Clay Minerals (2019), 54, 197–207

doi:10.1180/clm.2019.27

Article

Evaluation of the efficacy of halloysite nanotubes in the removal of

acidic and basic dyes from aqueous solution
Tholiso Ngulube1*, Jabulani Ray Gumbo2, Vhahangwele Masindi3,4 and Arjun Maity5,6
1
Department of Ecology and Resources Management, School of Environmental Sciences, University of Venda, Private Bag X5050, Thohoyandou, 0950, Limpopo,
South Africa; 2Department of Hydrology and Water Resources, School of Environmental Sciences, University of Venda, Private Bag X5050, Thohoyandou, 0950,
Limpopo, South Africa; 3Council for Scientific and Industrial Research (CSIR), Built Environment, Hydraulic Infrastructure Engineering, PO Box 395, Pretoria, 0001,
South Africa; 4Department of Environmental Sciences, School of Agriculture and Environmental Sciences, University of South Africa (UNISA), PO Box 392, Florida,
1710, South Africa; 5Department of Applied Chemistry, University of Johannesburg, Johannesburg, South Africa and 6DST/CSIR National Centre for Nanostructured
Materials, Council for Scientific and Industrial Research (CSIR), Pretoria, South Africa

Abstract
The present work describes the removal of Direct Red 81, Methyl Orange, Methylene Blue and Crystal Violet from aqueous solution
using halloysite nanotubes. The clay mineral was physicochemically characterized using various methods. The influences of pH, inter-
action time, initial dye concentration, adsorbent amount and temperature on adsorption were monitored and interpreted. Although pre-
vious work has shown that acidic pH conditions favour the adsorption of pollutants from aqueous systems by clay materials, in this study
maximum removal was possible over a wide range of pH conditions (pH ≥2–12). Adsorption was very rapid, and equilibrium was
attained within 30 min. For all four dyes studied, chemical reaction seemed significant in the rate-controlling step, and the pseudo-
second-order chemical reaction kinetics provided the best correlation of the experimental data. Thermodynamically, the process was
spontaneous, with Gibbs energy decreasing with increasing temperature. Halloysite would be suitable for removing dyes from aqueous
solution. This was further tested by using the halloysite nanotubes for the removal of complex dyes from printing and ink industry
effluents.

Keywords: halloysite nanotubes, acidic and basic dyes, adsorption, kinetics, isotherms, thermodynamics
(Received 31 August 2018; revised 17 March 2019; Associate Editor: C.-H. Zhou)

Coloured, toxic industrial waste is increasingly becoming a social
and environmental problem. The contaminants may spread
through living organisms via aquatic pathways (Ngulube et al.,
2017), necessitating the development of numerous techniques to
eliminate dyes from wastewater (Yang et al., 2018). Adsorption
is among the methods used for water treatment because of its
low start-up costs, straightforward design and ease of operation
and implementation, even in small plants (Mu & Wang, 2016).
Because of stringent laws concerning the removal of dyes from
wastewaters before their discharge into the aquatic environment
and the cost of conventional adsorbents, development of new,
low-cost adsorbents with improved adsorption properties has
become commonplace (Yagub et al., 2014).
Various abundant, naturally occurring materials have been
examined as possible adsorbents for dye treatment (Santos
et al., 2016; Sarma et al., 2016). There is increasing focus on nat-
ural adsorbents, and preferably the development of adsorbents
demonstrating both low costs and high adsorption capacities for
removing inorganic contaminants from polluted waters.
Although a variety of sorbents have been used for water
*E-mail: tholisongulube@gmail.com
Cite this article: Ngulube T, Gumbo JR, Masindi V, Maity A (2019). Evaluation of the
efficacy of halloysite nanotubes in the removal of acidic and basic dyes from aqueous
solution. Clay Minerals 54, 197–207. https://doi.org/10.1180/clm.2019.27
Copyright © Mineralogical Society of Great Britain and Ireland 2019
decontamination, naturally available clays have been applied in
most developing countries (Adebowale et al., 2014; Gamoudi &
Srasra, 2018; Kausar et al., 2018). It is extremely important to
choose ta echnique for water decontamination that is cheap and
requires minimal workload. Using clay minerals and soils fits
well with the above-mentioned requirements.
Halloysite clay is an inexpensive adsorbent applied for the deco-
lourization of dyed wastewater. Halloysite (Al2Si2O5(OH)4·nH2O,
where n is 0 in kaolinite and up to 4 in halloysite) is a dioctahedral
1:1 clay mineral belonging to the kaolin group (Berthier, 1826). It
has a similar structure to kaolinite, but it is rolled in tubes with dia-
meters of ∼50 nm and lengths of ∼1000 nm (Słomkiewicz et al.,
2015). Halloysite clay displays greater adsorption capacity for
both acidic and basic dyes because of the presence of a negatively
charged SiO2 outermost surface and positively charged Al2O3
inner surface; thus, it has effective bivalent adsorbing capacity
(Zhao et al., 2013).
Most previous studies have focused on an individual dye using
synthetic solutions. The objectives of the present study were to
evaluate the adsorption capacity of halloysite clay for two anionic
and two cationic dyes, Direct Red 81 (DR81), Methyl Orange
(MO), Methylene Blue (MB) and Crystal Violet (CV), which
are used in the textile industry, and to evaluate the influences
of several parameters on the adsorption capacity of the clay.
The adsorption kinetics and isotherms were studied in order to
198
determine the adsorption capacity of the clay. This provided an
opportunity to perform a comparative analysis on how the halloy-
site material adsorbs variously charged dyes under the same experi-
mental conditions. There have been few studies that test adsorbent
materials on real, coloured industrial effluents. In the present study,
halloysite was tested on real industrial wastewater in order to ascer-
tain the feasibility of the adsorbent under real conditions.
Materials and methods
Materials
The halloysite nanoclay–kaolin clay was purchased from Sigma
Aldrich (South Africa). MO, MB, CV, HCl, KCl and NaOH pellets
were purchased from Rochelle Chemicals (South Africa). DR81 was
purchased from Sigma Aldrich (South Africa). Real industrial effluent
was obtained from an operator in the printing and ink industry.
Batch removal studies
Deionized water (ELGA, Micra Veolia Water Solution and
Technologies, UK) was used to prepare dye solutions by dissolv-
ing appropriate amounts, accurately weighed on an electronic bal-
ance (RADWAG electronic balance, Wagi Elektroniczen, Poland),
of dry powder dye to prepare a stock solution (1000 mg/L).
Experimental solutions were obtained by serial dilutions to obtain
the working solutions at desired concentrations. The final concen-
trations of the dyes were estimated for each sample absorbance at
the wavelength corresponding to the maximum absorption peak
(λmax = 510, 505, 664 and 590 nm for DR81, MO, MB and CV,
respectively) using a Vis spectrophotometer (Thermoscientific
Orion Aqua Matte 7000, China) using a constructed calibration
graph from prepared standard solutions. Batch adsorption experi-
ments were performed in 250 mL glass Erlenmeyer flasks contain-
ing 50 mL of dye solution of desired concentrations at various pH
values (2, 4, 6, 8, 10 and 12), initial dye concentrations (1, 5, 10,
20, 30 and 40 mg/L), temperatures (25°C, 35°C, 45°C and 55°C),
contact times (10, 15, 20, 30, 60 and 90 min) and adsorbent
dosages (0.1, 0.2, 0.4, 0.8, 1.0 and 2 g). The solution pH was
adjusted using either 0.1 M HCl or 0.1 M NaOH solution. The
solutions were shaken on a reciprocating table shaker (Labotec,
Model 207, South Africa) at 250 rpm. After the equilibration
time, the solutions were allowed to settle for 30 min and the
absorbance of the supernatant solution was recorded. All of the
experiments besides those of temperature variation were carried
out at room temperature (25 ± 3°C). In order to verify the repro-
ducibility of the results, the experiments were carried out in trip-
licate and the mean values were reported.
Characterization
X-ray diffraction (XRD) traces of halloysite were acquired using a
PANalytical X’Pert PRO powder diffractometer in θ–θ configur-
ation with an X’Celerator detector and variable divergence and
fixed receiving slits with Fe-filtered Co-Kα radiation (λ = 1.789 Å).
The phases were identified using X’Pert Highscore Plus software.
The relative phase amounts (wt.%) were estimated using the
Rietveld method (Autoquan program). Fourier-transform infrared
(FTIR) spectroscopy was used to determine the functional groups
of halloysite. A powdered sample of the adsorbent material was
analyzed using ALPHA II’s Platinum attenuated total reflection
(ATR) single reflection diamond module with the ATR method of
Tholiso Ngulube et al.
analysis. The FTIR spectra were recorded using a FTIR spectrometer
(Bruker, Alpha, USA) with a scan range of 450–4500 cm–1.
Transmission electron microscopy (TEM) images were acquired
using a JEM-2100F Field Emission microscope (JEOL, Japan).
The point of zero charge (PZC) was determined using the solid
addition method described by Izuagie et al. (2016). The Brunauer–
Emmett–Teller (BET) specific surface area was determined by N2
adsorption (Micromeritics Tristar II, Norcross, USA).
Adsorbent regeneration
The regeneration potential of halloysite was evaluated with 0.01 M
NaOH. An adsorption experiment was performed using 2 g of clay,
50 mL of solution and a 10 mg/L concentration of each dye. The
amount of dye adsorbed was noted and the adsorbent was dried
in the oven for 12 h at 105°C. The adsorbent was then dispersed
in 50 mL of 0.01 M NaOH solution and the dispersion was centri-
fuged at 50,000 rpm for 15 min. The adsorbent was washed by 50
mL MilliQ water, dried in an oven for 12 h at 105°C and cooled
in a desiccator. The dried adsorbent was used for another adsorp-
tion experiment following the procedure described above. The
same procedure using the same adsorbent was repeated three times.
Results and discussion
Characterization
X-ray diffraction results
The XRD traces of the original halloysite and the halloysite after
adsorption of DR81, MO, MB and CV dyes are shown in Fig. 1.
There is no significant difference in the traces after adsorption
of the dyes. The diffractograms showed sharp peaks at 13.95,
23.23 and 31.02°2θ. The results agree with previous reports
on halloysite nanotubes (Jiang et al., 2015). The peaks identified
are characteristic of quartz (SiO2), kaolinite (Al2Si2O5OH4) and
halloysite (Al2Si2O5OH4) (Zhang et al., 2012). The similarity of
raw halloysite and dye-adsorbed halloysite diffractograms indi-
cates that the dye-adsorption process did not alter the crystallog-
raphy or major mineral phases of the sample.
FTIR results
The FTIR spectra of raw halloysite and the halloysite after adsorp-
tion of DR81, MO, MB and CV dyes are shown in Fig. 2. The
spectra display bands in the OH-stretching region (3700 cm–1)
(Luo et al., 2010) and bands associated with stretching and bend-
ing vibrations of the aluminosilicate framework (∼1200 cm–1)
typical of kaolin minerals (Prokop et al., 2015). The bands at
3696 and 3623 cm–1 are due to the stretching vibrations of
hydroxyl groups at the surfaces of the nanotubes (Xie et al.,
2011). Fourier-transform infrared analysis is an important tool
for identifying the characteristic functional groups that might be
responsible for dye binding (D’Souza et al., 2008). There are no
significant differences among the spectra before and after adsorp-
tion. Therefore, the functional groups (hydroxyls and aluminosili-
cate framework) noted in the FTIR spectra may not have been
involved in the dye-removal process.
TEM results
The TEM images of the original halloysite and the halloysite
after adsorption of DR81, MO, MB and CV dyes are shown in
Fig. 3. The original halloysite consists mainly of halloysite nano-
tubes, some of which exhibit hollow, rod-like structures
(Joussein et al., 2005; Ahmed et al., 2010). The halloysite
Clay Minerals
Fig. 1. XRD traces of the original halloysite and the halloysite after adsorption of
DR81, MO, MB and CV dyes.
nanotubes are 500–700 nm long, and their inner and outer dia-
meters are 40–60 nm. The nanotubes contain empty lumens,
with some rod structures being inside the empty lumens
(Fig. 3a,b). The nanotubes of halloysite after adsorption of dyes
contain additional material on the external walls (Fig. 3c–f).
Moreover, the halloysite maintains its tubular structure even
after dye adsorption.
SEM results
The SEM images of the original halloysite and the halloysite after
adsorption of DR81, MO, MB and CV dyes are shown in Fig. 4.
The halloysite consists of agglomerates of nanotubes with some
irregularities in their diameters and wall thicknesses and a fibrous
morphology (Kamble et al., 2012). The original halloysite has an
uneven surface, which nevertheless is smoother compared to its
counterpart after dye adsorption. After dye adsorption, the surface
morphology changed considerably, which indicates that dye mole-
cules were adsorbed onto the surface and interaggregate pores,
because the halloysite surface is more uniform, especially after
adsorption of MB and CV dyes (Fig. 4e,f). Previous studies also
revealed that the surface of the adsorbent became more homogen-
ous compared to the original materials (Sarma et al., 2016). In add-
ition, the halloysite has a different morphology after adsorption of
MO and CV (Fig. 4d,f). The images show the rod-like structures of
the halloysite, clearly confirming the tubular nature of the clay.
Figure 4d shows a homogenous surface consisting of fluffy flakes
of various sizes and shapes. The fibrous surface topography of the
clays is expected to increase the degree of unsaturation of the surface
with dangled bonds and free valences, thus increasing the total spe-
cific surface area of the clay (Ngulube et al., 2017).
BET results
The large adsorption capacities of clay materials are largely due to
their large specific surface areas (Cadena et al., 1990). The specific
surface area of a clay is directly proportional to its adsorption cap-
acity (Santos et al., 2016; Sarma et al., 2016). The halloysite has a
BET specific surface area of 41.94 m2/g (Table 1), which is greater
than or comparable to other clays (Park et al., 2011; Gu et al.,
2014; Sari & Tuzen, 2014). Comparison between the original hal-
loysite (H) and its counterparts after dye adsorption (HDR81,
HMO, HMB and HCV) showed an increase in the specific surface
area after dye adsorption, with the greatest surface area being for
199
Fig. 2. FTIR spectra of the original halloysite and the halloysite after adsorption of
DR81, MO, MB and CV dyes.
HMO. A large specific surface area is associated with significant
soil–water contaminant interaction, which indicates high reactiv-
ity (Pennel, 2016). Theoretical relationships for surfaces of various
particle geometries show that surface area is controlled by the
smallest particle size. With decreasing particle size, the specific
surface area increases and the small particles tend to have platy
and rod-like geometries (Santamarina et al., 2002). After adsorp-
tion of the four dyes, there is a clear change in the shape of the
particles (Fig. 4), particularly with the adsorption of DR81 show-
ing platy geometries; hence, this might have increased the specific
surface area after dye adsorption. The kaolinite pores are more
open, and this leads to a greater pore diameter of the slit-shaped
pores in the structure (Boukhemkhem & Rida, 2017). As
explained previously, the fibrous surface topography of the clays
is expected to increase the degree of unsaturation of the surface
with dangled bonds and free valences, thus increasing the total
surface area of the clay (Ngulube et al., 2017).
Batch dye adsorption studies
The effect of contact time, adsorbent dosage, initial concentration,
pH, temperature and PZC on the adsorption of dyes is shown in
Fig. 5.
Effect of time
The kinetics of the adsorption determine the optimum time at
which equilibrium is attained. Depending on wastewater-process
design, this information may be used in wastewater-treatment
plants. The results of kinetic tests are shown in Fig. 5a. The
adsorption of all dyes was comparable for all of the contact
times used. The removal of MB and CV was almost complete
(98–99%), that of DR81 was slightly lower (86–87%) and finally
that of MO was the lowest (79–80%). The near-constant percent-
age of removal after 30 min indicates that the adsorbent was
approaching its optimum performance; hence, 30 min was
selected as the optimum contact time for subsequent experiments.
Effect of adsorbent dose
The effect of adsorbent dosage is illustrated in Fig. 5b. With
increasing adsorbent dose, the percentage of removal of the
dyes increased, similarly to previous studies (Ciesielczyk et al.,
2017). Increasing adsorbent dosage at a constant volume and
dye concentration leads to the saturation of adsorption sites.
Due to the formation of aggregates at higher doses, there might
200
Fig. 3. TEM images of the original halloysite (a,b) and the halloy-
site after adsorption of (c) DR81, (d) MO, (e) MB and (f) CV dyes.
be a decrease in adsorption capacity because aggregation would
lead to a decrease in total surface area of the adsorbent and
increased diffusion path length (Sarma et al., 2016).
Effect of initial dye concentration
The effect of initial dye concentration is shown in Fig. 5c. By
increasing initial dye concentration to 20 mg/L, the percentage
of removal of DR81 and MO increased, decreasing at higher con-
centrations. However, the percentage of removal of CV and MB
showed a different trend, decreasing gradually with increasing ini-
tial dye concentration from 1 to 40 mg/L. This observation is in
accord with previous studies (e.g. Anirudhan & Ramachandran,
2015) in which the concentration of the dye was a driving force
for overcoming the mass transfer resistance of dye molecules
between the solid and the aqueous phases. At low dye concentra-
tions, there are more active sites available for adsorption; hence, at
this stage, adsorption is independent of initial concentration.
However, with increasing concentration, the available sites are
occupied and ultimately a decrease in dye removal is observed
(Ogunmodede et al., 2015).
Tholiso Ngulube et al.
Effect of pH
The pH affects the adsorption of dyes because it affects the surface
characteristics of the adsorbent (Ngulube et al., 2018). The pH of
a solution determines the degree of protonation of exchange sites
of the adsorbate due to variable charge, thereby influencing the
specific charge of exchange sites and eventually the adsorption
tendency of the adsorbent (Tomar et al., 2014). In the present
study, the pH had a negligible influence on the removal of the
DR81, MB and CV dyes in the pH range 2–12 (Fig. 5d), in
accordance with previous studies (Santos et al., 2016). For MO,
maximum removal (70.24%) was observed at pH 8, being lower
than 40% for the remaining pH values. The MO molecules have
different charges at different pH values (Subbaiah & Kim,
2016). The dissociation constant (pKa) for MO is 3.46 (Arshadi
et al., 2016); hence, the MO species will mainly exist as monova-
lent anions at this equilibrium pH. Below and above this pH, the
MO will go through a protonation process that will determine its
charge. Due to the protonation reaction (≡RN(CH3)2 + H+ →
≡RNH+(CH3)2), MO is positively charged at pH < 3.76 (Yao
et al., 2011). In addition, the halloysite surface is also positively
Clay Minerals 201

Fig. 4. SEM images of the original halloysite (a,b) and the halloy-
site after adsorption of (c) DR81, (d) MO, (e) MB and (f) CV dyes.

Table 1. Specific surface areas of the original halloysite (H) and the halloysite adsorption. An increase in adsorption capacity with temperature
after adsorption of DR81 (HDR81), MO (HMO), MB (HMB) and CV (HCV) dyes. indicates an endothermic reaction whereas a decrease in adsorp-
tion capacity with increasing temperature indicates an exothermic
BET surface
Single point surface area area Langmuir surface area process (Zulfikar, 2013). In the present study, temperature varia-
(m2/g) (m2/g) (m2/g) tions did not affect significantly the removal of all four dyes, indi-
cating that there is no need to adjust temperature in order to
Halloysite 41.0 41.9 57.4
effectively remove dyes from aqueous solutions using halloysite
HDR81 44.7 45.8 62.8
HMO 45.5 46.6 65.0 (Fig. 5f).
HMB 42.5 43.5 61.0
HCV 42.9 44.0 60.3 Point of zero charge studies
The PZC determines the type of surface-active centres on the
adsorbent, which affect the adsorption processes (Yagub et al.,
2014). Adsorption of positively charged dyes is enhanced at
charged; hence, adsorption is limited because of repulsive forces
pH > PZC due to the presence of functional groups such as
between the surface and the positively charged MO particles.
hydroxyl ions on the surface, whereas adsorption of negatively
With increasing pH, the MO has fewer positive charges. Hence,
charged dyes is enhanced at pH < PZC, because the surface of
the enhanced MO adsorption on halloysite is attributed to hydro-
the adsorbent is positively charged (Ngulube et al., 2017).
gen bonding, electrostatic attraction and strong surface complex-
When the pH is higher than the PZC, the surface charge of hal-
ation (Xiang et al., 2014). At alkaline pH up to 12, the electrostatic
loysite is negative, while it is positive when the pH is lower than
repulsion and OH– competition lead to a decrease in the adsorp-
the PZC. The PZC of the halloysite used in this study is 5
tion of anions (Cheah et al., 2013).
(Fig. 5f). It would be expected that the adsorption of MB and CV
would be greatest at pH > 5 and those of DR81 and MO would be
Effect of temperature greatest at pH < 5. However, the variation of pH did not affect the
Generally, temperature has a significant effect on reaction rate. removal of the dyes, except for MO (Fig. 5d), suggesting that the
With increasing temperature, chemical reaction rate also increases adsorption of the remaining three dyes was not predominantly
(Mekatel et al., 2015). Therefore, temperature might affect dependent on the surface charges of halloysite.
202 Tholiso Ngulube et al.

Fig. 5. Removal of DR81, MO, MB and CV dyes by halloysite as a function of (a) contact time, (b) halloysite dosage, (c) initial dye concentration, (d) pH, (e) tem-
perature and (f) PZC.

Treatment of real industrial effluent Table 2. Characterization of actual industrial effluent.

The physical characterization of textile mill raw wastewater has Industrial effluent Industrial effluent
been carried out for colour, total dissolved solids, electrical con- before treatment after treatment
ductivity, turbidity, total suspended solids and pH. The results Analyser parameter with halloysite with halloysite
of the wastewater characteristics before and after treatment with Total dissolved solids (mg/L) 1219 1068
halloysite nanoclay are presented in Table 2 and the progress of Total suspended solids (mg/L) 918 785
the reaction is illustrated in Fig. 6. The wastewater is classified Electrical conductivity (μS/m) 1764 1504
as ‘high-strength wastewater’ (Benefield, 2002). After treatment Turbidity (NTU, FNU) 0.01 246
with halloysite clay at the optimum conditions determined from pH 8.77 8.20
Colour Black Milky white
the batch study, the wastewater could be characterized as medium-
strength wastewater. The dye-removal rates were 79.25%, 90.01%, FNU = Formazin Nephelometric Unit; NTU = Nephelometric Turbidity Unit.
Clay Minerals 203

Table 3. The pseudo-second-order parameters for the adsorption of DR81, MO,

MB and CV dyes onto the halloysite clay.

Parameter DR81 MO MB CV

Qe (mg/g) experimental 4.3553 0.2055 4.9219 1.2419

Qe (mg/g) calculated 4.3668 4.7847 4.9285 5.2192
k2 (g/mg/h) 0.0001 1154.9 6.0725 630.56
R2 1 1 1 1

The fitting between experimental data and the model-predicted

values was expressed by the coefficient of determination, R2. The
curves of the plots are given in the Supplementary Material, and
the calculated kinetic parameters and the corresponding linear
regression correlation coefficient R2 values are summarized in
Table 3. There is good agreement between experimental and
calculated qe values for DR81 and MB dyes. The coefficients of
determination for the pseudo-second-order kinetics model (R2)
are all equal to 1, indicating the applicability of this kinetic model
and the second-order nature of the adsorption process of the
dyes onto halloysite clay. These results imply that the chemisorp-
tion mechanism may play an important role in the adsorption of
DR81, MO, MB and CV dyes.

Adsorption isotherm studies

An adsorption isotherm describes the relationship between the
Fig. 6. Real industrial effluent before and after treatment with halloysite nanoclay. amount of adsorbate adsorbed by the adsorbent and the remain-
ing adsorbate concentration in the solution at equilibrium.
Adsorption equilibrium studies were performed using two
92.22% and 92.22% for DR81, MO, MB and CV dyes, respect- adsorption isotherms.
ively. The colour of the textile wastewater changed from black The Langmuir isotherm describes the formation of a mono-
to milky white after treatment (Fig. 6). layer adsorbate on the outer surface of the adsorbent, beyond
which no further adsorption takes place (Langmuir, 1918). The
isotherm is expressed by the following equation:
Adsorption kinetics studies


Adsorption kinetics are important in determining the effective- Ce 1 1
= Ce + (3)
ness of adsorption. In this study, two models were used to predict qe Qm Qm b
the adsorption kinetics of DR81, MO, MB and CV onto halloysite.
where Ce is the equilibrium concentration (mg/L), Qe is the
amount adsorbed at equilibrium (mg/g), b represents the
The pseudo-first-order model Langmuir isotherm constant (L/mg) and Qm is the maximum
The linear form of the pseudo-first-order model was described by adsorption capacity (mg/g) for complete monolayer coverage.
Ho & McKay (1998) and it can be expressed as: The separation factor (RL) was calculated from the following

 equation:
k1 t
log(qe − qt ) = log(qe ) − (1) 1
2.303 RL = (4)
(1 + bCo )
Where qe (mg/g) is the adsorption capacity at equilibrium, qt
(mg/g) is the adsorption capacity at time t and k1 (1/min) is where Co is the initial concentration (mg/L). RL values between 0
the rate constant. and 1 indicate favourable adsorption (0 indicates irreversible
adsorption, 1 suggests linear adsorption), while a value greater
than 1 indicates unfavourable adsorption.
Pseudo-second-order model The Freundlich isotherm is commonly used to describe het-
The pseudo-second-order model, which has been applied for ana- erogeneous systems (Freundlich, 1906). The model is represented
lysing chemisorption kinetics on solid phases from liquid solu- in linear form via the following equation:
tions (Ho, 2006), is expressed linearly as:


 logQe = nlogCe + logKF (5)
t 1 1
= t+ (2)
qt qe k 2 q2e where KF (mg/g) and n are the Freundlich constants describing
the adsorption capacity and intensity, respectively. The constants
where k2 is the rate constant (g/mg/h) and k2 q2e (mg/g/h) is the n and KF are determined from the slope and the intercept,
initial adsorption rate. respectively, of the plot logQe versus logCe. Values of n between
204 Tholiso Ngulube et al.

Table 4. Parameters of the Langmuir adsorption isotherms for the adsorption Table 5. Thermodynamic parameters for the adsorption of DR81, MO, MB and
of DR81, MO, MB and CV dyes onto the halloysite clay. CV dyes onto the halloysite clay.

Parameters DR81 MO MB CV Parameters DR81 MO MB CV

Langmuir isotherm ΔG° (kJ/mol) –15,341.01 –7242.34 –4560.09 –12,917.68

Qm (mg/g) 67.57 104.17 185.16 5.22 ΔH° (kJ/mol) –25,776.73 3745.21 547.29 219.57
Ka (L/mg) 85.25 110.82 119.45 12.08 ΔS° (kJ/mol/K) –5.22 4.59 23.22 4.23
RL 0.3719 0.2775 0.1777 0.8846 Ka (L/g) 331,189.87 4.57 1.26 1.09
R2 0.0083 0.8033 0.9969 0.9784
Freundlich isotherm
R2 0.6589 0.6321 0.7975 0.8093
The adsorption occurs through the formation of an activated
n 0.8599 1.2097 0.1831 1.8278
KF (mg/g) 1.7037 0.0428 12.4824 4.3642 complex between the adsorbate and adsorbent, thus representing
the activation stage at that level of reaction. Spontaneous adsorp-
tion of chemical species on stevensite was also reported by Hajjaji
et al. (2018). However, in the case of MO, MB and CV, the
1 and 10 indicate favourable adsorption (Kadirvelu & Namasivayam, entropy change values were positive, indicating that there was a
2000). change in the internal structure of the halloysite during adsorp-
The equation parameters of the equilibrium models give insight tion (Ofomaja et al., 2010).
into the adsorption mechanism, surface properties and affinity of
the adsorbent for the adsorbates. The Langmuir isotherm yielded
high coefficients of determination for MO, MB and CV dyes, Regeneration studies
this being the best-fitting model for adsorption of the dyes onto The results of the regeneration of the halloysite clay for the
halloysite (Table 4). In contrast, the Freundlich isotherm yielded removal of acidic and basic dyes from aqueous solutions are
low correlation coefficients for all of the dyes, hence the parameters shown in Fig. 7. The spent adsorbent has less adsorption capacity
of the Langmuir isotherm were used to describe the mechanism of than the original adsorbent. The halloysite displayed a similar
adsorption. In accordance with this study, Hajjaji et al. (2016) used trend after adsorption of MB and DR81 dyes, whereas this
the Langmuir isotherm model parameters to fit their results, sug- trend was different after adsorption of CV and MO dyes. After
gesting that the adsorption corresponds to monolayer coverage of one adsorption cycle with MB and DR81 dyes, the spent adsorb-
MB molecules over the kaolinite surface. The dimensionless equi- ent lost its capacity to remove dyes on successive cycles. By con-
librium separation factor, RL, for all of the dyes was <1, indicating trast, after one adsorption cycle, the adsorption capacity for CV
that dye adsorption was a favourable process. and MO dyes decreased after the first regeneration cycle, but
for successive cycles, the dye removal increased as the halloysite
was regenerated. This behaviour indicates that the adsorption of
Thermodynamic study
CV and MO dyes is chemical in nature. The adsorption was
The enthalpy ΔH° (kJ/mol) and entropy ΔS° (J/mol/K) of the reversible and the adsorbed CV and MO dyes were almost com-
adsorption were determined using Eqs 6 and 7. pletely recovered with the alkaline solution. A probable explan-
The standard free energy change during adsorption, ΔG°, was ation for this behaviour would be that MO is an acidic dye
calculated from the following equation: causing electrostatic interactions with the alkaline solution and
hence reversible reactions. CV is a water-soluble organic com-
DG◦ = −RTlnKa (6) pound with a violet cation. Adding NaOH converts the cation
into a carbonyl base, and the polarity of oxygen also makes the
where ΔG is the free energy of sorption (kJ/mol), T is the tem- α-hydrogens of carbonyl compounds much more acidic, causing
perature in K, R is the universal gas constant (8.314 J/mol/K) possible acid–base electrostatic attractions (Cannon et al., 1994).
and Ka is the sorption equilibrium constant.
The sorption equilibrium constant Ka can be expressed in Dye-adsorption mechanisms
terms of enthalpy change (ΔH) and entropy change (ΔS) as a
function of temperature: The adsorption studies and characterization might allow the prop-
osition of mechanisms for the adsorption of the anionic and cat-
DH ◦ DS◦ ionic dyes on the halloysite clay. For clays, it is expected that the
lnKa = + (7) solution pH and ultimately the PZC influence the adsorption of
RT RT
anionic and cationic molecules depending on the extent of proton-
where ΔH° is the heat of sorption (kJ/mol) and ΔS° is the standard ation of the adsorbate and the adsorbent. According to the PZC
entropy change (kJ/mol/K). results, it is anticipated that the adsorption of MB and CV would
The calculated values for the thermodynamic parameters are be greatest at pH > 5 and that of DR81 and MO would be greatest
listed in Table 5. The enthalpy of activation, ΔH°, is positive for at pH < 5. However, Fig. 5d shows that the variation of pH had a
all of the dyes except for DR81, indicating that the adsorption negligible influence on the percentage of removal of the dyes, except
of MO, MB and CV dyes on the halloysite clay is endothermic, for MO. This might suggest that the solution pH did not cause not-
whereas that of DR81 dye is exothermic. The adsorption of all able protonation of the ions in solution and subsequently the impact
the dyes was spontaneous, as symbolized by the negative free of pH on the dye uptake process was negligible. Similarly the FTIR
energy of sorption values (–ΔG°). The negative value of entropy spectra did not show any notable activity or change of the functional
change, ΔS°, for DR81 indicates that no significant changes groups before and after adsorption of the dyes (Fig. 2).
occurred at the activation stage. A negative value of ΔS° suggests Nonetheless, the overall observation was that, of the four dyes,
that the adsorption process involves an associative mechanism. MO had the lowest percentage of dye removal. The molecular size
Clay Minerals 205

Fig. 7. Regeneration of the halloysite clay.

Table 6. Adsorption capacities for various adsorbent materials used to remove dyes.

Adsorbent Adsorption capacity (mg/g) Dye Reference

Halloysite clay 104.17 Methyl Orange Present study

Halloysite clay 185.16 Methylene Blue Present study
Halloysite clay 5.22 Crystal Violet Present study
Halloysite clay 67.57 Direct Red 81 Present study
HDTMA-modified halloysites 91.74 Methyl Orange Liu et al. (2012)
Halloysite nanotubes 54.85 Neutral Red Luo et al. (2010)
Halloysite nanotubes 113.64 Methyl Violet Liu et al. (2011)
Chitosan–halloysite composite 68.92 Methylene Blue Peng et al. (2015)
Magnetic halloysite nanotubules 37.38 Methylene Blue Xie et al. (2011)
Magnetic halloysite nanotubules 31.21 Nile Red Xie et al. (2011)
Magnetic halloysite nanotubules 0.68 Methyl Orange Xie et al. (2011)

HDTMA = hexadecyltrimethylammonium.

of the adsorbates also affects adsorption. Large molecules might not
be adsorbed because their size prevents their diffusion into the pores
of the adsorbent. The chemical formulae and molecular weights of
DR81, MB, CV and MO are C29H19N2O8S2 (675.598 g/mol),
C16H18N3ClS.xH2O (319.850 g/mol), C25N3H30Cl (407.979 g/mol)
and C14H14N3NaO3S (327.334 g/mol), respectively. Hence, MO
has the second smallest molecule, and if molecular size had affected
the adsorption of the dyes, MO would have presented a greater per-
centage of removal compared to MB and DR81.
As the dye uptake could not be explained in terms of molecu-
lar size, pH variation or characterization results, the adsorption
mechanism will have to be discussed in light of the isotherm
and kinetic modelling results. The pseudo-second-order model
showed the best fit with the experimental data for all four of
the dyes, whereas the Langmuir isotherm model described accur-
ately the adsorptions of MB, CV and MO, but not that of DR81.
Hence, the adsorption mechanisms may involve complexation or
ion exchange between the dye ions and the surface ions or SiO2 or
Al2O3 groups on the clay surfaces. The halloysite clay displayed
relatively high Langmuir adsorption capacities for all of the dyes
and therefore most of the dye ions might have been held in a
monolayer on the clay surface.
According to Errais et al. (2012), depending on the type of
clay, the possible processes involved in dye adsorption can be
summarized in the following processes:
Process 2: In basic pH conditions and at the particle edges of disso-
ciated aluminol groups, OH groups may be substituted by anions
(Errais et al., 2012).
Process 3: Halloysite is a kaolinite clay and these clays have a net layer
charge of zero (Sarma et al., 2011). However, a small net negative charge
may arise from broken edges on the clay crystals. This negative charge may
be responsible for holding the cations to the clay surface through coulom-
bic interactions. The charge on the edges is due to protonation or depro-
tonation of surface hydroxyl groups (Kausar et al., 2018).
In general, the uptake of dye molecules by clay minerals is due to
the trapping of dye molecules by exchangeable ions and the pro-
tonated edges of the clay layers.
Comparison with other studies
Table 6 illustrates the comparison of the adsorption capacity of hal-
loysite with other clay-based adsorbents. The adsorption capacity of
the halloysite clay used for this study for MO, MB and DR81 dyes
is greater than the capacities of other halloysite clays, whereas the
capacity for the removal of CV dye is notably lower. This difference
might be attributed to the various operational parameters used dur-
ing the adsorption experiments and to the various chemical mod-
ifications performed on the clay before use. Thus, the halloysite
used may be considered as an effective option for the removal of
both acidic and basic dyes from aqueous media.

Process 1: The polyvalent metal cations (Si4+ and Al3+) found on edge Conclusion
sites of the clay contribute to the surface charge being positive, hence
forming bridges between the particles of the clay and organic anions, The removal of DR81, MO, MB and CV dyes from aqueous solu-
allowing anionic dyes such as DR81 to be adsorbed. tion was carried out using a halloysite clay as an adsorbent. The
206
optimum contact time for the interaction of the adsorbent with
dye effluent was 30 min. The pseudo-second-order kinetic
model described sufficiently the adsorption, yielding a perfect
coefficient of determination (R2 = 1) for all of the dyes. The
Langmuir model described the adsorption process better than
did the Freundlich model in the order MB > CV > MO >
DR81 in terms of the R2 values. The untreated halloysite clay is
an effective material for adsorbing acidic and basic dyes at a nor-
mal temperature and pH of solution. The results have established
the potential for the halloysite clay to be used as an adsorbent for
the removal of dyes from wastewater in the textile industry.
Supplementary material. To view supplementary material for this article,
please visit https://doi.org/10.1180/clm.2019.27
Author ORCIDs. T. Ngulube, 0000-0003-0725-2203.
Acknowledgements. The authors thank the University of Venda, National
Research Foundation (NRF), Water Research Commission (WRC) for funding.
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