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PII: S0927-7757(17)30637-4
DOI: http://dx.doi.org/doi:10.1016/j.colsurfa.2017.06.075
Reference: COLSUA 21762
Please cite this article as: Jiali Guo, Yingchao Han, Yuting Mao, M.Nirmali
Wickramaratne, Influence of alginate fixation on the adsorption capacity of
hydroxyapatite nanocrystals to Cu2+ ions, Colloids and Surfaces A: Physicochemical
and Engineering Aspectshttp://dx.doi.org/10.1016/j.colsurfa.2017.06.075
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Influence of alginate fixation on the adsorption capacity of
Lanka
86-27-87880734
Graphical abstarct
ABSTRACT
metal ions. However, the agglomeration and precipitation of nano-HAP will result in the loss of
adsorption capacity to heavy metal ions. Herein, the stable nano-HAP suspension was
synthesized with the stabilization effect of polyacrylic acid and further fixed by alginate to form
nano-HAP-alginate composite. The effect of alginate fixation on the adsorption capacity of
nano-HAP to Cu2+ ions was studied. Results showed that the adsorption capacity to Cu2+ ions of
alginate fixed nano-HAP was depended on the mass ratio of nano-HAP to alginate. With the
increase of mass ratio of nano-HAP to alginate from 5:95 to 95:5, the displayed adsorption
capacity of nano-HAP to Cu2+ ions was gradually decreased due to the increasing agglomeration
of nano-HAP. Especially, while the mass ratio of nano-HAP to alginate was at 5:95-10:90, the
nano-HAP was fixed in alginate with single-particle distribution, showing adsorption capacity
comparable to that of nano-HAP suspension (60.99 mgg-1). The adsorption of Cu2+ on nano-HAP
was attributed to Langmuir isotherm model (monolayer sorption). After fixation by alginate, the
resulting nano-HAP-alginate (50:50) composite showed the adsorption to Cu2+ followed both the
Langmuir and Freundlich isotherm models, indicating the multilayer sorption of Cu2+ on
heterogeneous surface. Accordingly, the alginate fixation is an alternative way for nano-HAP as
Keywords: Nano hydroxyapatite; Alginate fixation; Composite; Heavy metal ions; Adsorption
1. Introduction
petrochemical industrial emissions, can cause serious pollution to the environment. In particular,
heavy metal ions causing water pollution will lead to long-term toxicity effects in plants, animals
and humans if the heavy metal ions are not effectively treated and removed from water.
Therefore, it is very important to seek effective methods for removing heavy metal ions in
extraction and membrane separation are commonly used methods for removing heavy metal ions
[1-6]. Due to its low cost, high efficiency and ease of use, the adsorption method is becoming a
The removal capacity of the adsorbent is a vital factor influencing the removal effect of heavy
metal ions. In addition, the adsorbent should be environmentally friendly and causes no
secondary pollution. Hydroxyapatite (HAP) is the main mineral constituent of teeth and bones of
mammals and has been widely used as biomaterials. HAP can also be utilized as an inorganic
adsorbent with good adsorption ability to a variety of heavy metal ions [11-15]. The adsorption
complexation with phosphate, calcium and hydroxyl groups. Due to a higher specific surface area,
nano-HAP has a higher adsorption capacity [16,17]. However, the aggregation of nano-HAP in
aqueous solutions without stabilizers will result in the loss of removal capacity; moreover, well
dispersed and highly stable nano-HAP is not easy to be isolated from aqueous solutions after
adsorption of heavy metal ions. An alternative is to disperse and fix nano-HAP in polymer, to
inhibit agglomeration of nano-HAP and to easily separate the material from the aqueous solution
after adsorption of heavy metal ions [7]. Sodium alginate (SA) is a biocompatible and
biodegradable material that can easily exchange its Na+ ion with heavy metal ions to form gels
and has a great application prospect in the adsorption of heavy metal ions [18, 19]. It can be used
to fix HAP particles and the resulting HAP-alginate composite shows good adsorption capacity
and removal efficiency due to the integrated function of different components [20].
In this paper, the stable nano-HAP suspension was synthesized with the stabilization effect of
polyacrylic acid and further fixed by alginate to form nano-HAP-alginate composite. The effect
of alginate fixation on the adsorption capacity of nano-HAP to Cu2+ ions was studied with varied
the Ca/P molar ratio of 1.67, 100 mL of Ca(NO3)2 aqueous solution (Ca2+: 0.0334 M) was mixed
quickly with 100 mL of (NH4)2HPO4 aqueous solution (PO43-: 0.02 M) to obtain precipitation at
80 °C under strong stirring. Then, ammonium hydroxide was added to adjust the pH value to
approximately 10, and the reaction was maintained at 80 °C for 1 h. Next, the precipitate was
separated by centrifugation and washed three times using deionized water. Finally, the obtained
polyacrylic acid (PAA, 0.3 mgmL-1) as the stabilizer and using a high intensity ultrasound probe
(6 min).
Under stirring, alginate was dissolved in the above nano-HAP suspension, and the mixture
was heated at 80 °C. After evaporation of water, gels were formed. The concentration of mixture
(nano-HAP and alginate) was controlled at 0.067 gmL-1. Next, the gels were shaped in a cylinder
mold and frozen at -20 °C. After the freeze drying process, a dried composite was obtained. The
mass ratio of nano-HAP to alginate was controlled from 5:95 to 95:5, corresponding to the
immersed into the mixture of alcohol and 10% CaCl2 aqueous solution (volume ratio of 5:1) for
the gelation process of 1 h. After washing and drying, the nano-HAP was fixed by alginate and
Thermo Nicolet, USA). X-ray diffraction analysis (XRD, D8 Advance, Germany) was utilized to
analyze HAP. Crystallite size of the powders was calculated by using the equation: X hkl = k λ/
(β1/2cosθ). Transmission electron microscope (TEM, JEM2100F, Japan) and scanning electron
microscope (SEM, ULTRA PLUS-43-13, Germany) were used to observe the morphology and
scattering (DLS, ZetaSizer 3000HS, UK) was used to determine the size distribution of the
nano-HAP suspension. The concentration of heavy metal ions were determined by Atomic
Cu2+ aqueous solution was added into nano-HAP suspension with resulting concentrations
from 20 mgL-1 to 500 mgL-1. Under stirring, the adsorption of Cu2+ on HAP was carried out for 1
h. After centrifugation, the concentration of Cu2+ in the supernatant was measured using the
The adsorption property of nano-HAP-alginate for Cu2+ was studied in detail. First, the
saturated adsorption time was determined. Adsorption time was set at 10 min, 20 min, 30 min, 40
min, 50 min, 60 min, 120 min, 180 min, 240 min, 360 min. For each time point, an independent
adsorption experiment was carried out as the following. The obtained nano-HAP-alginate (20 mg)
was immersed in 4 mL of Cu2+ aqueous solution (500 mgL-1). The concentration of Cu2+ in the
supernatant was measured by the AAS method at the setting time point. Next, for determining
the saturated adsorption capacity, the obtained nano-HAP-alginate (20 mg) was immersed in 4
mL of Cu2+ aqueous solution with increasing concentration from 20 mgL-1 to 500 mgL-1. After 1
h, the concentration of Cu2+ in the supernatant was measured by the AAS method.
All adsorption experiments were carried out at ambient temperature on a shaker working at
110 rpm. The removal capacity (Qt, mgg-1) was calculated according to the following equation:
Qt = (C0-Ct) Vm-1, where C0 and Ct are the metal ion concentrations at the initial time and an
arbitrary time, respectively, V is the volume of the solution, and m is the mass of the adsorbent.
The XRD pattern in Figure 1(a) shows that the sample was crystalline HAP. The calculated
crystallite sizes of HAP in the (002) and (310) crystallographic planes were 28.2 nm and 15.2 nm,
which corresponded to the sizes in the long axis and cross section directions, respectively. This
indicated that the HAP nanoparticles should be short rod-like. The FT-IR spectrum of the sample
(Figure 1(b)) also showed the characteristic vibrations assigned to HAP. The vibration bands of
PO43- were detected at 1048 cm-1, 890 cm-1, 605 cm-1 and 958 cm-1; the broad band centered at
3437 cm-1 was due to the adsorption of -OH groups in water, and the band at 3570 cm-1 was due
to the adsorption of -OH groups in HAP. As shown in the SEM micrograph (Figure 2(a)), the
obtained HAP nanoparticles were needle-like with sizes of 18.7±1.2 nm in diameter and
196.0±31.3 nm in length. The HAP nanopowders could be well dispersed in water to form a
stable suspension with PAA (0.3 mgmL-1) by ultrasound treatment. The size distribution (Figure
2(c)) of the HAP suspension was from 40 nm to 400 nm, and the intensity-averaged particle size
was 122.7 nm. The polydispersity index was 0.131, showing a narrow size distribution in the
HAP suspension. The good stability of HAP suspension is mainly attributed to the steric effect of
PAA. The TEM micrograph (Figure 2(b)) shows that HAP was needle-like nanoparticles with
sizes of 7.3-15.6 nm × 68.0-105.0 nm. The smaller value of the length from TEM compared with
that from SEM demonstrated that HAP nanoparticles were well dispersed in a stable suspension,
Nano-HAP-alginate composites with different mass ratio of nano-HAP to alginate (from 5:95
to 75:25), corresponding to HAP contents from 5 wt% to 75 wt%, were obtained. SEM images of
Nano-HAP-alginate composites are shown in Figure 3. It can be seen here that for the
composites with 5-10 wt% HAP, HAP nanoparticles were fixed and dispersed uniformly in the
alginate matrix with single-particle distribution. However, when the content of HAP was 20-50
wt%, the fixed nano-HAP showed some agglomeration. With a further increase of the HAP
nano-HAP are shown in Figure 4. The results showed that the intensity of the vibration bands of
HAP was gradually enhanced, demonstrating the increasing content of HAP in the composite. In
particular, the bands assigned to the asymmetric and symmetric stretching of the –COO- group of
alginate in the composite were moved to 1617-1628 cm-1 and 1416-1420 cm-1, respectively,
compared to those in pure SA (1609 cm-1 and 1431 cm-1). However, the positions of the –COO-
group of alginate in the composite were close to those in CaCl2 treated SA. In addition, the
intensity of the symmetric stretching of the –COO- group was lower than that of the asymmetric
stretching of the –COO- group in the composite, which is consistent with the change in
CaCl2-treated SA. The changes of bands in the position and intensity can be attributed to the
interaction between the –COO- group in alginate and Ca2+ on the surface of HAP via an
electrostatic attraction force. It can be concluded that the nano-HAP was integrated with alginate
in chemical bonds.
nano-HAP without alginate fixation. The adsorption capacity and removal efficiency of
nano-HAP for Cu2+ are shown in Figure 5. With increasing concentration of Cu2+ in the solution
to 250 mgL-1, the adsorption capacity of nano-HAP rapidly increased at a high removal
efficiency of 97-99 %. With a further increase of the Cu2+ concentration from 250 mgL-1 to 500
mgL-1, the removal rate gradually decreased. However, the adsorption capacity was still
increased and reached the highest value of 60.98 mgg-1 at a Cu2+ concentration of 350 mgL-1.
First, the adsorption equilibrium time of the nano-HAP-alginate composite (50 wt% of
nano-HAP) was studied at a Cu2+ concentration of 500 mgL-1. As shown in Figure 6, when the
adsorption time was below 60 min, the adsorption capacity was rapidly elevated. With the further
adsorption time of 60 min was selected as the best adsorption time and was adopted for all other
experiments. It was also observed that the adsorption efficiency decreased gradually with the
increase of Cu2+ concentration (20-500 mgL-1), and the highest adsorption capacity was 48.27
The effect of the mass ratio of nano-HAP to alginate on the adsorption capacity of the
nano-HAP-alginate composite for Cu2+ decreased gradually from 71.03 mgg-1 (0 wt% of
nano-HAP) to 40.48 mgg-1 (95 wt% of nano-HAP) with increasing content of nano-HAP due to
On the basis of the obtained experimental values of adsorption capacity of pure alginate
(EValginate) and pure nano-HAP (EVnano-HAP), the calculated value of adsorption capacity of
composite (CVcomposite) was obtained using equation: CVcomposite = EValginate × (1- HAP wt%) +
EVnano-HAP × HAP wt%, where EValginate was 71.0 mgg-1 (the value at 0 of HAP wt%); EVnano-HAP
was 61.0 mgg-1 (deriving from Figure 5). The calculated values were denoted by symbol ( ) in
Figure 8. In addition, the calculated value of alginate fixed nano-HAP (CVfixed nano-HAP) was
obtained based on the experimental values of adsorption capacity of pure alginate (EValginate) and
composite (EVcomposite) using equation: CVfixed nano-HAP = [EVcomposite - EValginate × (1- HAP wt%)] /
HAP wt%, where EValginate was 71.0 mgg-1 (the value at 0 of HAP wt%); EVcomposite was the
obtained experimental value. The calculated values were denoted by symbol (○) in Figure 8.
Results showed that while the mass ratio of nano-HAP to alginate was from 5:95 to 20:80, the
experimental adsorption capacity of composite was very close to the calculated adsorption
capacity; moreover, the calculated adsorption capacity of alginate fixed nano-HAP was very
close to the adsorption capacity of nano-HAP (61.0 mgg-1). These indicate that after being fixed
by alginate fixation, nano-HAP can maintain its adsorption capacity to Cu2+ with the mass ratio
with single-particle distribution. However, with the further increase of mass ratio of nano-HAP
to alginate, the experimental adsorption capacity of composite was becoming smaller than the
calculated adsorption capacity with an increasing disparity; moreover, the alginate fixed
nano-HAP showed many loss in adsorption capacity. This is due to the increasing agglomeration
solution, which are dissolution-precipitation, ionic exchange reaction and surface complexation
[21, 22]. First, nano-HAP has a higher solubility than bulk HAP and can be dissolved in solution
to form H2PO4- groups which can react with heavy metal ions (M2+) to form precipitation, i.e.,
(M10(PO4)6(OH)2). Second, the Ca2+ ions in the HAP lattice can be exchanged with heavy metal
ions, resulting in the removal of heavy metal ions from the aqueous solution by forming heavy
metal ions partially substituted with HAP (Ca(10-x )Mx(PO4)6(OH)2. Finally, the phosphate and
hydroxyl groups on the surface of HAP crystals can adsorb heavy metal ions by complexation.
For alginate, the abundant carboxyl groups can interact with divalent heavy metal ions by ion
exchange, facilitating the removal of heavy metal ions [23, 24]. Nano-HAP suspension is in a
high dispersity situtation and nano-HAP can provide large contact areas with heavy metal ions,
leading to a high removal capacity. After being fixed by alginate, the solubility and crystal nature
of nano-HAP are not be changed. Therefore, the removal capacity of nano-HAP to heavy metal
ions, which is based on dissolution-precipitation and ionic exchange reaction, should not be
adsorption sites (phosphate and hydroxyl groups) and decrease the contact areas with heavy
metal ions. Accordingly, the adsorption capacity of nano-HAP based on surface complexation is
declined.
The kinetic behavior of the metal ion removal by nano-HAP-alginate composite adsorbent was
investigated by using the dynamic data presented in Figure 6. The pseudo-first order kinetic
model, pseudo-second order kinetic model and intraparticle diffusion model were proposed to
clarify the adsorption kinetics (Figure 9) [7]. The results for the kinetic model parameters as well
as regression coefficient (R2) are shown in Table S1. The higher R2 value of 0.998 of
pseudo-second order kinetic model than other two models (0.943 and 0.824) as well as a close
calculated Qe to experimental Qe revealed that the pseudo-second order kinetic model was more
appropriate to describe the dynamic behavior of the metal ion removal by nano-HAP-alginate
composite. Also, the removal of metal ion by nano-HAP-alginate composite was mainly
The adsorption isotherm studies were done for nano-HAP and 50% nano-HAP-alginate
composite for Cu2+ removal by using the data presented in Figure 5 and Figure 7 respectively.
Langmuir model, Freundlich model and Tempkin model were considered to describe the
equilibrium behavior of nano-HAP (Figure 10) and 50% nano-HAP-alginate composite (Figure
11) and the results are shown in Table S2 [20]. For nano HAP, the higher R2 value of 0.999 and
the very close calculated Qmax to experimntal value indicated the Langmuir isotherm model was
more suitable to describe the adsorption of Cu2+ ions. For 50% nano-HAP-alginate composite,
the both higher R2 values of 0.998 and 0.993 show that the adsorption of Cu2+ onto composite
followed both the Langmuir and Freundlich isotherm models. That is to say, nano-HAP-alginate
composite may occur the multilayer sorption of Cu2+ on heterogeneous surface of adsorbent
4. Conclusions
PAA stabilized nano-HAP was successfully prepared and further fixed by alginate as
adsorbent for removing heavy metal ions. The mass ratio of nano-HAP to alginate influenced the
adsorption capacity to Cu2+ ions. With the mass ratio of nano-HAP to alginate from 5:95 to
20:80, the adsorption capacity of composite close to the calculated value was obtained and the
alginate fixed nano-HAP showed the adsorption capacity comparable to that of nano-HAP in
suspension (61.0 mgg-1). This is because that nano-HAP is uniformly fixed in alginate with
single-particle distribution. However, the further increasing mass ratio resulted in the loss of
Nano-HAP showed monolayer sorption of Cu2+ (Langmuir isotherm model). After alginate
heterogeneous surface (Langmuir and Freundlich isotherm models). So, nano-HAP can be used
as adsorbent for removing heavy metal ions in the form of alginate fixation, leading to easy
Acknowledgements
This work was supported by the Science and Technology Partnership Program, Ministry of
Science and Technology of China (KY201602002), the National Key Research and Development
Cooperation Project (2016030409020217), the Fundamental Research Funds for the Central
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Figure Captions
Figure 2. SEM image of nano-HAP(a), TEM image (b) and size distribution (c) of PAA
stabilized nano-HAP.
Figure 4. FT-IR spectra of CaCl2 treated SA (a), pure SA (b), CaCl2 untreated
nano-HAP-alginate composites with 5% (c), 10% (d), 20% (e), 40% (f), 50% (g), 75% (h) HAP,
time.
nano-HAP content for Cu2+ and the corresponding calculated values of nano-HAP-alginate
Figure 9. Pseudo-first order kinetic model fitting (a), pseudo-second order kinetic model fitting
(b) and intraparticle diffusion model fitting (c) for Cu2+ adsorption onto 50% nano-HAP-alginate
composite.
Figure 10. Langmuir model, Freundlich model and Tempkin model fittings for Cu2+ adsorption
onto nano-HAP
Figure 11. Langmuir model, Freundlich model and Tempkin model fittings for Cu2+ adsorption