Journal of Molecular Structure 1184 (2019) 389e399

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Preparation and characterisation of high performing magnesite-

halloysite nanocomposite and its application in the removal of
methylene blue dye
T. Ngulube a, *, J.R. Gumbo b, V. Masindi c, d, A. Maity e, f
a
Department of Ecology and Resources Management, School of Environmental Sciences, University of Venda, Private bag X5050, Thohoyandou, 0950,
Limpopo, South Africa
b
Department of Hydrology and Water Resources, School of Environmental Sciences, University of Venda, Private bag X5050, Thohoyandou, 0950, Limpopo,
South Africa
c
Council for Scientific and Industrial Research (CSIR), Built Environment, Hydraulic Infrastructure Engineering, P.O BOX 395, Pretoria, 0001, South Africa
d
Department of Environmental Sciences, School of Agriculture and Environmental Sciences, University of South Africa (UNISA), P. O. Box 392, Florida, 1710,
South Africa
e
Department of Applied Chemistry, University of Johannesburg, Johannesburg, South Africa
f
DST/CSIR National Centre for Nanostructured Materials, Council for Scientific and Industrial Research (CSIR), Pretoria, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: Nanoparticles have novel characteristics enabling them to efficiently decontaminate water hence the
Received 1 October 2018 application of nanotechnology in wastewater treatment is being widely explored to tackle water
Received in revised form pollution challenges. Industries are in a quest for decolouration and contaminant depollution technol-
9 February 2019
ogies. In that regard, this study was designed with the aim of preparing a nanocomposite from calcined
Accepted 11 February 2019
cryptocrystalline magnesite and halloysite nanoclay and then evaluating the influence of several pa-
Available online 16 February 2019
rameters in the removal of Methylene Blue (MB) from aqueous solution by the prepared nanocomposite.
Physicochemical characterisation was carried out to get an insight of pre- and - post adsorption char-
Keywords:
Adsorption
acteristics of the material. According to the results, the uptake of MB was rapid, and the maximum
Calcined cryptocrystalline magnesite adsorption capacity and percentage removal were observed to be 0.65 mg/g and 99.66% respectively. Two
Halloysite adsorption isotherms and kinetic models were applied to describe the dye adsorption behaviour.
Methylene blue Experimental results fitted the Langmuir (R2 ¼ 0.98) and pseudo-second order models (R2 ¼ 1) perfectly
Nanocomposite hence demonstrating that adsorption took place on a homogenous adsorbent layer via chemisorption.
Wastewater treatment Furthermore, regeneration results showed that the nanocomposite can be used repeatedly recording a
35% removal at the 4th regeneration cycle. In overall, the results suggested that the nanocomposite is a
suitable adsorbent for decolourising industrial wastewater. Due to its local availability and non-toxic
nature, calcined cryptocrystalline magnesite e halloysite nanocomposite can be considered a good
alternative of conventional dye adsorbents commonly used in wastewater treatment especially in
developing countries like South Africa.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
Raw earth materials like magnesite obtained directly from
mines have large crystallite sizes with low surface-area-to-volume
ratio [1], and such properties limit their application in nanotech-
nology especially in adsorption processes. For such a material to be
applicable in adsorption processes, it must be modified to increase
* Corresponding author.
E-mail address: tholisongulube@gmail.com (T. Ngulube).
its surface area which leads to high adsorption capacities. Several
studies have reported on the effect of mechanical modification on
the morphological and structural characteristics of different ad-
sorbents [2e4]. However there exists only a few research studies
evaluating the use of a ball miller to enhance the adsorption
characteristics of the developed adsorbent [2,4,5]. Disintegration,
alteration of the crystalline network, particle arrangement, particle
size reduction ultimately leads to a larger surface area which en-
hances contaminant removal efficiency of the adsorbent [4,6,7].
In practice, grinding has been widely used as a traditional

https://doi.org/10.1016/j.molstruc.2019.02.043
0022-2860/© 2019 Elsevier B.V. All rights reserved.
390 T. Ngulube et al. / Journal of Molecular Structure 1184 (2019) 389e399
method to process inorganic minerals before they are used in
various industrial application due to the inexpensiveness of the
method and the simplicity in operation [1]. It is practical to process
raw minerals preliminarily by crushing and grinding them to
augment their adsorption properties before any application in
water treatment purposes. In this study, halloysite nanoclay min-
eral and calcined cryptocrystalline magnesite were incorporated in
the preparation of a nanocomposite adsorbent. The synthesis
involved a simple physical method employing a vibratory ball mill
to mix the two materials. Usually, milling is used for reducing
particle size together with additional unforeseen changes, that
have a direct effect on the physical and chemical properties of the
inorganic clay minerals leading to the enhancement of their
contaminant removal potential.
Technologies applied for removal of dyes from wastewater can
be categorised into physical, biological and chemical. Though these
conventional methods have been extensively used, they do have
some limitations [8,9]. For instance, biological treatment methods
consume time and tend to be ineffective in the removal of highly
structured polymer dyes that are not easily biodegradable. More-
over, biological methods have a limitation in most wastewaters
because most commercial dyes are toxic to the organisms used [10].
On the other hand, chemical coagulation causes additional
contamination because of undesired reactions in treated water [8].
Moreover, these methods are generally expensive and most times
there is inadequate treatment efficiency due to the high variability
of textile wastewaters [11]. There are however some methods like
photodegradation which are gaining much attention because of
their effectiveness, less toxic after effects and low cost in treating
coloured water [12e16]. Nevertheless, adsorption tends to be
amongst the most favoured waste water treatment techniques. In
the adsorption method, raw effluent is contacted with the adsor-
bent material. The adsorbent material retains the dye molecules
either by physical, chemical or ion exchange mechanisms. The
adsorbent gets saturated after a certain period of time and requires
regeneration. The adsorption process is extensively used and gives
satisfactory results [17]. For this reason, adsorption seems to be a
more attractive method in terms of cost, simplicity of design and
operation. Moreover, the adsorbent can be easily recovered and
reused. Even though a wide variety of adsorbents have been
applied in the process of wastewater treatment, naturally available
earth materials have been the adsorbents of choice in most
developed countries.
The objective of this study was therefore to prepare a nano-
composite adsorbent from halloysite nanoclay and calcined cryp-
tocrystalline magnesite and assess the performance of the calcined
cryptocrystalline magnesite - halloysite nanocomposite (CCMHN)
in MB removal from aqueous solution. MB is usually used to dye
silk, wood and cotton [18]. MB is reported to be less hazardous,
however, it has numerous harmful effects where severe exposure to
humans may cause jaundice, cyanosis, shock, nausea and quadri-
plegia [19].
When compared to other studies that have used composite
materials for dye removal purposes, this work is better because the
composite used was prepared from naturally occurring earth ma-
terials that do not require chemical pre-treatment, the method of
composite preparation is simple and very quick. Moreover, the
composite material can be regenerated and reused many times for
the removal of MB.
2. Experimental procedure
2.1. Chemicals and materials
Calcined cryptocrystalline magnesite was obtained from
Sterkfontein carbonate group Pty (Ltd). Cryptocrystalline magnesite
was calcined at 900 K using a thermal oven. Halloysite nanoclay e
kaolin clay was purchased from Sigma Aldrich, Germany. HCl (32%),
NaOH pellets (AR grade) and Methylene Blue trihydrate (analytical
reagent) with a molecular weight of 373.89 g/mol were bought
from Rochelle chemicals, South Africa.
2.2. Preparation of calcined cryptocrystalline magnesite - halloysite
nanocomposite (CCMHN)
To prepare CCMHN, the optimised parameters reported by
Ref. [20] were used. To achieve that equal portions of calcined
cryptocrystalline magnesite (100 g) and halloysite (100 g) were
mixed together in a glass beaker and portions of 50 g of the mixture
were milled using a stainless-steel vibratory ball mill (Retsch RS
200, Germany) for 30 min at 1000 rpm. After the nanocomposite
was milled into a fine powder (<50 nm) it was put in a plastic zip
lock back, sealed and stored until utilisation.
2.3. Preparation of MB working solutions
To prepare the stock solution (1000 mg/L), a specific amount of
dye powder was dissolved in deionised water (ELGA Micra, Veolia
Water Solution and Technologies, UK). All dye solutions were pre-
pared using deionised water to prevent possible ion interferences.
Deionised water was used to dilute the stock solution to obtain the
desired working solutions concentration range (1e30 mg/L). MB
concentration in the experimental solution determination was
done by measuring solution absorbance at lmax ¼ 664 nm using an
UVeVIS spectrophotometer (Thermo Scientific Orion Aqua matte
7000, China).
2.4. Characterisation of the adsorbent
Point of zero charge (PZC) was performed via the solid addition
method as described by Ref. [21]. X ray Diffraction analysis was
done using a PANalytical X'Pert Pro powder diffractometer in qeq
configuration with an X'Celerator detector and variable divergence-
and fixed receiving slits with Fe filtered Co-Ka radiation
(l ¼ 1.789 Å). Fourier Transform Infra-Red analysis was done using
FTIR spectrometer (Bruker Alpha model, USA). TEM images were
attained with a JEOL JEM-2100 F Field Emission Transmission
Electron Microscope (JEOL, Japan). SEM images were attained on a
Zeiss Ultra Plus and Zeiss Cross Beam 540 Field Emission Scanning
Electron microscopes (Carl Zeiss, Germany). Thermal stability of the
nanocomposite was studied, using a Thermo Gravimetric Analyser
(TGA Q500, TA instrument) under air atmosphere with a flow rate
of 50 mL/min and a heating rate of 10  C/min. Surface area was
determined using Brunauer Emmett Teller (BET) analysis (Micro-
meritics Tristar II, Norcross, GA, USA).
2.5. Adsorption studies
The batch study was done using 250 mL glass Erlenmeyer flasks
and a fixed volume of 50 mL dye solutions was used for all exper-
iments. The flasks were shaken at a specified time at 250 rpm in a
waterbath shaker (Labotec, Model 207, South Africa). The effect of
several variables of contact time (15e90 min), CCMHN dose
(0.5e3 g), pH (2 - 12), temperature (25e55  C) and initial dye
concentration (1 - 30 mg/L) were studied. The initial pH of the
solution was adjusted using 0.1 M NaOH or HCl as required. The pH
of the solution was measured with a CRISON MM40 þ multimeter
probe (Hach Lange, Spain) for pH, Electrical Conductivity, Total
Dissolved Solids and temperature. At the end of the adsorption
experiments the concentration of dye was given by measuring the
 T. Ngulube et al. / Journal of Molecular Structure 1184 (2019) 389e399
absorbance of the solution with l ¼ 664 nm using a UV-visible
spectrophotometer. For quality control and assurance, all the ex-
periments were carried out in triplicate and the mean values were
presented.
2.6. Adsorption kinetics
Studying dye adsorption kinetics of adsorbent materials is
necessary to choose the optimum operational settings for the
complete batch system. Adsorption kinetics demonstrates the rate
of dye uptake. In this study, two adsorption kinetic models were
applied.
2.6.1. The lagergren pseudo-first-order model
The pseudo first order kinetic model is usually applied for weak
concentrated aqueous solutions. This model is given by the
Lagergren relationship [22] based on adsorbed quantities. It is the
first equation recognized to describe adsorption kinetics in a liquid/
solid system. Its linear form is given as:
 
k1 t
logðqe  qt Þ ¼ logðqe Þ 
2:303
where qe and qt are the amounts of dye adsorbed (mg/g) at equi-
librium and at time t (min) respectively and K1 (min1) is the
pseudo-first-order rate constant.
2.6.2. The pseudo-second-order model on dye adsorption
Adsorption kinetics may also be described by the pseudo-
second order model [23] generally known and described as:
   
t 1 1
¼ tþ
qt qe k2 q2e
where K2 (g/mg/min) is the pseudo-second-order rate, qe and qt
are the amounts of dye adsorbed (mg/g) at equilibrium and at time
t (min).
2.7. Adsorption isotherms
Adsorption isotherms generally define the equilibrium adsor-
bate concentration in the bulk of the solution and the amount
adsorbed on the adsorbent surface. Studying adsorption isotherms
helps in predicting the ability of the adsorbent to take up an
adsorbate and to design adsorption systems [24]. Data obtained in
this study was analysed using the conventional Langmuir and
Freundlich models.
2.7.1. The Langmuir model
The Langmuir model [25] is based on these assumptions: for-
mation of a single layer of adsorbate on the adsorbent surface, the
presence of defined adsorption sites and a uniform surface short of
interaction between the adsorbed molecules.
The Langmuir equation is written as follows:
 
Ce 1 1
¼ Ce þ
qe Qm Qm b
Where Ce is the equilibrium concentration (mg/L), Qe is the amount
adsorbed at equilibrium (mg/g), b represents the Langmuir
isotherm constant and Qm is the maximum adsorption capacity for
a complete monolayer coverage.
2.7.2. The Freundlich model
The Freundlich model assumes that the distribution of
391
interaction energies can be explained by heterogeneity of adsorp-
tion sites [26]. Contrary to the Langmuir model, the Freundlich
model does not give an upper limit for adsorption which restricts
its application to dilute media. Nevertheless, the Freundlich model
acknowledges that adsorbed molecules interact.
The equation is written as follows:
logQe ¼ n log Ce þ log KF (4)
KF and 1/n are the Freundlich constants, describing the
adsorption capacity and intensity respectively. The constants n and
KF are determined from the slope and the intercept respectively.
2.8. Regeneration studies
To determine if CCMHN could be regenerated and re used after
adsorption, its regeneration potential was evaluated using 0.01 M
NaOH. An MB solution of 10 mg/L and 2 g/50 mL solid/liquid ratio
was used to perform the adsorption experiment. The adsorption
capacity was calculated and then the remaining CCMHN was placed
in the oven to dry for 12 h at 105  C. The dried CCMHN was poured
(1) into 100 mL, 0.01 M NaOH solution and then centrifuged at
5000 rpm for 15 min using an MRC Labs BLCEN-208 (LabGear, USA)
centrifuge. Thereafter it was rinsed in 100 mL deionised water and
then dried for 12 h at 105  C in an oven. As described above, the
procedure of adsorption e desorption cycles were carried out three
times.
3. Results and discussion
3.1. Optimization of the synthesis of the nanocomposite adsorbent
(2)
To determine the optimum conditions for fabricating the
nanocomposite that would effectively remove dyes from aqueous
solution, a dye adsorption experiment was carried out at each stage
of optimization to determine which conditions gave the highest MB
dye removal. Three ratios of the calcined cryptocrystalline
magnesite and halloysite nanoclay respectively (1:1; 2:1; 1:2) were
evaluated and the results of dye removal experiment were as fol-
lows: 1:1 ¼ 96%, 1:2 ¼ 95% and 2:1 ¼ 92%. The highest MB dye
removal was recorded when ratio of calcined cryptocrystalline
magnesite and halloysite nanoclay was 1:1. Based on that, 1:1 ratio
was chosen as the best to prepare the nanocomposite to use for the
dye adsorption experiments.
3.2. Adsorbent physicochemical characteristics
3.2.1. Point of zero charge (PZC)
Fig. 1 shows PZC analysis of CCMHN. Fig. 1 displays that the 3
(3)
Fig. 1. Point of zero charge of CCMHN
392 T. Ngulube et al. / Journal of Molecular Structure 1184 (2019) 389e399

curves (various KCl electrolyte concentrations) had no common

intersection point at DpH ¼ 0 thus a specific pH could not be
considered as pHpzc. However, the curves almost intersected at pH
10 hence for the purposes of this adsorption study, it can be
assumed that CCMHN has a PZC of 10. At pH < pHpzc the surface of
the adsorbent is positive, at pH ¼ pHpzc, the surface charges are
neutral and at pH > pHpzc, the surface of the adsorbent is negative
[27]. Therefore, the adsorption of MB (a cationic dye) is expected to
be high at pH greater than 10 because of electrostatic attraction
between positively charged MB ions and the negatively charged
surface of the adsorbent [28].

3.2.2. X-ray diffraction (XRD)

XRD analysis is displayed on Fig. 2 and it shows that calcined
cryptocrystalline magnesite consists of magnesite and periclase as
the main mineral phases. Halloysite nanoclay was observed to
contain halloysite, quartz and kaolinite minerals. The composite
(CCMHN) is seen to contain halloysite, quartz, brucite, periclase and Fig. 3. FTIR spectra of calcined cryptocrystalline magnesite, halloysite, CCMHN and MB
magnesite. Preparing the nanocomposite via ball milling evidently adsorbed CCMHN.
modified the material. From the diffractogram of CCMHN, the in-
tensity and number of peaks that were observed on unmodified
while that at 3697 cm1 is given to the interlayer hydroxyl
halloysite nanoclay and calcined cryptocrystalline magnesite were
stretching mode [33]. The spectrum of MB adsorbed CCMHN and
reduced. MB adsorbed CCMHN was observed to contain brucite,
raw CCMHN exhibited minor differences in some bands but
periclase, quartz and kaolinite. Similar observations were reported
generally, the bands were almost the same before and after MB
by Ref. [20] for their magnesite-bentonite composite used in the
adsorption. The intensity of the peak for MB adsorbed CCMHN
remediation of metalliferous mine drainage. Brucite is basically
increased at 515, 911 and 1028 cm1. These bands are characteristic
Mg(OH)2 and its high presence on MB adsorbed CCMHN could be a
of Si-O-Si bending and OH groups and the change in their in-
result of periclase (MgO) reacting in aqueous solution of dyes to
tensities shows that these functional groups took part in MB
form Mg(OH)2. Hence, the presence of brucite after adsorption of
adsorption from aqueous solution. The mechanisms of adsorption
the dye could be evidence of a precipitation reaction taking place
involving these functional groups is shown illustrated under sec-
with hydroxides precipitating out of the solution [29].
tion 3.7.

3.2.3. Fourier transform infrared (FTIR)
The FTIR spectra of calcined cryptocrystalline magnesite, hal-
loysite, CCMHN and MB adsorbed CCMHN are shown in Fig. 3. On
the CCMHN, the presence of an absorption band at 505.92 cm1 on
the spectrum corresponds to the Si-O-Si bending hence showing
that the material contains silicate which makes up halloysite [30].
The absorbance at wavelength number 858 cm1 corresponds to
OH deformations linked to Al3þ found in halloysite material. The
band at 1058 cm1 is given to perpendicular SieOeSi stretching
vibrations [31,32]. The band at 1550 cm1 corresponds to asym-
metric stretching vibrations of carbonate. The band at 3620 cm1 is
given to the kaolinite internal hydroxyl group stretching vibration
3.2.4. Transmission electron microscopy (TEM)
Fig. 4 shows TEM images of calcined cryptocrystalline magne-
site, halloysite, CCMHN - and MB adsorbed CCMHN. From image (A)
and (B), it can be observed that calcined cryptocrystalline magne-
site particles have spheroidal and hexagonal morphology. The
dominant morphology of halloysite (C) and (D), is tubular. Some
tubules are long and thin, and others are short and stubby or
emerging from other tubes. A closer look at the TEM images of
CCMHN, images (E) and (F) shows a large rod particle which is
hollow, characteristic of the tubular morphology of halloysite.
Other particles have different hexagonal and circular shapes while
most of the particles in MB adsorbed CCMHN - (G) and (H) have
undefined similar morphology but conspicuous hollow tubular
rods can be seen on image (H). The slight change in the particle
shapes suggests possible interaction between MB and CCMHN. MB
adsorption could further be evidenced by images (G) and (H)
showing some particles being attached on the inside wall of
nanotubes. The particle diameter of the materials was in the range
of 20e50 nm.

3.2.5. Scanning electron microscopy (SEM)

Fig. 5 shows the SEM images of calcined cryptocrystalline
magnesite - (A) and (B), halloysite - (C) and (D), CCMHN - (E) and (F)
and MB adsorbed CCMHN - (G) and (H). Some spherical and hex-
agonal aggregate particles (largely crystallized) are seen on all the
images. No notable difference in the morphology of particles is
shown before and after MB adsorption.

3.2.6. Thermogravimetric analysis (TGA) study

The thermogravimetric analysis of CCMHN and MB adsorbed
Fig. 2. XRD diffraction patterns of calcined cryptocrystalline magnesite, halloysite, CCMHN is presented in Fig. 6. Both thermograms showed a similar
CCMHN and MB adsorbed CCMHN. trend of multistage decomposition corresponding to the loss of
 T. Ngulube et al. / Journal of Molecular Structure 1184 (2019) 389e399 393

Fig. 5. SEM images of calcined cryptocrystalline magnesite- (A) and (B), halloysite - (C)
and (D), CCMHN - (E) and (F) and MB adsorbed CCMHN - (G) and (H).

Fig. 4. TEM images of calcined cryptocrystalline magnesite - (A) and (B), halloysite -
(C) and (D), CCMHN - (E) and (F) and MB adsorbed CCMHN - (G) and (H).

moisture and the exit of water adsorbed on the surface of clay

colloids. The CCMHN and MB adsorbed CCMHN thermograms
showed weight losses of 15.39% and 21.99% respectively. This
means that MB adsorbed CCMHN decomposed more than the raw
CCMHN. Since MB is an organic compound, it might have decom-
posed at about 350  C where most organic residues start to
decompose. Since the profiles were almost similar, the thermal Fig. 6. Thermogravimetric analysis of raw CCMHN and MB adsorbed CCMHN.
stability will be highlighted using the MB adsorbed CCMHN ther-
mogram. At temperatures less than 150  C, a total mass of 1.75% was there was a high mass loss (7.94%) from 330 to 550  C consistent
lost, which corresponds to adsorbed water phase change [34]. Be- with kaolinite dehydroxylation. Lastly, the mass loss in the range
tween 150  C and 330  C, a 1.92% mass loss was observed. This mass 550  C to 726  C (3.42%) corresponds to a combination of illite
loss tallies with phase change of interfoliar water and thereafter dihydroxylation, crystalline water phase change and
394 T. Ngulube et al. / Journal of Molecular Structure 1184 (2019) 389e399
decomposition of calcite [35]. Above 600  C, the observed mass loss
can be ascribed to the decomposition of dolomite and calcite found
in the magnesite material. Furthermore, the loss mass at this final
stage can be ascribed to volatization of all the impurities attached
onto the nanocomposite surfaces. Similar trends of thermogravi-
metric profiles were also reported by Bentahar et al. (2016.). A
further increase in temperature above 726  C shows no further
decomposition, meaning that above that temperature the nano-
composite material is thermally stable.
3.2.7. Brunauereemmetteteller (BET) analysis
One of the reasons why clay-based materials are favourite
candidates used in adsorption systems is because of their high
surface areas which ultimately leads to high adsorption capacities
[36]. Table 1 shows the surface areas of raw and MB reacted CCMHN
and the general observation is that after MB adsorption, there was a
reduction in surface area. The surface area decrease designates the
entry of MB molecules into nanocomposite interlayers leading to
the obstruction of layer channels and consequent reduction of the
overall surface area of the material [37].
3.3. Study of the influence of various parameters on the adsorption
of MB
The effect of contact time, adsorbent dosage, initial MB con-
centration, pH and temperature on the adsorption of MB is shown
in Fig. 7.
3.3.1. The influence of time of contact on the adsorption of MB
The study of the kinetics of MB removal by CCMHN is presented
in Fig. 7(A). The study of the progressive development of the MB
percent removal, displayed that it rose rapidly within the first
60 min and then reached equilibrium after. The observed percent-
age increase during the first 60 min is possibly due to adsorption
sites availability on the surface of the adsorbent [19]. According to
the curve on Fig. 7(A), the contact time required to reach equilib-
rium condition was 60 min and thus it was taken as the optimum
time for subsequent experiments.
3.3.2. The influence of adsorbent dosage on the adsorption of MB
The trend of dye removal percentage with adsorbent dose is
given in Fig. 7(B). Dosage is among the chief parameters that in-
fluence the adsorption process by affecting the adsorbent's
adsorption capacity. The dye percentage removal increased as the
adsorbent dose was increased from 0.5 to 1.5 g and then gradually
increased until 3 g. The rapid increase at the initial stages is asso-
ciated with an increased surface area of the adsorbent and abun-
dance of vacant adsorbent sites [38]. The further continual constant
adsorption is probably due to the binding of almost all MB mole-
cules on the surface of the adsorbent surface and equilibrium
attainment in solution between the adsorbate and the adsorbent
[39,40]. Consequently, in all the subsequent experiments, 2 g of
adsorbent dose was used. A similar trend was described for MB
adsorption by modified lignocellulosic materials [41].
3.3.3. The influence of initial dye concentration on adsorption of MB
Fig. 7(C) shows the trend of CCMHN adsorption capacity and MB
percentage removal vs initial MB concentration. The results show a
Table 1
Surface areas of raw (CCMHN) and MB reacted CCMHN (MB-CCMHN).
Single point surface area (m2/g)
CCMHN 17.9525
MB-CCMHN 16.9215
general trend of decreasing percentage removal as the initial MB
concentration is increased. Adsorption capacity however showed
an opposite trend wherein adsorption capacity increased as initial
MB concentration was increased. The results of the decrease in
percentage removal with increasing dye concentration are similar
to those reported for MB adsorption onto mesoporous birnessite
where an increase of adsorption capacity from 33.3 to 106.1 mg/g
was observed [42]. Such a trend could be credited to the concen-
tration gradient driving force increasing with increasing the initial
dye concentration.
3.3.4. The influence of pH on the on adsorption of MB
The initial solution pH usually has a notable influence on
adsorption processes by affecting the molecular structure of dyes in
aqueous solution and affecting the surface charges of the adsorbent
material too. In this study, the pH of the solution was maintained
between 2 and 12. Fig. 7(D) shows that percentage dye removal
decreased from 93.80% to 65.47% from pH 2 e pH 4. The overall
observation is that as the pH increased, the percent removal of MB
by CCMHN decreased. From the PZC results, it is expected that, the
removal of MB, a cationic dye is expected to be high when the
adsorbent is negatively charged at pH above 10, however MB
percent removal was lower, possibly implying that the solution pH
had a negligible influence on the charges of the adsorbent's surface.
Nevertheless, the adsorption capacity of the material increased
with increase in pH.
3.3.5. The influence of temperature on the adsorption of MB
Assessment of the effect of solution temperature on the
adsorption process was done to evaluate the capability of CCMHN
in dye adsorption in cases of a variety of wastewaters, considering
different conditions that dye wastewater exists in. The influence of
solution temperature on MB adsorption was done at four temper-
atures ranging from 25 to 55  C. The quantity of MB adsorbed on
CCMHN at different temperatures is given in Fig. 7(E). It is seen that,
increasing the temperature of the solution decreased the amount of
MB adsorbed. The drop of adsorption capacity with rising tem-
perature shows that adsorption was an exothermic process [43].
This may probably be because high temperatures reduce forces of
adsorption between the available adsorbent sites and the dye
molecules as a result, decreasing the rate of adsorption [44]. For this
reason, it can be said that there is no need to increase the solution
temperature since the maximum adsorption capacity of CCMHN is
recorded at room temperature. Like results were recorded by
Ref. [45] where they noted that the MB adsorption was less affected
by temperature, the adsorbed amounts slightly decreased with the
increase of solution temperature from 10 to 50  C.
3.4. MB adsorption kinetic studies
3.4.1. Application of lagergren pseudo-first-order model on dye
adsorption
For the Lagergren pseudo-first-order model to be deemed fit,
the plot of t vs log (qe-qt) must be linear and the calculated results
from this study did not give any linear relationship. This indicates
that the kinetics of adsorption of MB on CCMHN does not corre-
spond to the kinetics of the pseudo-first order.
BET Surface Area (m2/g) Langmuir Surface Area (m2/g)
18.1753 25.3153
17.0475 23.6503
 T. Ngulube et al. / Journal of Molecular Structure 1184 (2019) 389e399 395

Fig. 7. Removal of MB by CCMHN as a function of (A) - contact time [1 g, 10 mg/L, 50 mL, 250 rpm, room temperature] (B) e dosage [60 min, 10 mg/L, 50 mL, 250 rpm, room
temperature] (C) - initial MB concentration [60 min, 2 g, 50 mL, 250 rpm, room temperature] (D) - pH [60 min, 2 g, 10 mg/L, 50 mL, 250 rpm, room temperature] (E) -temperature
[60 min, 2 g, 10 mg/L, pH4, 50 mL, 250 rpm].

3.4.2. Application of pseudo-second-order model on dye adsorption

Modelling of MB adsorption kinetics onto CCMHN by the
pseudo-second order model is presented on Fig. 8. The kinetic
parameters attained by fitting MB adsorption kinetics data are
displayed on Table 2. The kinetic models’ cogency is derived from
the correlation coefficients values (R2). From Fig. 8 is noted that the
data fitted well to the pseudo-second order kinetic model. There-
fore, the pseudo-second order is the appropriate adsorption model
to describe MB dye adsorption onto CCMHN hence indicating that
the rate limiting step during the adsorption process could be
chemisorption. However, the experimental and calculated adsorp-
Fig. 8. Pseudo second order kinetic model.
tion capacities shown on Table 2 are not very close to each other.

3.5. Isotherms of MB adsorption

The data obtained in this study was analysed using the common
396 T. Ngulube et al. / Journal of Molecular Structure 1184 (2019) 389e399

Table 2
Adsorption kinetics and isotherm parameters for MB removal by CCMHN.

Pseudo-second-order
Parameter values Qe (exp) mg/g Qe (cal) mg/g K2 (g/mg/min) R2
0.6547 0.0006 0.001 1
Langmuir model
Parameter values Qm (mg/g) Ka (L/mg) RL R2
0.7079 1.3570 0.0445 0.9766
Freundlich model
Parameter values KF (mg/g) 1/n n R2
2349 0.5245 1.9066 0.8812

Langmuir and Freundlich adsorption isotherm models. When the

correlation coefficients values (R2) of the applied isotherm models
where compared, the best fit was given by the Langmuir model
(Fig. 9(a)) than the Freundlich model (Fig. 9(b)) for MB adsorption
onto CCMHN with a high R2 value of 0.98. Data fitting onto the
Langmuir model shows that adsorption of MB took place on ho-
mogeneous surfaces [36]. RL (the separation factor) values indicate
the nature of adsorption to be unfavorable if RL > 1, linear if RL ¼ 1,
favourable if 0 < RL < 1 and irreversible if RL ¼ 0. From the data in
Table 2, the RL value is greater than 0 but less than 1 indicating that
Langmuir isotherm is favourable. The maximum Langmuir mono-
layer coverage capacity (Qm) was determined to be 0.7079 mg/g.
Accordingly, it was close to the experimental adsorption capacity
(0.6547 mg/g) confirming the fit. Similar results were also obtained
by Ref. [37]. Fig. 10. Regeneration of CCMHN

3.6. Regeneration study

It is very vital to regenerate spent adsorbents to determine their
reusability to mechanise a cost-effective adsorption medium in
wastewater treatment plants. Chemical regeneration by 0.01 M
NaOH was done on the nanocomposite adsorbent and the regen-
eration restored 71.55 and 35% MB removal from cycle 2 to 4
respectively (Fig. 10). From the recovery efficiency, it was evident
that as the spent adsorbent was regenerated more, its capacity to
adsorb MB was decreasing but it still managed to remove an
appreciable amount of MB from aqueous solution after 4 cycles. The
outcomes evidently demonstrated the stability and good reus-
ability of the nanocomposite prepared in this work.
FTIR analysis study showed bands at 3600e3700 cm1 which are
associated with OH groups adsorbed water shifted after dye
adsorption indicating that the hydroxyl groups played an important
role in the adsorption process. MB is a basic dye and its interactions
with the surface of the adsorbent and the dyes are chemical. It
seems that there is a formation of covalent bonds between oxides
(CaO, MgO and SiO2) available on the adsorbent surface with hy-
droxyl groups and the positively charged MB ions. Moreover, many
studies report that organic dye adsorption oxide materials usually
occur via electrostatic attraction [46]. A schematic representation
of hydrogen bonding and electrostatic interaction between the
adsorbent's surface and MB dye molecules is presented in Fig. 11.

3.7. Proposed mechanism 3.8. Comparison of adsorption capacity of CCMHN for MB with
other adsorbents
From the characterisation studies of the adsorbent, before and
after dye removal, mechanisms of dye uptake can be established. Table 3 is showing several adsorbents for MB and their

Fig. 9. (a) - Langmuir (b) - Freundlich isotherm model for MB adsorption onto CCMHN.
 T. Ngulube et al. / Journal of Molecular Structure 1184 (2019) 389e399 397

Fig. 11. Hydrogen bonding and electrostatic interaction between the surface of the adsorbent and MB ions.

Table 3
Comparison of the maximum adsorption of MB from this study with previous studies.

Material Maximum adsorption capacity qm (mg/g) References

CCMHN 0.71 Present study

Acid-bound iron oxide magnetic nanoparticles 0.19 [47]
Fly ash 1.10 [48]
Fly ash 1.47 [49]
Red mud 2.49 [50]
Fly ash 5.57 [51]
Fly ash 7.99 [52]
Aminofunctionalized attapulgite clay nanoparticles 13.698 [53]
Coal fly ash 16.6 [17]
Natural illitic clay mineral 24.87 [54]
Activated lignin-chitosan extruded blends 36.25 [55]
Heat-treated palygorskite clay 78.11 [56]
Brown macroalga 95.45 [57]
Montmorillonite/CoFe2O4 composite 97.75 [58]
Aminofunctionalized attapulgite clay nanoparticles 215 [59]
Plasma-surface modification on bentonite clay 303 [60]
MOF nanocomposite 325.62 [61]

adsorption capacities. In contrast with some of the reported ad-
sorbents, the adsorption capacity for CCMHN is fairly low compared
to many adsorbents especially the chemically modified ones.
However, a lot of factors affect the variances in adsorption capac-
ities for example operational conditions including dosage, pH and
time.
4. Conclusion
This study demonstrated that calcined cryptocrystalline
magnesite - halloysite nanocomposite can be utilised as an effective
adsorbent for the removal of methylene blue from aqueous solu-
tions. The characterisation results showed that the nanocomposite
has particles size ranging between 20 nm and 50 nm. It was further
shown that the nanocomposite contained halloysite, quartz, bru-
cite, periclase and magnesite and some of the compounds found in
these minerals assisted in the uptake of MB dye by the
nanocomposite via electrostatic interactions. XRD analysis showed
good variations of mineralogy before and after adsorption with
reduction in peak intensities after MB adsorption especially for
periclase with a 54.67% reduction. The results showed that
adsorption was also largely affected by parameters like adsorbent
concentration and adsorbent dosage. pH however had a negligible
influence in the adsorption of MB by CCMHN. The Langmuir
isotherm was the most suitable model for MB adsorption with an R2
of 0.9766 compared to the Freundlich which had an R2 value of
0.8812. The kinetics data was described well by the pseudo second
order implying that the process of adsorption was dependant on
both time and concentration. The batch study showed that opti-
mum conditions to remove MB by CCMHN are: 60 min contact
time, dosage of 2 g, temperature at 25  C and initial MB concen-
tration of 5 mg/L of MB.
398 T. Ngulube et al. / Journal of Molecular Structure 1184 (2019) 389e399
Conflicts of interest
The authors declare no conflict of interest.
Acknowledgments
This research was funded by the University of Venda Research
Directorate (grant number S839), National Research Foundation of
South Africa (grant number 102221) and Water Research Com-
mission (grant number K5/2756/3). The authors are also thankful to
the Council for Scientific and Industrial Research (CSIR), Depart-
ment of Ecology and Resource Management & Hydrology and
Water Resources labs (University of Venda) for extending all facil-
ities required for this research.
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