Clean Techn Environ Policy (2016) 18:81–94
DOI 10.1007/s10098-015-0993-y
ORIGINAL PAPER
Nano-TiO2 modified with natural and chemical compounds
as efficient adsorbents for the removal of Cd+2, Cu+2,
and Ni+2 from water
Shahriar Mahdavi1
Received: 24 February 2015 / Accepted: 6 June 2015 / Published online: 14 June 2015
 Springer-Verlag Berlin Heidelberg 2015
Abstract Nanoparticles (NPs) modified with proper
compounds are now gaining much attention for their
function as new adsorbents for environmental remediation.
The main objective of this study is to determine the
effectiveness of modified nanoparticles (MNPs) as sorbents
in removing Cd?2, Cu?2, and Ni?2 from single and com-
petitive solutions by TiO2 NPs modified with humic acid
(Ti–H), extractant of Walnut shell (Ti–W), and 1, 5
diphenyl-Carbazon (Ti–C). MNPs were characterized by
XRD, FT-IR, and SEM–EDX analyzer. The MNPs were
spherical in shape. The mean diameter of MNPs was
determined to be 64.7 nm. The sorption of Cd?2 and Cu?2
on MNPs fitted better in Langmuir model than Freundlich
model. But Ni?2 sorption better fitted in Freundlich model.
Kinetics of adsorption follow pseudo-second order kinetic
model than pseudo-first-order kinetic model. The adsorp-
tion maximum was observed at pH 7. Adsorption capacities
of MNPs were obtained from Langmuir model and final
point of isotherm. Comparison with published adsorption
capacities for other adsorbents indicated that Ti–W and Ti–
C had potential as proper adsorbents for the removal of
Cd?2 and Cu?2 from single and competitive aqueous
solution and Ti–H was a good candidate for Ni?2 removal
from single and competitive solutions.
Keywords Modified TiO2  Removal  Heavy metals 
Water
& Shahriar Mahdavi
smahdaviha@yahoo.com; sh.mahdavi@malayeru.ac.ir
1
Department of Soil Science, College of Agriculture, Malayer
University, Malayer, Iran
Introduction
Water is a very limited natural resource, and in many cases
there is not enough water supply with appropriate quality
for sanitary, industrial, and domestic use. Many toxic
compounds which are harmful to the environment and
human health have been identified in water (Vaclavikova
et al. 2008). Among a variety of pollutants in water, heavy
metals with non-biodegradable properties have a perma-
nent impact on the environment and must be removed from
it. The main sources of metal contamination are industrial
development and human activities (Jalbani and Soylak
2014). Heavy metals like Cd2? and Cu2? and Ni2? enter
human body by ingestion of contaminated food, air, and
water, and harm the vital organs of the human body such as
the liver, kidney tissues, and the brain (Jalbani and Soylak
2014). These detrimental compounds produce toxicity even
at such low concentrations as 0.1–0.3 mg L-1 (Lai et al.
2010). Therefore, selecting a proper method to separate
metals from water can improve its quality to a safe level. A
great number of methods including chemical precipitation,
ion exchange, membrane filtration, electrolysis, reverse
osmosis, and solvent extraction have been used in order to
clean contaminated water (Zamani et al. 2013). Adsorption
is regarded as one of the most effective and attractive
processes with no chemical sludge and high removal effi-
ciency compared with the above-mentioned technologies
(Foo et al. 2012).
A number of adsorbents including biopolymers, acti-
vated carbon, metal oxides, clays, dried plant parts,
microorganisms, and sewage sludge have been used for the
removal of heavy metals (Boparai et al. 2013).
In recent years, NPs have become promising adsorbents
for water treatment. Nanoparticles have unique large surface
areas, well-defined pore sizes, high pore volume,
123
82
high adsorption capacity, ease of modification, and diversity
in surface functionalization (Mahdavi et al. 2013). Nano-
sized titanium oxide powders are now widely produced on
an industrial basis, and the average grain size of commer-
cialized nanopowders usually varies from 10 to 30 nm
(Baraton and Merhari 2004). The ability of TiO2-NPs to
remove heavy metals from water has also been reported
(Engates and Shipley 2011; Mahdavi et al. 2013). They can
also be functionalized to increase affinity to metal ions and
to improve selectivity in the removal of metal ions (Hua
et al. 2012; Chen et al. 2012). In this research, humic acid
(HA) (Ti–H), extractant of walnut shell (Ti–W), and 1,5
diphenyl-carbazon (Ti–C) were immobilized on the surface
of nano-TiO2 and used as new solid-phase adsorbents to
remove Cd?2, Cu?2, and Ni?2 from single and competitive
solutions. The new modified nanoparticles (MNPs) were
characterized by SEM, XRD, and FT-IR analysis. The
removal of metal ions depends on pH, contact time, and
metals concentration. Thus, the optimal conditions for
adsorption were established. With these conditions, the
adsorption isotherms were measured and the results were
fitted to Langmuir and Freundlich models. To interpret the
sorption mechanism better, SEM–EDX spectroscopic anal-
ysis was carried out. Finally, the stability of the MNPs
adsorbents (with 0.01 M CaCl2) for heavy metals (desorp-
tion experiments) was also determined.
Materials and methods
Chemicals and methods used for NPs
characterization
All chemicals used in this investigation were of analytical
grade and used without further purification treatment.
Nanostructured TiO2 was purchased (purity, 99.5 %) from
Tecnan (www.tecnan-nanomat.es, Spain). The concentra-
tion of metal ions was determined by flame atomic
absorption spectrometer (FAAS) (Varian Spectra AA 220).
Power X-ray diffraction (XRD) spectra were measured by
means of a Misone diffractometer (38066 RIVA, d/g. Via
M. Misone, 11/D (T/N) ITALY) operating at 40 kV and
40 mA with Cu-Ka monochromatic radiation in the
Bragg’s angle range of 20–80. The nanostructures of
MNPs were observed by scanning electron microscopy–
energy dispersive X-ray (SEM–EDX Cam Scan MV2300,
Philips XL30) to determine their morphology, size, and
purity on the surfaces of three MNPs. Adsorption of
organic species on TiO2 particles was studied by FT-IR
spectroscopy (Perkin–ElmerFTIR Spectrum 1000) (KBr
pellets). The spectra obtained in the range of
400–4000 cm-1 were analyzed. A sonicator (Elmasonic,
S30H) was used for sonication.
123
S. Mahdavi
Preparation of organic compound (modifiers)
HA stock solution (500 mg L-1) was prepared according to
Mahdavi et al.’s (2015) method. Extractant of walnut shell
was obtained by rinsing walnut shell in 0.1 N HNO3 (at
solid/solution = 1 g: 10 mL) for 24 h at 70 C to obtain the
active functional groups (Kim et al. 2001). 1,5 diphenyl-
carbazon (MW = 243.28,C6H5NHNHCONHNHC6H5), was
dissolved in 20 C methanol and was then diluted with
deionized water to make the concentration of 500 mg L-1 of
Cabazon and was stored at 4 C before use (with native pH).
The modification processes were done according to
Mahdavi et al.’s (2015) method with the above-mentioned
modifiers.
Preparation of MNPs
0.5 g of TiO2 NPs was suspended in 30 mL of modifier
solution (Mahdavi et al. 2015). Then, the suspension was
sonicated at 70 for 6 h followed by evaporation of the
solvent, washed with deionized water, air-dried, and finally
stored in a closed bottle for subsequent use.
Studies on point of zero charge (pHpzc) and zeta
potential
In pHpzc determination, 0.01 M NaCl was prepared and its
pH was adjusted in the range of 2–12 by adding NaOH or
HCl according to Gupta and Nayak’s (2012) method.
Zeta potential (f in mV) measurements are measures of
the magnitude of charge expressed in the DDL at the plane
of slippage. If we set f * w0 (given the very short distance
of the plane of slippage from the surface), then the rela-
tionship between f and the PZC can be simply represented
as follows:
f  W0 ¼ 59:2ðpH0  pHÞ; ð1Þ
where w0 is the surface electrostatic potential, pH0 = pH
of the PZC, and pH = the pH of the bulk solution
(Chappell 2009).
Batch removal procedure
The adsorption of Cd2?, Cu2?, Ni2? in single and com-
petitive solutions by modified nano-TiO2 was performed by
a batch operation at room temperature. 25 mg of the
adsorbent was suspended in 25 mL solution containing
50 mg L-1 of Cd2?, Cu2?, and Ni2? in single and com-
petitive solutions. The solutions were not buffered to
mimic potential industrial practice. The solutions were
sonicated for 120 min and were then left in equilibrium for
22 h. After a time period of agitation, the suspensions were
centrifuged at 5000 rpm for 5 min. The residual
Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of…
concentration of the ions in the supernatant solutions was
determined by FAAS. The percentage removal of Cd2?,
Cu2?, Ni2? by the adsorbents was calculated according to
the following equation:
 
C0  Ce
% Removal ¼  100; ð2Þ
C0
where C0 and Ce are the initial and final concentrations of
heavy metals in the solution phase, respectively. All the
investigations were carried out in triplicate to avoid any
discrepancy in experimental results with the repeatability
and the relative deviation of the order of ±3.5 %.
Adsorption isotherm studies were carried out with dif-
ferent initial concentrations of Cd2?, Cu2? and Ni2? in
single and competitive solutions while maintaining the
sorbent’s dosage at constant level. The pH of primary
solutions was adjusted for Cd2? and Ni2? ions at 7 and 8,
respectively (according to the results of pH effect). But for
Cu2? ions solution, native pH was considered. In order to
inspect any adsorption of Cd2?, Cu2?, and Ni2? on the
container’s surface, control experiments were carried out
without the sorbent. It was found that no adsorption
occurred on the container’s wall. The isotherms’ data were
fitted to the linear Freundlich and Langmuir adsorption
models. The Freundlich model describes the logarithmic
decrease in adsorption energy with increasing surface
coverage. This model assumes no combination or dissoci-
ation of the absorbed molecules. Thus, equal concentration
of surface site and adsorption occur by means of physical
rather than chemical adsorption. The linearised equation is
usually expressed as follows:
Log qe ¼ Log KF þ 1=n Log Ce ; ð3Þ
where qe and Ce are equilibrium solid-phase (mg g-1) and
liquid-phase (mg L-1) concentrations, respectively. KF
(mg g-1) is the Freundlich constant related to the adsorp-
tion capacity of the adsorbent and n is the heterogeneity
factor indicating the adsorption intensity of the adsorbent.
(Mahdavi et al. 2012; Zha et al. 2014).
The Langmuir equation is based on the assumption of a
structurally homogeneous adsorbent and is described using
the following equation:
Ce Ce 1 1
¼ þ ; ð4Þ
qe qm qm b
where qm (mg g-1) is the maximum adsorption capacity
corresponding to complete monolayer coverage and b (KL)
(L mg-1) is the Langmuir constant related to the energy of
adsorption which quantitatively reflects the affinity of the
binding sites (Peng et al. 2012). RL is another essential
feature of a Langmuir isotherm which can be expressed in
terms of a dimensionless constant separation factor or
83
equilibrium parameter that is used to predict whether an
adsorption system is ‘‘favorable’’ or ‘‘unfavorable.’’ RL is
defined by
1
RL ¼ ; ð5Þ
1 þ bC0
where C0 is the initial concentration of Cd2?, Cu2?, and
Ni2? (mg L-1) and b is the Langmuir adsorption equilib-
rium constant (L mg-1). Based on the effect of separation
factor on isotherm shape, the RL values are in the range of
0–1, which indicates that the adsorption of Cd2?, Cu2?,
and Ni2? on MNPs is favorable (Zhang et al. 2009).
The effect of pH
The effects of pH on sorption of Cd2?, Cu2?, and Ni2? ions
were studied by varying the pH of heavy metal solution
from 3 to 8. These samples were sonicated for 120 min and
were then left in equilibrium for 22 h. Then, the aliquots
were filtered and analyzed for Cd2?, Cu2?, Ni2? by FAAS,
as mentioned above. To determine the influence of pH, the
tests were performed in triplicate.
The effect of contact time
Batch experimental procedures were conducted with dif-
ferent shaking times of 10, 20, 30, 40, 50, 60, 90, 120, and
180, 1440 min, while other conditions remained the same
as in Batch removal experiments.
Kinetics modeling study
The adsorption kinetics of metal ions with MNPs was
investigated by 2 kinetic models: pseudo-first-order and
pseudo-second-order models for Eqs. (6) and (7),
respectively.
Pseudo-first-order model
lnðqe  qt Þ = ln qe  K1 t: ð6Þ
Pseudo-second-order model
1 t
¼ þ ; ð7Þ
qt K2 q2e qe
where qt (mg g-1) is adsorption at time t (min); qe
(mg g-1) is adsorption capacity at adsorption equilib-
rium; and K1 (min-1) and K2 (g mg-1 min-1) are the
kinetic rate constants for the pseudo-first-order and the
pseudo-second-order models, respectively. The kinetic
adsorption data were fitted to Eqs. (6) and (7) (Azizian
2004).
123
84 S. Mahdavi

Fig. 1 XRD powder pattern of MNPs (TiO2, Ti–C, Ti–H, and Ti–W)

123
Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of…
Desorption experiments
Desorption of adsorbed Cd2?, Cu2?, Ni2? from MNPs
loaded with metal ions (in isotherms experiments at
300 mg L-1 of primary concentration in single and com-
petitive (com) solutions of heavy metals) was washed three
times with deionized water to remove the unadsorbed metal
ions and was then dried at 60 C in an air-oven. 0.025 g of
dry Cd- MNPs, Cu- MNPs, Ni- MNPs, and Com-MNPs
were taken separately with 30 mL of 0.01 M CaCl2 solu-
tions and were added to the tubes, and shaken for 4.0 h
(Mahdavi et al. 2015). Before measuring the equilibrium
concentrations of Cd2?, Cu2?, Ni2? in the supernatant
solutions, the MNPs were separated from the solutions by
centrifugation at 5000 rpm.
Results and discussion
Characterization of MNPs
All MNPs are crystallized and have an anatase structure as
evidenced by the XRD patterns (Fig. 1). The sharp peaks at
25.29, 37.78, and 48.20 can be attributed to anatase (Zha
et al. 2014; Pourreza et al. 2014). From Scherrer’s equa-
tion, the estimated average crystal sizes are presented in
Table 1. The XRD patterns of the 2 MNPs (Ti–H, Ti–W)
showed that the peaks of TiO2 NPs in bare and pure par-
ticles were not different. But the phase property of TiO2
cores with Ti–C NPs showed change in the crystalline
structure of particles (Fig. 2). This suggested that absorp-
tion had taken place in the structure of particles. According
to Fig. 2 and Table 1, MNPs have a diameter of less than
100 nm. SEM images indicated a relatively large size
distribution ranging from approximately 60–90 nm, the
larger particles probably being aggregates of the smaller
ones (Fig. 2). A comparison of the FTIR spectra of the
TiO2 powders in bare and treated with HA (Ti–H),
extractant of walnut shell (Ti–W), and 1,5 diphenyl-car-
bazon (Ti–C) are presented in Fig. 3. Like all metal oxides,
the surface of TiO2 NPs presents hydroxyl (OH) groups
Table 1 Structural properties
Nanoparticles Crystal size (nm)a
of nanoparticles
Ti–H 24.6
Ti–W 23.8
Ti–C 22.5
TiO2 24.4
a
Data calculated from Scherrer’s equation
b
Data from average of particles size with SEM images
c
Data from Mahdavi et al. (2013)
85
originating from the surface hydrolysis as soon as the
material is in contact with moisture or regular atmosphere
(Baraton and Merhari 2004). In bare TiO2, the broad peak
observed at 3422 cm-1 corresponds to the stretching
vibration of surface hydroxyls and adsorbed water; the
peak at 1627 cm-1 was due to the bending vibration of Ti–
OH; the band at about 1364 cm-1 was related to the
bending vibration of Ti–O–Ti, and the bands below
800 cm-1 are due to the Ti–O stretching vibration (Fig. 3).
These results are consistent with those reported by Zha
et al. (2014). The incorporation of organic groups in the
TiO2 was confirmed by the FT-IR spectra (Fig. 3). In Ti–H,
the broader bands in 3394 and 1627 cm-1 were attributed
to more adsorption of OH functional group from humic
acid.
In Ti–W, the bands at 1384, 2920 cm-1 were assigned
to the –CH2 bending vibration, and C–H stretching vibra-
tions (Shahbazi et al. 2014). In Ti–C, carbazone treatment
either masks or shifts the bands more in comparison with
bare TiO2. The broader band in 3415 and 1621 cm-1 can
reveal more OH and N–H adsorption (Fig. 3). The chem-
ical analysis of humic acid, walnut shell, and 1,5 diphenyl-
carbazon confirms the results from IR. These materials
have C, H, O, N, and S elements that are linked together
and make functional groups such as aromatic, carboxylic,
and phenolic. These groups can link to NPs surfaces via
chemical or physical bonding and improve properties of
NPs (Mahdavi et al. 2015).
The point zero charges (pHpzc) were determined for 3
adsorbents, i.e., Ti–H, Ti–W, and Ti–C. pHpzc is an
important property and indicates the electrical neutrality of
the adsorbent. From Table 1, it is obvious that the pHpzc
shifted from 4.2 (TiO2) to 3.9 for Ti–C, 6.9 for Ti–W, and
7.3 for Ti–H NPs. Zeta potential is another parameter
which is strongly affected by the media used to stabilize the
NPs and prevent their agglomeration. TiO2 and Ti–C with
the exception of Ti–W and Ti–H had negative value,
indicating that they were negatively charged. Higher
absolute values indicate an increase in the stability of the
suspensions. Values that are larger than 30 mv are con-
sidered stable (Mosh et al. 2010).
Particle sizeb Zeta potential (mV) PZC
63.7 ?5.9 7.3
44.0 ?5.9 6.9
86.6 -230.8 3.9
12c -207.2 4.2
123
86 S. Mahdavi

Fig. 2 SEM images of Ti–C,

Ti–H, and Ti–W MNPs

123
Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 87

Fig. 3 FT-IR spectra of

(a) TiO2, and (b) Ti–W,
(c) Ti–H, and (d) Ti–C

123
88
Fig. 4 Effect of pH on the adsorption efficiency of Cd2?, Cu2?, and
Ni2? on Ti–W, Ti–H, and Ti–C
The effect of pH
We applied 25.0 mL of 50.0 mg L-1 of Cd2?, Cu2?, and
Ni2? to test the sorption of metals onto MNPs at different
pH values. The results showed that the maximum adsorp-
tion (Fig. 4) for both Ni2? and Cu2? species took place at a
pH between 7and 8. But the maximum affinity for Cd2?
was generally in the pH range of 4–5. It was found that the
adsorption capacity of the two metal ions (Cu2?, Ni2?) had
a similar way. An increase of adsorption capacity was
observed when pH increased from 2 to 8. The surface
charge of MNPs varied tremendously with increasing pH
from 2 to 8, and there was always an electrical inversion
from positive to negative (Fig. 4). At low pH (e.g. 2 for
most MNPs), negatively charged (TiO-) on the surface
tended to bind with H? and formed positively charged
TiOH? or TiOH2?. Consequently, Cu2? and Ni2? could
hardly contact with MNPs surface due to electrostatic
repulsion between metal cations and the positively charged
surface. Moreover, excessive H? would compete with
123
S. Mahdavi
metal cations for limited active sites at a low pH which was
not beneficial for adsorption. While at high pH, the amount
of negatively charged active sites increased due to depro-
tonation under high OH-concentration conditions, thus
increasing the possibility of metal ions adsorption (Yang
et al. 2011; Xie and Gao 2009). In addition, Cu(OH)2
began to form at pH 6 (Fig. 4), so precipitation would not
be ignored when pH was high (Liu et al. 2014). In Cd2?, at
a pH value of 5, the Cd 2? ions began to hydrolyze and then
formed a small quantity of Cd(OH)2 or Cd(OH)3-, CdCl2,
CdCl? species. Compared with Cd 2? ions, these species
are disadvantageous for adsorption, especially for nega-
tively charged varieties, which accounts for the little
decline in the adsorption capacity. Consequently, the
maximum adsorption takes place at around pH 5.0 (Tan
et al. 2012; Mahdavi et al. 2013).
The effect of contact time
The effect of contact time on the removal of Cd2?, Cu2?,
and Ni2? was investigated to determine the optimum
contact time. Figure 5 shows the removal percentage of
Cd2?, Cu2?, and Ni2? ions as a function of contact time for
different concentrations. Rapid adsorption kinetics of
Cd2?, Cu2?, and Ni2? ions can obviously be seen within
the first 60 min and an increase in contact time had no
sensible effects on the adsorption percentage. Hence,
60 min was selected as the optimum contact time.
The kinetics of Cd2?, Cu2?, Ni2? adsorption in MNPs
have been evaluated and the kinetic parameters are listed in
Table 1. To understand the adsorption mechanisms, the
uptake rate of Cd2?, Cu2?, Ni2? at an initial concentration
of 50 mg L-1 was analyzed by two kinetic models, i.e.,
pseudo-first-order and pseudo-second-order kinetics,
respectively. All the adsorption curves can be fitted to the
pseudo-second-order kinetic model with a high correlation
coefficient (R2 of 0.999) in comparison with pseudo-first-
order kinetic model, indicating that the adsorption process
of Cd2?, Cu2?, and Ni2? in MNPs is very fast and close to
chemisorption (Zha et al. 2014).
Adsorption isotherms
Both Langmuir and Freundlich isotherms were applied to
determine the adsorption capacity of Cd2?, Cu2?, and Ni2?
on MNPs in single and competitive solutions of heavy
metals. The experimental data can be well fitted to the
Langmuir isotherm model rather than the Freundlich model
with the exception of Ni2?. For Ni2?, the Freundlich can
better illustrate the data trend. The Langmuir model
assumes that the monolayer surface adsorption occurs on
specific homogeneous sites and no interaction exists
between the adsorbed pollutants (Zha et al. 2014).
Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 89

Fig. 5 Effect of contact time

and initial concentration of
Cd2?, Cu2?, Ni2? (50 mg L-1)
on sorption capacity of Ti–H,
Ti–W, and Ti–C

Table 2 The pseudo-second-order kinetics model constant (at concentration 50 mg L-1)

Metal Ti–H Ti–W Ti–C
qe (mg g-1) K2 (g mg-1 min-1) R2 qe (mg g-1) K2 (g mg-1 min-1) R2 qe (mg g-1) K2 (g mg-1 min-1) R2

Cd2? 12.34 9 9 10-3 0.941 30.30 5 9 10-3 0.961 6.12 14 9 10-3 0.973
2? -3 -3
Cu 14.71 3 9 10 0.972 14.71 3 9 10 0.961 9.26 6 9 10-3 0.967
2? -2 -2 -2
Ni 5.00 6 9 10 0.992 4.71 -4 9 10 0.994 3.37 -38 9 10 0.941

Moreover, the monolayer maximum adsorption capacities adsorbents in previous studies (listed in Tables 4, 5, and 6),
of Cd2? (in single solution) were calculated from the it is apparent that Ti–C in this work has much higher
Langmuir isotherm to be 9.9, 25.7 .8, and 31.7 mg g-1 for adsorption capacities for Cd2?and Cu2?. Therefore, Ti–C is
Ti–H, Ti–W, and Ti–C, respectively. Compared with other very promising for the effective removal of Cd2? and Cu2?

123
90 S. Mahdavi

Table 3 Langmuir and

Langmuir Ti–H Ti–W Ti–C
Freundlich constants for Cd2?,
Cu2?, and Ni2? adsorption on qmax kL R 2
RL qmax kL R 2
RL qmax kL R2 RL
the MNPs in single and
competitive isotherms Single
Cd2? 9.9 0.08 0.9260 0.21 25.7 0.02 0.9871 0.47 31.7 0.01 0.9984 0.62
Cu2? 5.3 0.07 0.8916 0.20 15.2 0.004 0.9327 0.71 20.5 0.002 0.9827 0.90
Freundlich kf n R2 – kf n R2 – kf n R2 –
2?
Ni 3.6 2.5 0.8895 – 4.2 3.2 0.8998 – 1.9 2.0 0.8425 –
Competitive
Cd2? 19.3 0.01 0.9957 0.63 9.9 0.01 0.9306 0.59 14.4 0.01 0.9859 0.62
Cu2? 16.5 0.004 0.7806 0.70 45.8 0.005 0.9881 0.69 38.3 0.005 0.9551 0.94
Freundlich kf n R2 – kf n R2 – kf n R2 –
Ni2? 0.1 1.1 0.9278 – 0.1 1.0 0.9837 – 2.7 2.5 0.8412 –

Table 4 Comparison of adsorption capacity of the proposed with some sorbents reported for the adsorption of Cd2?
Adsorbent Capacity (mg g1-Cd2?) Capacity (mg g1-Cd2?) Reference
(single) (competitive)

Biochar (prepared at 200 C) 31.9 Xu et al. (2013)

TiO2-nano 15.2 Engates and Shipley (2011)
Ananas comosus 18.2 Foo et al. (2012)
Modified kaolinite clay 41.0 Unuabonah et al. (2008)
Iron oxide modified with sewage sludge 14.7 Phuengprasop et al. (2011)
Mixture of fly ash and TiO2 9.5 Visa and Duta (2013)
Fly ash 16.7 Visa and Duta (2013)
Lignin 25.4 Guo et al. (2008)
Flower-like TiO2-graphene oxide 14.9 Lee and Yang. (2012)
Ti–H 9.9 19.3 This study
Ti–W 25.7 9.9 This study
Ti–C 31.7 14.4 This study

from the environment in single solution while Ti-H adsorbs
few Cd2? and Cu2? (Tables 4, 5 and 6). HA adsorption can
generally decrease and block the micropore surface area of
nano-TiO2 which in turn decreases adsorption (Yang et al.
2009). This operation decreases the surface area of Ti–H in
comparison with Ti–W and Ti–C. Ti–H has the highest
adsorption capacity for Ni2? in comparison with other
adsorbents. In competitive solutions, the high concentration
of Cu2? can precipitate some of Cu2? ions. The values of
KL, Qmax, RL, n, KF, and R2 for different MNPs and models
are listed in Table 3. The best model was judged from the
higher correlation coefficients (R2) and the results indicated
that the adsorption process in Ni2? best fitted to Freundlich
model but in Cd2? and Cu2? Langmuir model better illus-
trated the adsorption phenomena.
treatment with heavy metals in final equilibrium concen-
tration of isotherms Tables 4, 5, and 6. In Ti–H NPs with
Ni2? and single solution, the accumulation of heavy metals
(in white color) (Fig. 6) in surfaces was obvious. In Ti–C,
accumulation of Cd2? is very prominent (Fig. 6) and in Ti–
H, Cu2? is more prominent (Fig. 6). For these images,
EDX analysis showed the peaks of Cd2?, Cu2?, and Ni2?
in single solutions. The EDX spectra provided a direct
evidence for Cd2?, Cu2?, and Ni2 adsorbed on MNPs.
Other studies also used EDX analysis to give a direct
detection of the presence of elements on the adsorbents
(Yuwei and Jialong, 2011; Sica et al. 2014).
Desorption

For an effective adsorption process, adsorbed metal ions

SEM–EDX analysis should not be easily desorbed under suitable conditions. In
this work, desorption experiments were carried out using
The SEM images from 3 MNPs revealed the changes in 0.01 M CaCl2 as the desorption agent. Calcium is a dominant
morphology and surface precipitation in particles after cation in natural water and can replace heavy metals that were

123
Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 91

Table 5 Comparison of adsorption capacity of the proposed with some sorbents reported for the adsorption of Cu2?
Adsorbent Capacity (mg g1-Cu2?) Capacity (mg g1-Cu2?) Reference
(single) (competitive)

Amino-functionalized magnetic 25.8 Meyi et al. (2010)

nanoparticles
Mixture of fly ash and TiO2 9.5 Visa and Duta (2013)
Modified rice husk 4.5 Jaman and Chakraborty
(2009)
Iron oxide modified with sewage sludge 17.3 Phuengprasop et al. (2011)
Magnetic chitosan NPS 35.5 Yuwei and Jialong (2011)
PVA/TiO2/APTES nanohybrid 13.1 Abbasizadeh et al. 2014)
Sugar beet pulp 30.9 Pehlivan et al. (2006)
Lignin 22.9 Guo et al. (2008)
Biochar (prepared at 200 C) 48.4 Xu et al. (2013)
Ti–H 5.3 16.5 This study
Ti–W 15.2 45.9 This study
Ti–C 20.5 38.3 This study

Table 6 Comparison of adsorption capacity of the proposed with some sorbents reported for the adsorption of Ni2?
Adsorbent Capacity (mg g1-Ni2?) Capacity (mg g1-Ni2?) Reference
(single) (competitive)

Nano alumina 30.0 – Sharma et al. (2008)

Waste tea 18.4 Malkoc and Nahoglu
(2005)
Magnetic nanoparticles modified with 41.3 – Chen et al. (2014)
EDTA
Natural clinoptilolite 2.0 Alvarez-Ayuso et al.
(2003)
Thuja orientalis (cone) 12.4 – Malkoc and Nahoglu
(2006)
TiO2 nano 6.7 Engates and Shipley
(2011)
Activated carbon 133.3 Ucar et al. (2015)
Iron oxide modified with sewage sludge 7.8 Phuengprasop et al. (2011)
Lignin 6.0 Guo et al. (2008)
Activated sludge 8.8 Hammaini et al. (2007)
PVA/TiO2/APTES nano 13.1 Abbasizadeh et al. (2014)
Ti–H 24.2 22.6 This study
Ti–W 24.5 21.8 This study
Ti–C 22.0 24.6 This study

sorbed via electrostatic mechanism and release them into the
aquatic environment. The data in Fig. 7 show the desorption
amount of Cd2?, Cu2?, and Ni2? as a function of CaCl2
solution in different MNPs and solutions. It is apparent that
Ni2? metals in single solutions have the highest average
desorption (4.4 mg/g) in total MNPs and give the best des-
orption result. These results can reveal that some of sorption
of Ni2? in MNPs is electrostatic adsorption. In competitive
solutions, Cu2? metals have the highest average desorption
(9.2 mg g-1). Other data are represented in Fig. 7. In general,
in single solutions, the sequence of mean desorption of 3
MNPs for each metal was Ni2? (4.4 mg/g [ Cd2? (3.5 mg/
g) [ Cu 2? (1.4 mg/g). This trend for competitive solutions
was Cu 2? (9.2 mg/g) [ Cd2? (3.1 mg/g) [ Ni2? (1.2 mg/
g). Therefore, the modified TiO2 particles could be operated
as stable adsorbents particularly in single solutions.

123
92 S. Mahdavi

Fig. 6 SEM–EDX images of Ti–H, Ti–C, and Ti–H NPs, after treatment with single Ni2?, Cd2?, and Cu2? solutions, respectively

123
Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 93

Azizian S (2004) Kinetic models of sorption: a theoretical analysis.

a Desorpon- single J Colloid Interface Sci 276:47–52
8
7
Baraton MI, Merhari L (2004) Surface chemistry of TiO2 nanopar-
6 ticles: influence on electrical and gas sensing properties. J Eur
Desorption (mg/g)

5 Ceram Soc 24:399–1404

4 Boparai HK, Joseph M, O’Carroll DM (2013) Cadmium (Cd2?)
3 removal by nano zero-valent iron: surface analysis, effects of
2 solution chemistry and surface complexation modeling. Environ
1 Sci Pollut Res 20:6210–6221
0 Chappell MA (2009) Nanomaterials: risks and benefits, I. Linkov and
J. Steevens (eds.), 111 Springer Science ? Business Media
B.V
Chen Q, Yin D, Zhu S, Hu X (2012) Adsorption of Cadmium (II) on
humic acid coated Titanium dioxide. J Colloid Interface Sci
b Desorpon- compeve 367:241–248
14 Chen J, Hao Y, Chen M (2014) Rapid and efficient removal of Ni2?
12 from aqueous solution by the one-pot synthesized EDTA-
Desorption (mg/g)

10 modified magnetic nanoparticles. Environ Sci Pollut Res

8
6 Zn2?, and Ni2? to Titanium dioxide nanoparticles: effect of
4 particles size, solid concentration, and exhaustion. Environ Sci
2 Pollut Res 18:386–395
0
Fig. 7 Desorption of Cd2?, Cu2?, and Ni2? in a single and
b competitive solutions using Ti–W, Ti–H, and Ti–C
Conclusions
This investigation highlights the effectiveness of Ti–C and
Ti–W and Ti–H adsorbents for the removal of Cd2? and
Cu2?and Ni2? ions from single and competitive solutions.
The adsorption process was investigated as a function of
the contact time of Cd2?, Cu2?, and Ni2? ions with the
sorbents, initial Cd2?, Cu2?, and Ni2? ions concentration
in single and competitive solutions and pH. The kinetics of
the sorption process could be fitted to a pseudo-second-
order reaction model. The maximum adsorption took place
at the pH of 7. The Freundlich and Langmuir adsorption
isotherms were employed to evaluate the adsorption
behavior, where maximum adsorption capacities for Ti–C
and Ti–W were obtained in Cd2? and Cu2? and for Ti–H in
Ni2?. Maximum desorption efficiency could be achieved
for the Ni2? (4.4 mg/g) and Cu2? (9.2 mg g-1) after the
adsorption process by treating CaCl2 in single and com-
petitive solution, respectively.
References
Abbasizadeh S, Keshtkar AR, Mousavian MA (2014) Sorption of
heavy metal ions from aqueous solution by a novel cast PVA/
TiO2 nanohybrid adsorbent functionalized with amine groups.
J Ind Eng Chem 20:1656–1664
Alvarez-Ayuso E, Garcıa-Sánchez A, Querol X (2003) Purification of
metal electroplating waste waters using zeolites. Water Res
37:4855–4862
21:1671–1679
Engates KE, Shipley HJ (2011) Adsorption of Pb2?, Cd2?, Cu2?,
Foo LPY, Tee CZ, Raimy NR, Hassell DG, Lee LY (2012) Potential
Malaysia agricultural waste materials for the biosorption of
cadmium (II) from aqueous solution. Clean Technol Environ
Policy 14:273–280
Guo XY, Zhang SZ, Shan XQ (2008) Adsorption of metal ions on
lignin. J Hazard Mater 15:134–142
Gupta RK, Nayak A (2012) Cadmium Removal and recovery from
aqueous solution by novel adsorbents prepared from orange peel
and Fe2O3 nanoparticles. Chem Eng J 180:81–90
Hammaini A, Gonzalez F, Ballester A, Blá zquez ML, Muñ oz JA
(2007) Biosorption of heavy metals by activated sludge and their
desorption characteristics. J Environ Manag 84:419–426
Hua M, Zhang S, Pan B, Zhang W, Lv L, Zhang Q (2012) Heavy
metal removal from water/wastewater by nanosized metal
oxides: a review. J Hazard Mater 211–212:317–331
Jalbani N, Soylak M (2014) Ligandless surfactant mediated solid
phase extraction combined with Fe3O4 nano-particle for the
preconcentration and determination of cadmium and lead in
water and soil samples followed by flame atomic absorption
spectrometry: multivariate strategy. Ecotoxicol Environ Saf
102:174–178
Jaman H, Chakraborty D (2009) a study of the thermodynamics and
kinetics of Copper adsorption using chemically modified rice
husk. Clean Technol Environ Policy 37:704–711
Kim JW, Sohn MH, Kim DS, Sohn SM, Kwon YS (2001) Production
of granular activated carbon from waste walnnt shell and its
adsorption characteristics of Cu2? ion. J Hazard Mater
85(3):301–315
Lai YL, Thirumavalavan M, Lee JF (2010) Effective adsorption of
heavy metal ions (Cu2?, Pb2?, and Zn2?) from aqueous solution
by immobilization of adsorbents on Ca-alginate beads. Toxicol
Environ Chem 92:697–705
Lee YC, Yang JW (2012) Self-assembled flower-like TiO2 on
exfoliated graphite oxide for heavy metal removal. J Ind Eng
Chem 18:1178–1185
Liu W, Sun W, Han Y, Ahmad Muhammad, Ni Jinren (2014)
Adsorption of Cu(II) and Cd(II) on titanate nanomaterials
synthesizedvia hydrothermal method under different NaOH
concentrations: role of sodium content. Colloid Surf A
452:138–147
Mahdavi S, Jalali M, Afkhami A (2012) Removal of heavy metals
from aqueous solutions using Fe3O4, ZnO, and CuO nanopar-
ticles. J Nanopart Res 14:1–18

123
94
Mahdavi S, Jalali M, Afkhami A (2013) Heavy metals removal from
aqueous solutions using TiO2, MgO, and Al2O3 nanoparticles.
Chem Eng Commun 200:448–470
Mahdavi S, Jalali M, Afkhami A (2015) Heavy metals removal from
aqueous solutions by Al2O3 nanoparticles modified with natural
and chemical modifiers. Clean Technol Environ Policy
17:85–102
Malkoc E, Nuhoglu Y (2005) Ni (II) removal from aqueous solution
using tea factory waste. J Hazard Mater 127:120–128
Malkoc E, Nuhoglu Y (2006) Ni (II) removal from aqueous solutions
using cone biomass of Thuja orientalis. J Hazard Mater
137:899–908
Meyi HY, Man C, Bo HZ (2010) Effective removal of Cu (II) ions
from aqueous solution by amino-functionalized magnetic
nanoparticles. J Hazard Mater 184:392–399
Mosh TB, Dror I, Berkowitz B (2010) Transport of metal oxide
nanoparticles in saturated porous media. Chemosphere
81:387–393
Pehlivan E, Cetin S, Yank BH (2006) Equilibrium studies for the
sorption of zinc and copper from aqueous solutions using sugar
beet pulp and fly ash. J Hazard Mater B135:193–199
Peng L, Qin P, Lei M, Zeng Q, Song H, Yang J, Shao J, Liao B, Gu J
(2012) Modifying Fe3O4 nanoparticles with humic acid for
removal of Rhodamine B in water. J Hazard Mater
209–2010:193–198
PhuengPrasop T, Sittiwong J, Unob F (2011) Removal of heavy
metals ions by iron oxide coated sewage sludge. J Hazard Mater
186:502–507
Pourreza N, Rastegarzadeh S, Larki A (2014) Nano-TiO2 modified
with 2-mercaptobenzimidazole as an efficient adsorbent for
removal of Ag(I) from aqueous solutions. J Ind Eng Chem
20:127–132
Shahbazi A, Younesi H, Badiei A (2014) Functionalized nanostruc-
tured silica by tetra dentate-amine chelating ligand as efficient
heavy metals adsorbent : applications to industrial effluent
treatment. Korean J Chem Eng 31:1598–1607
Sharma YC, Srivastava VU, Padhyay SN, Weng CH (2008) Alumina
nanoparticles for the removal of Ni (II) from aqueous solution.
Ind Eng Chem Res 47:8095–8100
Sica M, Duta A, Teodosiu C, Draghici C (2014) Thermodynamic and
kinetic study on ammonium removal from a synthetic water
solution using ion exchange resin. Clean Techn Environ Policy
16:351–359
123
S. Mahdavi
Tan Y, Chen M, Hao Y (2012) High efficient removal of Pb(II) by
amino-functionalized Fe3O4 magnetic nano-particles. Chem Eng
J 191:104–111
Ucar S, Erdem M, Tay T, Karagöz S (2015) Removal of lead (II) and
nickel (II) ions from aqueous solution using activated carbon
prepared from rapeseed oil cake by Na2CO3 activation. Clean
Techn Environ Policy 17:747–756
Unuabonah EI, Adebowale KO, Olu-Owolabi BI, Yang LZ, Kong LX
(2008) Adsorption of Pb(II) and Cd(II) from aqueous solutions
onto sodium tetraborate-modified kaolinite clay: equilibrium and
thermodynamic studies. Hydrometallurgy 93:1–9
Vaclavikova M, Gallios PG, Slavomir H, Jakabsky S (2008) Removal
of arsenic from water streams: an overview of available
techniques. Clean Technol Environ Policy 10:89–95
Visa M, Duta A (2013) TiO2/fly ash novel substrate for simultaneous
removal of heavy metals and surfactants. Chem Eng J
223:860–868
Xie X, Gao L (2009) Effect of crystal structure on adsorption
behaviors of nanosized TiO2 for heavy-metal cations. Curr Appl
Phys 9:S185–S188
Xu X, Cao X, Zhao L, Wang H, Yu H, Gao B (2013) Removal of Cu,
Zn, and Cd from aqueous solutions by the dairy manure-derived
biochar. Environ Sci Pollut Res 20:358–368
Yang K, Lin D, Xing B (2009) Interactions of humic acid with
nanosized inorganic oxides. Langmuir 25:3571–3576
Yang J, Liang Zhou L, Zhao L, Zhang H, Yin J, Wei G, Qian K,
Wangb Y, Yu C (2011) A designed nanoporous material for
phosphate removal with high efficiency. J Mater Chem
21:2489–2494
Yuwei C, Jialong W (2011) Preparation and characterization of
magnetic chitosan nanoparticles and it, s application for Cu(II)
removal. Chem Eng J 168:286–292
Zamani AA, Shokri R, Yaftian MR, Parizanganeh AA (2013)
Adsorption of lead, zinc and cadmium ions from contaminated
water on to Peganum harmala seeds as biosorbent. Int J Environ
Sci Technol 10:93–102
Zha R, Nadimicherla R, Guo X (2014) Cadmium removal in waste
water by nanostructured TiO2 particles. J Mater Chem
A2:13932–13941
Zhang L, Na Liu, Yang L, Lin Q (2009) Sorption behavior of nano-
TiO2 for the removal of selenium ions from aqueous solution.
J Hazard Mater 170:1197–1203