Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-021-13285-y

RESEARCH ARTICLE

Utilization of red mud waste into mesoporous ZSM-5 for methylene

blue adsorption-desorption studies
Hellna Tehubijuluw 1 & Riki Subagyo 1 & Maulil Fatma Yulita 1 & Reva Edra Nugraha 1 & Yuly Kusumawati 1 &
Hasliza Bahruji 2 & Aishah Abdul Jalil 3 & Hartati Hartati 4 & Didik Prasetyoko 1

Received: 6 November 2020 / Accepted: 1 March 2021

# The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2021

Abstract
Red mud as industrial waste from bauxite was utilized as a precursor for the synthesis of mesoporous ZSM-5. A high concen-
tration of iron oxide in red mud was successfully removed using alkali fusion treatment. Mesoporous ZSM-5 was synthesized
using cetyltrimethylammonium bromide (CTABr) as a template via dual-hydrothermal method, and the effect of crystallization
time was investigated towards the formation of mesopores. Characterization using X-ray diffraction (XRD), Fourier transform
infrared spectroscopy (FTIR), N2 adsorption-desorption, scanning electron microscopy (SEM), and transmission electron mi-
croscopy (TEM) indicated the formation of cubic crystallite ZSM-5 with high surface area and mesopore volume within 6 h of
crystallization. Increasing the crystallization time revealed the evolution of highly crystalline ZSM-5; however, the surface area
and mesoporosity were significantly reduced. The effect of mesoporosity was investigated on the adsorption of methylene blue
(MB). Kinetic and thermodynamic analysis of MB adsorption on mesoporous ZSM-5 was carried out at a variation of adsorption
parameters such as the concentration of MB solution, the temperatures of solution, and the amount of adsorbent. Finally,
methanol, 1-butanol, acetone, hydrochloric acid (HCl), and acetonitrile were used as desorbing agents to investigate the reus-
ability and stability of mesoporous ZSM-5 as an adsorbent for MB removal.

Keywords Red mud . Mesoporous ZSM-5 . Adsorbent . Adsorption . Desorption . Methylene blue

Introduction
The improper disposal of synthetic dyes from industries has a
devastating effect on water quality (Chala et al. 2014; Xia
et al. 2015; Ghalajkhani et al. 2018; Vaez and Javanbakht
Responsible Editor: Tito Roberto Cadaval Jr
* Didik Prasetyoko
didikp@chem.its.ac.id; didik.prasetyoko@gmail.com
1
Department of Chemistry, Faculty of Science and Data Analytics,
Institut Teknologi Sepuluh Nopember (ITS), Sukolilo,
Surabaya 60111, Indonesia
2
Centre for Advanced Material and Energy Sciences, Universiti
Brunei Darussalam, Jl. Tungku, Link BE1410, Brunei Darussalam
3
Department of Chemical Engineering, Faculty of Chemical and
Energy Engineering, Universiti Teknologi Malaysia, Johor Bahru,
81310 Skudai, Johor, Malaysia
4
Department of Chemistry, Faculty of Science and Technology,
Universitas Airlangga, Campus C UNAIR, Mulyorejo,
Surabaya, Indonesia
2020). Toxicity studies of the synthetic dye and the products
from its decomposition revealed the carcinogenic effects that
can trigger cancer cells in humans (Lellis et al. 2019).
Methylene blue (MB) is a stable heterocyclic aromatic with
a thiazine-based structure and has been widely used in textile
industry as a coloring agent (Yuan et al. 2019). A high dose of
methylene blue in the human body caused accumulation and
dimerization in the cell (Oz et al. 2009), while the carcinogen-
ic studies in rat and mice cells indicated the increase of tumor
incidence (Auerbach et al. 2010). Disposal of dye from indus-
trial waste has been carried out via physical process (adsorp-
tion, filtration, etc.), chemical purification (photocatalytic,
chemical oxidation, etc.), and biological degradation methods
(Xu et al. 2014; Jing et al. 2014; Xia et al. 2015). Removal of
MB via chemical oxidation or photooxidation produced
undesirable/toxic by-products such as 2-aminophenol and 2-
amino-5-(N-methylformamido)-benzenesulfonic acid (Xia
et al. 2015). In biodegradation method, the microorganism
destroyed the biodegradable compound, while the non-
biodegradable waste remained in the sludge and was released
to the environment (Zakaria et al. 2015; Nurhayati et al. 2020).
 Environ Sci Pollut Res

Adsorbent is a flexible material that can be modified to adsorb high-purity mesoporous ZSM-5 was synthesized from red
different types of dye, while its cost for production of adsor- mud following removal of iron oxide via alkali fusion.
bent is relatively low (Shu et al. 2015; Dolatabadi et al. 2018; ZSM-5 with different surface areas, micro/mesoporous, and
Li et al. 2019). However, the real challenge for removal of dye crystallinity was synthesized by controlling the crystallization
via adsorption is to improve the adsorption capacity, the ki- time. The micro/mesoporosity of ZSM-5 was correlated with
netic of adsorption, and the mechanical-chemical resistance of the efficiency of adsorption-desorption of MB. The effects of
the adsorbent (Gupta and Khatri 2017; Brião et al. 2017). MB concentration, contact time, initial concentration, and
Increasing the surface area and the porosity of adsorbent will temperatures were investigated in order to provide detailed
enhance the adsorption capacity, while modification of the kinetic and thermodynamic analysis. Desorption of MB was
mechanical and chemical properties will increase the stability also investigated using a different desorbing agent to deter-
and the reusability of adsorbent (Santoso et al. 2020). mine the reusability and stability of ZSM-5 as an adsorbent.
Aluminosilicate zeolite consists of a three-dimensional
framework of repeating SiO4 and AlO4 tetrahedral units
(Narayanan et al. 2014). Natural zeolite (Liu et al. 2014;
Zhang et al. 2018), zeolite Y (Guesh et al. 2016; El- Experimental
Mekkawi et al. 2016), zeolite A (Pereira et al. 2018), ZSM-5
(Wang et al. 2014; Panic and Velickovic 2014; Brião et al. Materials
2017; Sabarish and Unnikrishnan 2018), ZSM-11 (Gomez
et al. 2013), mordenite (Nassar et al. 2017), sodalite The materials used are sodium hydroxide (NaOH 99%,
(Mahmoodi and Saffar-Dastgerdi 2019), etc., have been syn- M e r c k ) , c o ll o i d a l s i l i c a ( L u d o x 3 0 % , A l d r i c h ) ,
thesized and modified to increase their efficiency for removal tetrapropylammonium hydroxide (TPAOH, 40 wt% solution
of dye from wastewater. ZSM-5 has high mechanical and in water, Merck), distilled water, cetyltrimethylammonium
chemical stabilities with a negatively charged lattice and is bromide (C19H42BrN, Aldrich), HCl, acetone, acetonitrile,
ideal as an adsorbent for positively charged dye such as meth- methanol, and methylene blue (C 16 H 18 ClN 3 S, Merck
ylene blue (Wang et al. 2014; Brião et al. 2017). However, Millipore). Red mud was obtained from Bintan Island,
conventional ZSM-5 consists of a small micropore with the Indonesia. The composition of red mud was analyzed using
average pore diameter of 0.56 nm and prevents the diffusion XRF that showed a high concentration of iron oxide, alumina,
of large MB molecules (Zhang et al. 2014; Fawaz et al. 2020). and silica with trace amounts of other minerals such as TiO2,
Mesoporous ZSM-5 with secondary porosity alleviated the K2O, and Ca2O (Table 1).
diffusion limitation and increased the mass transfer of large
molecules within the pore channel (Wang et al. 2017; Chen
et al. 2018). Naturally occurring mineral and industrial waste
such as kaolin, red mud, illite, rectorite, and diatomite have Table 1 Chemical composition of red mud and red mud after alkali
been used for the synthesis of zeolite that aimed to reduce fusion by XRF
production cost and to increase the economic value of the
mineral/waste (Qoniah et al. 2015; Belviso et al. 2018; Oxide compounds Weight (%)
Hartati et al. 2020). Red mud is an industrial waste from baux- Red mud RM after alkali fusion
ite refining to produce alumina, with a high concentration of
Fe2O3, Al2O3, and SiO2 (Ramdhani et al. 2018) suitable for Fe2O3 35.51 0.52
the synthesis of ZSM-5. Al2O3 31.00 74.09
In this study, mesoporous ZSM-5 was synthesized using SiO2 29.6 13.36
red mud as an adsorbent for methylene blue. Red mud was TiO2 2.820 –
reported as a catalyst for catalytic pyrolysis of plastic waste K2O 0.140 0.36
(de Marco et al. 2009); however, the surface area and acidity CaO 0.260 6.68
of red mud were significantly lower than those of ZSM-5, V2O5 0.074 1.21
which consequently reduced the distribution of pyrolysis Cr2O3 0.030 0.72
products (López et al. 2011; Fekhar et al. 2019). Red mud SO3 0.300 –
was also utilized as a precursor in the synthesis of ZSM-5 BaO 0.100 –
without prior pretreatment (Zhang et al. 2019). The presence CuO 0.120 2.06
of iron oxide in red mud can be detrimental for the synthesis of ZnO 0.048 –
high-purity ZSM-5. Furthermore, iron oxide is readily dis- PbO 0.180 0.97
solved in a desorbing agent such as hydrochloric acid (HCl), MnO 0.033 –
thus limiting the reusability of the adsorbent. In this study,
Environ Sci Pollut Res
Synthesis of mesoporous ZSM-5
A high concentration of iron oxide may be detrimental for the
synthesis of ZSM-5; therefore, red mud was treated with
NaOH (1:1 w/w) to remove iron oxide by extracting alumina
and silica via alkali fusion treatment. The extraction of alumi-
na and silica from red mud was carried out by mixing the red
mud with NaOH (1:1 w/w) and fused at 450 °C for 2 h. The
temperature for alkali fusion was determined using TGA anal-
ysis. Red mud showed complete decomposition at 450 °C
which corresponded to the formation of sodium silicate and
aluminate (Fig. 1). Distilled water was added to the mixture
and stirred for 24 h at room temperature. The solution was
filtered and dried at 105 °C for 24 h. The solid was subse-
quently used as sodium aluminate and sodium silicate sources
for the synthesis of mesoporous ZSM-5.
Mesoporous ZSM-5 was prepared at a molar composition
of 0.2SiO2:0.004Al2O3:0.04TPA:3.6H2O (Prasetyoko et al.
2017). The solid extracted from red mud was dissolved in
distilled water, and Ludox was added into the solution with
stirring for 8 h. TPAOH was dissolved in water and added to
the mixture. The mixture was then transferred into a polypro-
pylene bottle and heated at 80 °C for 6 h, 9 h, and 24 h. The
reaction mixture was cooled at room temperature and subse-
quently added with CTAB (molar ratio SiO2/CTAB = 3.85)
with gentle stirring for 1 h. The resulted gel was transferred
into an autoclave for the second stage of the crystallization
process at 150 °C for 24 h. The solid was filtered and thor-
oughly washed with water. Finally, the solid was dried at 60
°C for 24 h followed by calcination at 550 °C for 1 h in N2
flow and 6 h in air. Samples were labeled as ZSM-5_6h, ZSM-
5_9h, and ZSM-5_24h based on the crystallization time at 6 h,
Fig. 1 TGA-DTG profile of the
NaOH-red mud mixture
9 h, and 24 h. Figure 2 summarizes the synthesis step of
mesoporous ZSM-5 from red mud.
Characterization of mesoporous ZSM-5
The samples were characterized by X-ray diffraction (XRD),
FTIR, nitrogen adsorption-desorption, transmission electron
microscopy (TEM), and scanning electron microscopy
(SEM) methods. XRD measurement was carried out using
Cu Kα radiation on the Phillips Expert Diffractometer in the
range of 5–50° (2θ), and λ = 1.54056 for phase identification
and determination of the relative crystallinity. The infrared
spectra were recorded using the KBr pellets and Shimadzu
FTIR spectrometer in the range between 1800 and 400
cm−1. The nitrogen sorption isotherm was obtained using a
Quantachrome Corporation (Nova-1200) instrument. Prior to
the analysis, approximately 0.05 g of each sample was treated
under vacuum for 3 h at 300 °C. The specific surface area
(SBET) was estimated by the BET equation, while the pore size
distribution was determined by non-local density functional
theory (NLDFT) method. The SEM and the TEM micro-
graphs were obtained on ZEISS EVO MA 10 and Tecnai
G2 20 S-Twin, respectively.
Adsorption study
Methylene blue (0.01 g) was dissolved in 100 mL of distilled
water as an initial stock solution. Then, the initial stock solu-
tion was diluted to produce 20 mg L−1, 25 mg L−1, 30 mg L−1,
and 35 mg L−1 MB solutions. MB adsorption on ZSM-5 was
carried out using 10 mL of MB solution (20 mg L−1) and
0.005 g of ZSM-5. After the adsorption process, the mixtures

Fig. 2 The schematic synthesis of mesoporous ZSM-5 from red mud waste and the application for methylene blue adsorption
were centrifuged at 1500 rpm to separate the solution from the
adsorbent. The concentration of MB dye solution before and
after adsorption was determined using a UV spectrophotom-
eter at 664 nm wavelength. The amount of MB dye adsorbed
on the adsorbent (mg dye g−1 of adsorbent) and the percentage
of adsorption of MB were calculated using Eqs. (1)–(3), re-
spectively (Varghese et al. 2017).
ðC 0 −C e ÞV
qe ¼ ð1Þ
W %Desorption efficiency
ðC 0 −C t ÞV
qt ¼ ð2Þ
W Amount of the adsorbed by the adsorbent
ðC 0 −C e Þ
Removal ð%Þ ¼  100 ð3Þ
Co
where C0 is the initial concentration of MB in the solution; Ct
and Ce represent the final dye concentrations (mg/L) at given
contact time (t) and at equilibrium, respectively; V is the vol-
ume of MB solution; W is the weight of the ZSM-5; and Qe
and Qt are the adsorption capacities per unit mass of mesopo-
rous ZSM-5 at equilibrium and at a given time (t),
respectively.
Desorption study
Desorption studies were carried out using methanol, n-buta-
nol, acetonitrile, acetone, and hydrochloric acid as desorbing
agents. In a typical desorption procedure, 0.005 g of ZSM-5
Environ Sci Pollut Res
that has been used for MB adsorption was dispersed in 10 mL
of HCl. The mixtures were stirred for 30 min and centrifuged
to separate ZSM-5 from the solution. The filtrate was analyzed
using a UV-vis spectrophotometer to determine the concen-
tration of methylene blue. The adsorption was repeated as in
the section “Characterization of mesoporous ZSM-5” to de-
termine the reusability of ZSM-5. The % desorption efficiency
was calculated using Eq. (4) (Varghese et al. 2017).
Amount of dye desorbed from the adsorbent
¼
 100 ð4Þ
The possibility of regeneration and reusability was also
investigated by carrying out the adsorption-desorption process
for 3 cycles using HCl.
Results
Characterization of mesoporous ZSM-5
XRD analysis
Red mud, alkali-treated red mud, and mesoporous ZSM-5
synthesized at 6 h, 9 h, and 24 h were characterized using
Environ Sci Pollut Res

X-ray diffraction analysis (Fig. 3). Based on the JCPDS and

ICSD data, red mud consisted of a mixture of gibbsite (18.28°;
20.31°; 20.54°; 36.59°; 37.64°), boehmite (38.38°; 49.93°;
49.21°), hematite (24.14°; 33.15°; 35.61°; 40.86°; 49.48°;
54.90°), magnetite (30.91°; 35.42°; 43.04°), goethite
(21.27°; 33.28°; 34.74°; 36.72°), quartz (20.86°; 26.64°;
36.54°; 39.47°), TiO2 anatase (25.28°; 37.80°; 48.05°),
tsaregorodtsevite (19.84°; 24.88°), and SiO2 polymorph
(12.29°). After alkali treatment for removal of iron, the XRD
analysis indicated the red mud was converted into NaAlSiO4
(37°) and Na2SiO3 (17°, 19°, 23°) (Hu et al. 2017). The char-
acteristic peaks of ZSM-5 with MFI structures were observed
at 7.9°, 8.8°, 23.1°, 23.9°, and 24.3° following hydrothermal
synthesis at 6 h, 9 h, and 24 h (Pan et al. 2014). The XRD peak
intensity was increased with crystallization time indicating the
formation of high crystalline ZSM-5. The relative intensity of
ZSM-5 synthesized from red mud was calculated using com-
mercial ZSM-5 as a standard (Table 2) that showed the crys-
tallinity increased with increasing the crystallization time.

FTIR analysis

FTIR spectra of red mud showed the typical quartz and hema-
tite absorption band at 999–1008 cm−1, 549–540 cm−1, and
462–468 cm−1 (Singh et al. 2019). The absorption band at 960
cm−1 corresponded to the Si–O bond in quartz. The presence
of hematite was confirmed by the absorption bands at 559
cm−1 and 479 cm−1 assigned to the Fe3+–O2− bond (Wang
et al. 1998). The absorption bands which appeared at 874
cm−1, 712 cm−1, and 628 cm−1 were assigned to Al3+–O2−
bonds (Dodoo-Arhin et al. 2013). Following alkali fusion,
the bands associated with Fe–O phases disappeared, indicat-
ing a complete removal of iron oxide in the treated red mud.
The new emergence of absorption peaks at 870 cm−1 and 1420
cm−1 was assigned to sodium aluminate (Ma et al. 2007) and
sodium silicate (Ma et al. 2007; Wei et al. 2019), respectively.
The as-synthesized mesoporous ZSM-5 in Fig. 4 shows the
bending vibration of T-O-T (T is Al or Si atom) appeared at
450 cm−1, while the external symmetric and internal symmet-
ric asymmetric stretching modes of T-O-T (between TO4 tet-
rahedral) were observed at 798 cm−1 and 1100 cm−1, respec-
tively. These absorptions were insensitive towards the chang-
es of tetrahedral structures of ZSM-5 (Yue et al. 2018). The
absorption bands at 540 cm−1 attributed to the as-asymmetric
stretching vibration of the double five-membered ring (D5R)
as the characteristic of pentasil MFI-type zeolite. The absorp-
tion band at 1220 cm−1 indicated the asymmetric stretching
mode of T-O-T (between TO4 tetrahedral) that was sensitive
towards the changes in the structure of tetrahedral external
vibrations. It was apparent that the intensity of the peaks in-
creased with increasing the crystallization time that implied
the formation of high crystalline structures of ZSM-5 (Somani
et al. 2003).
Fig. 3 XRD pattern of (a) red mud waste, (b) red mud waste after alkali
fusion, (c) commercial ZSM-5, and as-synthesized samples: (d) ZSM-5_
24h, (e) ZSM-5_9h, and (f) ZSM-5_6h with JCPDS data of gibbsite (00-
007-0324), TiO2 anatase (00-021-1272), boehmite (00-021-1307), hema-
tite (00-033-0664), magnetite (00-019-0629), goethite (01-075-5065),
quartz (00-046-1045), and ICDD data of tsaregorodtsevite (96-900-
9561) and silica polymorph (96-412-4034)
N2 adsorption-desorption
N2 adsorption-desorption isotherms in Fig. 5a indicates the
isotherms of ZSM-5 were varied depending on the crystalli-
zation time. Rapid adsorption of N2 at low relative pressure
(P/P0) was the main characteristic of adsorption in micropores
(type I) and was observed in all samples. The increase of
adsorbed N2 at higher P/P0 indicated the adsorption occurred
within the mesopores (type IV). ZSM-5_6h showed a much
higher N2 adsorption at P/P0 = 0.3–0.9 followed by ZSM-
5_9h and ZSM-5_24h. The results revealed that ZSM-5 with
high mesoporosity was obtained at reduced crystallization
time. The presence of hysteresis loop in the lower P/P0 range
(started at 0.3) was also observed in ZSM-5_6h and ZSM-
5_9h due to the condensation within the intraparticle
mesopores (Yu et al. 2007; Teh et al. 2015). Meanwhile, the
hysteresis loop at higher P/P0 (P/P0 = 0.9–1.0) for ZSM-
5_24h suggests the formation of inter-aggregated mesopores
 Environ Sci Pollut Res

27.5, 49.2
29.8, 47.5
27.5, 49.3
Inter
dmeso (nm)

–
Intra

2.89
3.02
2.79
3.32
dmicro (nm)

1.18
1.18
1.24
1.47
0.023
0.021
0.018
Inter2

–
(cm3 g−1)

Intra3
Vmeso

0.57
0.58
0.53
0.21
(cm3 g−1)
Vmicro

0.25
0.25
0.20
0.16
(cm3 g−1)

0.853
0.751
0.388
0.825
Vtotal
(m2 g−1)4
Smicro

233
261
238
204
Intra3

562
590
355
564
(m2 g−1)

Inter2
Smeso

Fig. 4 FTIR spectra of (a) red mud waste, (b) red mud waste after alkali
252
223
112
276

fusion, and as-synthesized samples: (c) ZSM-5_6h, (d) ZSM-5_9h, (e)

The textural properties of mesoporous ZSM-5 synthesized from red mud

ZSM-5_24h, and (f) commercial ZSM-5

(m2 g−1)
SBET

Calculated by the NLDFT method at a relative pressure range of 0.24–0.9

734
721
388
683

Calculated by the NLDFT method at a relative pressure range of 0.9–1.0

within the ZSM-5 structure (Yu et al. 2007; Shi et al. 2018).
Mesopore volume and surface area decreased with prolonged
Particle size (μm)1

crystallization time due to the formation of a well-defined

zeolite structure that reduced the mesoporosity of ZSM-5
(Mohiuddin et al. 2016).
2.12
3.52
2.68

Pore size distribution of ZSM-5 obtained at different crys-

–

tallization times is shown in Fig. 5b, and the calculated data

using the NLDFT method is summarized in Table 2. All
Crystallinity (%)

ZSM-5 samples revealed a narrow distribution of micropores

at ~1.18–1.24 nm; however, the pore volume was increased
Calculated by the t-plot method

when the crystallization time was reduced to 6 h. The presence

29.21
32.07
55.35

Determined by SEM analysis

of intraparticle mesopores was observed between 2.5 and 4.0

6

nm. The volume of adsorbed N2 was significantly higher for

ZSM-5_6h desorption

ZSM-5_6h followed by ZSM-5_9h and ZSM-5_24h. The in-

set in Fig. 5c exhibits the pore size distribution of the inter-
particle mesopore calculated within P/P0 = 0.9–1.0 using the
ZSM-5_24h
ZSM-5_6h
ZSM-5_9h

NLDFT method. It is apparent that the volume of N2 uptake

Sample
Table 2

was significantly reduced on large pores, suggesting that the

number of interparticle pores within the ZSM-5 structure was
1

4
Environ Sci Pollut Res

Fig. 5 a N2 adsorption-
desorption isotherm. b NLDFT
pore size distribution of all as-
synthesized samples (the dashed
line at 2 nm shows the separation
of micropore and mesopore). c
(Inset) NLDFT pore size distri-
bution for interparticle mesopore
(P/P0 = 0.9–1.0)

much lower than that of intraparticle pores. The results further
proved the effect of controlling crystallization time towards
the formation of mesoporous ZSM-5 from red mud waste.
Morphology analysis using SEM and TEM
SEM images in Fig. 6a–c show the formation of cubic
microcrystallites of ZSM-5 obtained at 6 h, 9 h, and 24 h.
However, non-uniformed aggregates scattered on the surface
of the microcrystalline cubes were also observed on ZSM-5
that were produced at 6 h and 9 h. The formation of non-
uniformed particles was due to the incomplete crystallization
of amorphous aluminosilicate (Ye et al. 2017). The results
were in a good agreement with the XRD analysis that revealed
a longer crystallization time increased the crystallinity of
ZSM-5. The particle size distribution histograms are shown
 Environ Sci Pollut Res

Fig. 6 SEM micrographs of a

ZSM-5_6h, b ZSM-5_9h, and c
ZSM-5_24h. The particle size
distribution of ZSM-5 produced
at d 6 h, e 9 h, and f 24 h of hy-
drothermal time

in Fig. 6d–f. The average particle size of ZSM-5_6h, ZSM-
5_9h, and ZSM-5_24h were determined at 2.12 μm, 3.52 μm,
and 2.68 μm, respectively.
The morphology of ZSM-5_6h was further analyzed using
HRTEM analysis to show the formation of mesopores. TEM
analysis of ZSM-5_6h (Fig. 7) showed the presence of
intraparticle pores evidenced from the appearance of clear-
lighter areas within the dark-field features. Meanwhile, the
formation of interparticle porosity was observed from the in-
teraction of ZSM-5 crystallites to form pore with an estimated
diameter of ~31.4 nm and 51.5 nm. The results were in
agreement with calculated data obtained from N2 adsorption-
desorption analysis.
Methylene blue adsorption of mesoporous ZSM-5
The adsorption of MB was carried out using red mud, ZSM-
5_6h, ZSM-5_9h, and ZSM-5_24h to indicate the effect of
mesoporosity on the efficiency of MB adsorption. The
amounts of adsorbents were varied at 2.5 mg, 5 mg, 10 mg,
and 15 mg while using 20 mg L−1 of MB solution (Fig. 8). At
2.5 mg of adsorbent, significant differences on the percentage

Fig. 7 a, b TEM images of the

ZSM-5_6h sample
Environ Sci Pollut Res
Fig. 8 Effect of the amount of adsorbent dosage on the MB adsorption
of removal were observed, with ZSM-5_6h showing ~80% of
MB removal followed by ZSM-5_9h at 68% and ZSM-5_24h
at 48%. Adsorption studies using red mud only showed 5% of
MB removal. Increasing the amount of adsorbent at 5 mg
increased the removal efficiency to 95% on ZSM-5_6h and
ZSM-5_9h, while ZSM-5_24h exhibited only 70% of remov-
al. Poor MB adsorption of red mud was improved when the
amount of red mud used during the adsorption was increased
to 15 mg, to give 60% of MB removal. In general, a large-
surface-area adsorbent provided more adsorption sites for
MB. At a low amount of adsorbent, ZSM-5_6h with high
surface area and mesopore volume increased the adsorption
by providing a high number of accessible active sites for MB
adsorption. However, when the amount of ZSM-5 was in-
creased from 5 to 15 mg, the effect of mesopores was less
significant due to the number of available adsorption sites that
was compensated by the amount of adsorbent.
Effect of initial dye concentration on methylene blue
adsorption
The effect of initial dye concentration on the adsorption ca-
pacity was carried out at 20 mg L−1, 25 mg L−1, 30 mg L−1,
and 35 mg L−1 using 5 mg of ZSM-5_6h (Fig. 9). The adsorp-
tion rapidly occurred when using 20 mg L−1 of MB solution,
reaching equilibrium within 5 min into the adsorption process.
Increasing the concentration of MB significantly enhanced the
adsorption capacity and the equilibrium time to 30 min. The
results suggested that rapid adsorption at low MB concentra-
tion was due to the adsorption on the external surface of ZSM-
5. Increasing the concentration of MB required diffusion of
MB molecules into the mesopores following the saturation at
the external surface of ZSM-5. The repulsion between the
adsorbed MB molecules and the MB in the solution may also
Fig. 9 Effect of initial dye concentration on MB adsorption using ZSM-
5_6h
contribute to the increase of equilibrium time. Nevertheless,
the driving forces which resulted from the high concentration
of MB overcame the mass transfer restriction between the
aqueous MB solution and the solid adsorbent phase. The pres-
ence of mesopores in ZSM-5_6h with an average diameter of
~3 nm which allowed the diffusion of MB molecules within
the pores consequently increased the adsorption capacity at
high MB concentration.
Effect of temperature
Increasing the temperature of the MB solution during the ad-
sorption process enhanced the kinetic and the adsorption ca-
pacity. The adsorption of 20 mg L−1 MB solution onto meso-
porous ZSM-5_6h was investigated at 30 °C, 40 °C, and 50
°C. The adsorption was determined at 5 min, 10 min, 20 min,
30 min, and 60 min under a constant stirring speed of 450 rpm.
The adsorption capacity (Fig. 10) was improved with increas-
ing the adsorption temperatures. In general, the adsorption of
MB on solid adsorbent usually reached equilibrium when the
surface of adsorbent was covered with a monolayer of
adsorbed MB. However, adsorption at high temperatures en-
hanced the adsorption capacity presumably due to the in-
creased electrostatic interaction between MB and ZSM-5.
Water molecules also exhibited dipole-dipole interactions
with ZSM-5 that can occupy the adsorption sites. Increasing
the temperatures enhanced the adsorbate-adsorbent intermo-
lecular forces by reducing the adsorbate-solvent interaction.
At low temperatures, the poor electrostatic interaction be-
tween methylene blue and ZSM-5 allowed water to attach
on the adsorption sites. The increase of adsorption capacity
at higher temperature indicates the endothermic nature of MB
adsorption process.

Fig. 10 Effect of temperature on MB adsorption using the ZSM-5_6h
adsorbent
Desorption of methylene blue from ZSM-5
Desorption of MB from ZSM-5_6h was carried out using
methanol (CH3OH), 1-butanol (C4H9OH), acetonitrile, ace-
tone, and HCl as the desorbing agent (Fig. 11a). The
desorbing agent was added on the ZSM-5_6h after it reached
saturation following adsorption with 20 mg/L of MB. When
HCl was used as a desorbing agent, ~33% of MB was recov-
ered, followed by acetone to give ~30% of MB desorption; 1-
butanol, methanol, and acetonitrile were less effective with
only 15% of MB which were recovered from ZSM-5. HCl
was previously used as a desorbing agent of MB from TiO2
hydrosol (Yu et al. 2010), nano-Fe3O4 (Xia et al. 2019), and
brown macroalgae (Daneshvar et al. 2017) with the desorption
efficiency varied between 40 and 91%. Although the amount
of MB recovered from ZSM-5 was only 35%, HCl exhibited
better desorption efficiency in comparison to the other
Fig. 11 Desorption efficiency plot with various desorbing agents (a) and multi-cycle efficiency of ZSM-5_6h (b)
Environ Sci Pollut Res
desorbing agents due to the ability to increase the electrostatic
repulsion between MB and ZSM-5. MB is a cationic dye that
adsorbed on ZSM-5 presumably via hydrogen bridge forma-
tion (Santoso et al. 2020). The presence of HCl weakens the
strength of the hydrogen bond between the N-H functional
group in the MB and the surface hydroxyl on the ZSM-5, thus
releasing the MB.
The adsorption-desorption studies were further investi-
gated on ZSM-5_6h, ZSM-5_9h, and ZSM-5_24h using
HCl. The adsorption-desorption cycles were repeated
three times that indicated the percentages of MB removal
were decreased with every cycle (Fig. 11b). The strong
interaction between methylene blue and ZSM-5 prevented
the complete desorption of MB to regenerate the adsorp-
tion sites. There were no significant differences in the
effect of ZSM-5 mesoporosity and crystallinity towards
the ability to desorb MB, suggesting the removal process
was generally dictated by chemical functionality rather
than textural properties. XRD and N 2 adsorption-
desorption analysis were carried out on ZSM-5_6h after
adsorption-desorption studies to determine the stability of
t h e a d s or b e nt . F i g u r e 12 s h o w s th e p e ak s th a t
corresponded to ZSM-5 were still visible with no signifi-
cant reduction of intensity, indicating the stability of
ZSM-5_6h in acidic condition.
On the other hand, the results of N2 adsorption-desorption
in Fig. 13 exhibit a similar type of isotherm on ZSM-5_6h
after desorption. The hysteresis loop of ZSM-5 after desorp-
tion also occurred at P/P0 of 0.3–0.9, but with a very small N2
uptake, indicating the presence of interparticle mesopores.
The pore distribution of ZSM-5_6h after MB desorption was
calculated by the NLDFT method and is summarized in
Table 2. The results showed that the surface area and pore
volume were decreased after MB desorption, suggesting the
accumulation of MB molecules on the external surface and
within the pores of ZSM-5.
Environ Sci Pollut Res

Fig. 12 XRD pattern of (a) ZSM-5_6h recovered after adsorption- Fig. 14 The adsorption isotherm of ZSM-5_6h using Langmuir,
desorption studies and (b) the fresh ZSM-5_6h Freundlich, and Temkin isotherm models

Adsorption isotherm adsorbed at equilibrium, qm (mg g−1) is the maximum adsorp-

Adsorption isotherm was analyzed using Langmuir,
Freundlich, and Temkin isotherm models in order to provide
insight into the mechanism of MB adsorption on ZSM-5 (Fig.
14). The non-linear equations of the Langmuir, Freundlich,
and Temkin models (Hammud et al. 2014) are shown in
Eqs. (5), (6), and (7), respectively.
Qt KL Ce
Qe ¼
1 þ K L Ce
Qe ¼ K F ðC e Þ1=n
Qe ¼ BlnK T þ BlnC e
where Ce (mg/L) is the concentration of methylene blue dye at
equilibrium, qe (mg g−1) is the amount of methylene blue dye
tion capacity of Langmuir, and KL (L mg−1) is the Langmuir
constant, KF (mg g−1)(mg L−1)−1/n is the Freundlich constant,
n is the dimensionless constant which indicates the adsorption
intensity, K T (L mg −1 ) is the Temkin constant, and B
−1
bT ; L mol Þ is the Temkin constant in relation to the heat
( RT
of adsorption.
Table 3 summarizes the parameters calculated from the
isotherm models. The RMSE value determined using the
Langmuir model was 0.042, which was significantly low in
ð5Þ comparison to the RMSE values of Freundlich and Temkin
models. The results suggest the adsorption of MB on meso-
ð6Þ porous ZSM-5 follows the Langmuir isotherm with a maxi-
mum adsorption capacity of 270.72 mg g−1. According to the
ð7Þ
Langmuir model, the adsorption of MB on ZSM-5 surfaces
involved monolayer adsorption. The adsorption nature of MB
on ZSM-5 using the Langmuir model can also be presented

Fig. 13 a N2 adsorption-
desorption isotherm and b
NLDFT pore size distribution of
ZSM-5_6h and ZSM-5_6h after
desorption. The dashed line at
2 nm shows the separation of mi-
cropore and mesopore
 Environ Sci Pollut Res

Table 3 Isotherm model parameter for adsorption of MB onto ZSM-5_ t 1 t

¼ þ ð12Þ
6h Qt k2 Q2e Qe
Isotherm model Parameter Value
where k1 (min−1) is the rate constant of the pseudo-first-order
Langmuir qm (mg g−1) 270.27 model and k2 (g mg−1 min−1) is the rate constant of the
KL (L mg−1) 0.008 pseudo-second-order model.
RL, average 0.867 The kinetic of adsorption was determined using linear and
RMSE 0.042 non-linear kinetic models (Fig. 15). Figure 15 clearly indicates
Freundlich n (mg g−1)(L mg−1)1/n 1.090
that the kinetic of methylene blue adsorption on ZSM-5 fol-
KF ((mg g−1)((mg L−1)−1/n)) 2.246
lows the pseudo-second-order model. The calculated qe deter-
RMSE 0.093
mined from the pseudo-second-order model was in agreement
with the experimental qe in comparison to the calculated qe
Temkin B (L mol−1) 23.438
values of the pseudo-first-order kinetic model. All the param-
KT (L mg−1) 0.310
eters of adsorption kinetic are summarized in Table 4.
RMSE 7.597

Adsorption thermodynamics
using the separation factor (RL) calculated using this following Thermodynamic parameters, i.e., the entropy change (ΔS°),
equation: the enthalpy change (ΔH°), and the Gibbs free energy change
(ΔG°) were determined using the equilibrium constant (Kd).
1 Kd was calculated using Eq. (13) based on the adsorption at
RL ¼ ð8Þ different temperatures. Cad, e (mg/L) refers to the equilibrium
1 þ K L C0
concentration of methylene blue adsorbed on ZSM-5, and Ce
The average of separation factors (RL) was determined be- (mg/L) is the concentration of methylene blue in solution at
tween 0 and 1, which indicates the nature of adsorption fa- equilibrium. The relationship between the equilibrium distri-
vored the equilibrium (Saxena et al. 2020). bution constant (Kd) and the thermodynamic parameter (ΔS°
and ΔH°) is given in Eq. (14), and T (K) refers to the absolute
temperature. The slope and the intercept values of ln Kd
Adsorption kinetics
against T−1 were used to calculate ΔH° and ΔS° values, re-
spectively. The ΔG° values are calculated using Eq. (15) (Dali
The kinetic of adsorption was determined using the Lagergren
Youcef et al. 2019).
kinetic models for the pseudo-first-order and pseudo-second-
order models. These two kinetic models are expressed in non-
linear (Eqs. (11) and (12)) (Mahmoud et al. 2017) and linear C ad;e
Kd ¼ ð13Þ
(Eqs. (9) and (10)) forms (Liu et al. 2011) as follows: Ce
ΔS° ΔH°

lnK d ¼ þ ð14Þ
−k 1 t
Qt ¼ Qe 1−e ð9Þ R RT
ΔG° ¼ ΔH°−T ΔS° ð15Þ
lnðQe −Qt Þ ¼ lnQe þ k 1 t ð10Þ
Q2e k 2 t The calculated thermodynamic parameters summarized in
Qt ¼ ð11Þ Table 5 show the negative values of ΔG° with increasing the
ð1 þ Qe k 2 t Þ
temperatures, which implied the adsorption of MB on ZSM-5

Table 4 The kinetic parameters

of the pseudo-first-order and the C0 (mg L−1) Qe, exp Pseudo-first-order Pseudo-second-order
pseudo-second-order models for (mg g−1)
the sorption of MB onto ZSM-5_ k1 (min−1) qe (mg g−1) R2 k2 (g mg−1 min−1) qe (mg g−1) R2
6h
20 32.32 −0.31 10.81 0.87 0.50 32.36 1.00
25 42.40 −0.16 21.07 0.84 0.07 42.01 0.99
30 44.87 −0.20 32.29 0.96 0.02 45.45 0.99
35 48.09 −0.10 21.29 0.60 0.01 48.54 0.99
Environ Sci Pollut Res

Fig. 15 a, c Pseudo-first-order
and b, d pseudo-second-order
sorption kinetics of methylene
blue (MB) on ZSM-5. a, b Non-
linear fitting. c, d Linear fitting

was a spontaneous process (Rida et al. 2013). The adsorption
of MB on ZSM-5 is an endothermic process based on the
positive value of ΔH° = +38.06 kJ mol−1, suggesting the
adsorption favored a high-temperature condition in order to
enhance the adsorption capacity. The entropy change (ΔS°)
was determined at 0.13 kJ mol−1 K−1, which indicated the
increase of freedom of the adsorbed species during the surface
adsorption (Ge et al. 2009). The value of ΔS° was determined
at 0.13 kJ mol−1 K−1, which was significantly low, suggesting
no significant changes of the entropy have occurred (Fu 2015;
El-Wakil et al. 2015; Shittu et al. 2019).

Adsorption mechanism
Table 5 Thermodynamic parameters for the adsorption of MB dye on
ZSM-5_6h at different temperatures
FTIR analysis was carried out to investigate the interaction
T (K) ΔG° (kJ mol−1) ΔH° (kJ mol−1) ΔS° (kJ mol−1 K−1) between methylene blue and ZSM-5. Methylene blue
contained OH, C=C, C=N, C=S, C–S, and C–H functionali-
303 −2.69 38.06 0.13
313 −4.04 ties that were able to interact with ZSM-5 surfaces during
323 −5.38 adsorption (Gong et al. 2015). The FTIR spectra of ZSM-
5_6h, MB, and ZSM-5_6h following adsorption with MB
 Environ Sci Pollut Res

at 1541 cm−1 and 1385 cm−1 corresponded to the stretching

vibration of C=N and CH2 of MB, respectively. FTIR analysis
of the adsorption of MB dye onto ZSM-5 provided insight into
the nature of the adsorbent-adsorbate interaction. Based on the
results obtained from FTIR and thermodynamic analysis, two
mechanisms were suggested to describe the adsorption of MB
on ZSM-5. MB adsorbed on ZSM-5 via the formation of a
hydrogen bridge between the lone pair electrons of nitrogen
atom in the methylene blue with the Si–OH in the zeolite
framework. Apart from that, MB was also adsorbed via the
electrostatic attraction between the negative charge of Al−
(ZSM-5 structure) and the positive charge of N+ (methylene
blue structure) (Lyu et al. 2020). The adsorption mechanism is
illustrated in Fig. 17. There was no evidence of a donor-
acceptor interaction between the electron-deficient sulfur
atoms in MB with ZSM-5 due to the absence of the S–O
adsorption band from the FTIR analysis.

Conclusion

Mesoporous ZSM-5 was successfully synthesized using baux-

Fig. 16 FTIR spectra of (a) ZSM-5, (b) MB, and (c) ZSM-5_MB
are shown in Fig. 16, and the adsorption bands are summa-
rized in Table 6. The adsorption bands of ZSM-5 have been
discussed in the section “FTIR analysis.” FTIR analysis of
MB showed the strong adsorption bands at 1590 cm−1 and
1385 cm −1 ascribed to the stretching vibration of C=N
(C=C) and C–N bonds in the heterocyclic of MB, respective-
ly. Analysis of ZSM-5 following MB adsorption showed the
adsorption bands which corresponded to ZSM-5 were ob-
served at similar wavenumber, with the appearance of bands
ite industrial waste (red mud) as an adsorbent for MB removal.
Red mud was treated via alkali fusion in order to remove iron
oxide prior to the synthesis of zeolite. Mesoporous ZSM-5
with high surface area and mesopore volume was obtained
within 6 h of crystallization time, while increasing the crystal-
lization time produced ZSM-5 with high crystallinity but low
in mesoporosity. The presence of mesopores in ZSM-5 signif-
icantly enhanced MB adsorption via diffusion of MB to access
the adsorption sites within the mesopores. The kinetic and
thermodynamic analysis indicated that MB is adsorbed on
mesoporous ZSM-5 via physical interaction, and the negative
value of Gibb’s free energy change indicated the feasibility of
the process. The desorption studies using different types of
desorbing agents, i.e., methanol, HCl, acetonitrile, n-butanol,
and acetone, revealed that the highest desorption efficiency

Table 6 Functional groups ZSM-

5_6h, MB, and MB-ZSM-5_6h Assignments ZSM-5_6h (cm−1) MB (cm−1) MB-ZSM-5_6h (cm−1)

Bonded –OH groups 3452 3450 3452

Stretching vibration of C=N – 1590 1541
– 1493
Stretching vibration of C=C – 1385 1385
CH2 deformation vibration – 1170
External asymmetric stretching 1230
Internal asymmetric stretching 1080 1080
TO4 symmetric stretching 788 788
TO4 bending vibration 543 543
Environ Sci Pollut Res
Fig. 17 Illustration of the
interaction between ZSM-5 and
methylene blue
was exhibited when using HCl due to the ability to reduce the
hydrogen bridge interaction between MB and ZSM-5.
Acknowledgements The authors gratefully acknowledge Dr. Eko
Santoso from the Department of Chemistry, ITS, for the discussion on
the kinetic studies.
Author contribution HT conceptualized and planned the study, per-
formed the experiments and data analysis, and prepared the original draft
of the manuscript. RS performed the experiments and data analysis and
prepared the original draft of the manuscript. MFY performed the exper-
iments and data analysis. REN performed the experiments and data anal-
ysis. YK supervised the study, acquired funding, and reviewed and edited
the manuscript. HB reviewed and edited the manuscript. AAJ reviewed
and edited the manuscript. HH reviewed and edited the manuscript. DP
supervised the study, acquired funding, and reviewed and edited the man-
uscript. All authors have read and approved the final manuscript.
Funding The authors are grateful to the Ministry of Research,
Technology and Higher Education of Republic Indonesia for supporting
a research fund under the research grant of PDUPT, number PDUPT-
1193/PKS/ITS/2020.
Data availability The datasets used and analyzed during the current study
are available from the corresponding author on reasonable request.
Declarations
Ethics approval and consent to participate Not applicable
Consent for publication Not applicable
Competing interests The authors declare no competing interests.
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