as interactions between the positively charged metal center of
compared with previously reported studies are shown in Table MOF-5 and negative charge on GO surface, MOF-5 and GO
2. The synthesized nanocomposites demonstrate a strong resulted in MOF-5@GO nanocomposite. MOF-5@GO nano-
9595 https://doi.org/10.1021/acsomega.1c00143
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Figure 10. Schematic possible interaction in the adsorption
mechanism of RhB on MOF-5@GO nanocomposites.
composites have an excellent adsorption capacity at a ratio of
1:1 for RhB, proving its application in the remediation of toxic
dye. The physicochemical properties of nanocomposites were
explained with different structural and morphological charac-
terization techniques. The morphology of RhB-adsorbed
MOF-5@GO nanocomposites reveals the growth of irregular
form MOF-5 nanoparticles with sizes varying between 50 and
200 nm. Results of XPS and EDS spectra revealed the presence
of carbon, oxygen, and zinc metal cluster. The adsorption
kinetics data reveals pseudo-second-order (R2 = 0.9908),
although the adsorption isotherm model was well defined by
the Langmuir adsorption isotherm (R2 = 0.9703). The effect of
adsorption capacity in the presence of heavy metal ions, i.e.,
Ni2+ and Cu2+, shows a decrease in the presence of Cu2+ ion
but insignificant in the presence of Ni2+ ion. The adsorption
capacity of MOF-5@GO nanocomposites was found to be
99.58% with 20 ppm at pH 2. In conclusion, MOF-5@GO
nanocomposite is synthesized in one step, it is environmentally
friendly, and cost-effective with high adsorption efficiency and
outstanding reusability, which makes it a better adsorbent
material for the removal of RhB from waste water.
Scheme 1. Simple Representation of the Synthesis of MOF-5@GO Nanocomposites
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4. EXPERIMENTAL SECTION
4.1. Synthesis of Graphene Oxide. GO was synthesized
according to previous reports,70−72 with some modifications
via the improved Hummer’s method. In brief, 90:10 mL of
concentrated H2SO4:H3PO4 and graphite powder (1.5 g) were
added with constant stirring for 15 min. Afterward, potassium
permanganate (8 g) was added slowly into the above mixture
and was heated at 50−55 °C with constant stirring for 12 h.
The reaction was cooled to room temperature and poured into
ice-cold water followed by the addition of hydrogen peroxide
(3.5 mL) and stirred for 1 h, yielding the bright yellow
precipitate. The mixture was kept overnight and centrifuged for
20 min at 7000 rpm (Sigma, Laboratory Centrifuges 3K30
Sartorius). The remaining solid material was then washed with
hydrogen chloride, ethanol (2x), and diethyl ether (2x) twice
for purification. The final solid brownish color GO sample was
vacuum dried at 45 °C for 10 h.
4.2. Synthesis of MOF-5 and MOF-5@GO Nano-
composite. Zinc acetate (4.24 g) and benzene dicarboxylic
acid (1.26 g) were dissolved in N,N-dimethylformamide
(DMF) in a beaker with constant stirring up to 2 h to obtain
a homogeneous mixture and placed in an oven at 125 °C for
24 h in a Teflon-lined sealed solvothermal vessel, resulting in a
solid colorless precipitate. It was gradually cooled to room
temperature and centrifuged at 7000 rpm for 15 min. The
product was washed with N,N-dimethylformamide (100 x 2),
dried under vacuum at room temperature, and stored under a
desiccator.
MOF-5 was synthesized according to a previously reported
method73,74 with minor modifications. MOF-5@GO nano-
composites were synthesized by a grinding method at different
ratios (1:1, 1:2, and 2:1). The mixture was then dried at room
temperature for 12 h and used as an adsorbent, and the
synthesis is schematically depicted in Scheme 1.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.1c00143.
https://doi.org/10.1021/acsomega.1c00143
ACS Omega 2021, 6, 9587−9599
ACS Omega http://pubs.acs.org/journal/acsodf
Materials and method; description of adsorption kinetics
and adsorption isotherm; N2 adsorption−desorption of
GO, MOF-5, and MOF-5@GO nanocomposites; and
EDS elemental analysis (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Dhanraj T. Masram − Department of Chemistry, University of
Delhi, Delhi 110007, India; orcid.org/0000-0001-6273-
8199; Email: dhanraj_masram27@rediffmail.com
Author
Gyanendra Kumar − Department of Chemistry, University of
Delhi, Delhi 110007, India; orcid.org/0000-0002-1975-
5310
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.1c00143
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We are grateful to the Head, Department of Chemistry, and
Director, USIC, University of Delhi, India for providing
instrumentation facilities. The authors acknowledge SAIF-
AIIMS, New Delhi, for HRTEM facilities. G.K. is also thankful
to the UGC-SRF (file no. 19/06/2016(i)EU-V) for providing
financial support.
■
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ACS Omega 2021, 6, 9587−9599