Journal of Solid State Chemistry 245 (2017) 200–206

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Journal of Solid State Chemistry

journal homepage: www.elsevier.com/locate/jssc

Precursor preparation for Ca-Al layered double hydroxide to remove

hexavalent chromium coexisting with calcium and magnesium chlorides
crossmark
⁎
Lihua Zhonga, Xiaoman Hea, Jun Qua, Xuewei Lia, Zhiwu Leia, Qiwu Zhanga, , Xinzhong Liub
a
School of Resources and Environment Engineering, Wuhan University of Technology, Wuhan 430070, China
b
College of Ecological Environment and Urban Construction, Fujian University of Technology, Fuzhou 350118, China

A R T I C L E I N F O A BS T RAC T

Keywords: Al(OH)3 and Ca(OH)2 powders are co-ground to prepare a precursor which hydrates into a layered double
Precursor hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room
Cr(VI) removal temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation
Al-Ca-CrO4 LDH into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the
High salinity
solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when
they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca
precursor fit a pseudo-second-order kinetics with a Langmuir adsorption capacity of 59.45 mg/g. Besides,
characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray
diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand
the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase
formation.

1. Introduction sented as [Ca2Al(OH)6](X)(x)·yH2O, X including OH−, Cl−, NO3−,

Chromium has different valences under different conditions in the
environment, including trivalent Cr(III), tetravalent Cr(IV) and hex-
avalent Cr(VI). Cr(VI) is a well known toxic composition with carcino-
genic and mutagenic activities. In industrial wastewater, Cr(VI) may
exist in the forms of CrO42− and Cr2O72−. It had been widely used in
chrome-plated parts, industrial grade leather, rubber paint and ceramic
raw material. Many technologies have been developed for the treat-
ment of wastewater with Cr(VI): including reduction precipitation by
reducer into trivalent ion, evaporation recovery [1]，ion exchange
[2]，electrochemical reduction [3], membrane separation [4], solvent
extraction and adsorption [5,6]. Although various adsorbents such as
activated carbon [7], agricultural and industrial by-products [8–10]，
natural akadama clay [11], as well as some composite materials and
modified materials of magnetic naturalzeolite-polypyrrole (MZ-PPy)
composites [12,13], heat-activated bauxite [14]，and activated carbo-
aluminosilicate material [15] were widely studied for Cr(VI) removal, it
remains as an environmental concern and further effort is needed to
deal with some complex cases, where it may be difficult to reduce it into
trivalent ions by chemical reducers. Coexisting with high salinity
usually results in significant decrease in the adsorption efficiency of
Cr(VI) with the reported adsorbents.
Ca-Al LDH was introduced as AFm phases and it can be repre-
CO32−, SO42− or Al(OH)4− [16]. Various methods have been developed
to synthesize Ca-Al LDH, including co-precipitation [17], microwave
irradiation [18], a solvent-free mechanochemical way [19]. It have
been widely used in many domains such as environmental applications
[16] and multifunctional materials [20]. Layered double hydroxides
(LDHs) as a group of clay minerals have been applied to the removal of
various anionic pollutants [21]. Several LDHs in different compositions
of (Al+Zr)-Zn, (Al+Zr)-Mg, Ni-Fe and Mg-Al-CO3/Cl have been
reported to demonstrate adsorption effects on the Cr(VI) removal as
adsorbents [22–25], Ultrasound assisted synthesis of Ca–Al layered
double hydroxide using the co-precipitation method has been reported
and the removals of chromium and uranium are attributed to a unique
structure with interconnected ion-exchange performance [26], In
addition, Mn-doped Zn/Al layered double hydroxides (LDH) materials
were also synthesized by co-precipitation method, and it was evaluated
in the photocatalytic degradation of phenol in aqueous medium, under
the condition of UV radiation with and without O2 source [27].
Recently during our researches to improve the adsorption capacity
of LDH and ettringite adsorbents etc. through mechanochemical
activations [16,28–30], a novel phenomenon was discovered. When
dry grinding the starting hydroxides to stimulate chemical bonding, the
obtained sample may be taken as a precursor since it transform into the
target LDH phase or other purpose phases easily through just agitation

⁎
Corresponding author.

http://dx.doi.org/10.1016/j.jssc.2016.10.022
Received 3 August 2016; Received in revised form 30 September 2016; Accepted 21 October 2016
Available online 24 October 2016
0022-4596/ © 2016 Published by Elsevier Inc.
L. Zhong et al.
in water. It is more interesting to note that the adsorption capacity of
the precursor sample is much higher than that of the finally synthesized
adsorbent. Furthermore, in the case of Ca-Al hydroxides, different from
the easy formation of Mg/Al LDH from the Mg-Al hydroxides [31], the
existence of a third phase of carbonate or chloride was found to be
necessary to synthesize Ca-Al-X LDH phase [16].
In this paper, we report the preparation of Al-Ca precursor from the
co-ground hydroxides and the subsequent transformation into LDH
phases by agitating the precursor in solutions containing Cr(VI), Ca/
Mg chlorides and the mixture of both. Cr(VI) composition serves as a
third phase to be incorporated into Ca-Al-CrO4 LDH phase and high
efficiency of Cr(VI) removal is obtained even with coexistence of the
chlorides. The prepared precursor simply by dry grinding demonstrates
super performance for removing Cr(VI) from the wastewater difficult to
treat due to the high salinity.
2. Experimental procedure
2.1. Sample preparation and characterization
All the chemical reagents Al(OH)3, Ca(OH)2, CaCl2·2H2O, MgCl2
and K2CrO4 were supplied by Sinopharm Chemical-China and used as
received without further treatment. Al(OH)3 and Ca(OH)2 were mixed
at a molar ratio of 2:3 and total mass 2 g of the mixture were put in a
zirconia mill pot (45 cm3 inner volume) with 7 zirconia balls of 15 mm
diameter and ground by a planetary ball mill (Pulverisette-7, Fritsch,
Germany) for 3 h at the rotational speed of 500 rpm, serving as the Al-
Ca precursor in this research. The samples with molar ratio of
2:3:x(x=0.5,1) for Al(OH)3:Ca(OH)2:M(M=CaCl2 or MgCl2), were also
ground at the same conditions as chloride mixed precursors for
comparative studies. As to the formations of Al-Ca LDH samples,
0.5g of the ground samples were stirred in 50 ml deionized water and
solutions with target CaCl2, MgCl2 and/or K2CrO4 at specific concen-
trations for 3 h in a sealed plastic wrap. The solutions were filtered and
solid samples were recovered and put in a vacuum vial at room
temperature up to 24 h for drying.
XRD patterns of the samples prepared and the ones after adsorp-
tion were recorded on a Rigaku MAX-RB RU-200B diffractometer
using CuKαradiation (λ=1.5403 Å). Transmission electron microscopy
(TEM) observation of the prepared precursor and the sample after
adsorption was conducted on a FEI field-emission transmitting elec-
tron microscope (JEM2100F/JEM2100F, Japan) at an acceleration
voltage of 200 kV. The lattice resolution of scanning transmission
image was 0.20 nm. Fourier transformed infrared (FT-IR)
(Nicolet6700, Thermo) spectra of the samples were measured over
4000–500 cm−1 using KBr as a diluent.
2.2. Adsorption experiments
Batch adsorption experiments were carried out with temperature
controlled by a thermostatic water-wash shaker (SHA-C-2, Changzhou
Guohua 71 Electric Appliance Co., Ltd) operated at 250 rpm and all the
hexavalent chromium solutions required for experiments were pre-
pared freshly for each time.
The adsorption equilibrium experiments were performed using
50 ml of Cr(VI) solutions with concentrations of 5–90 mg/l and
0.08 g of the prepared Al-Ca precursor or chloride mixed precursor
at constant temperature of 25 °C. The suspensions were shaken for 3 h
to attain equilibrium. All the samples after experiments were centri-
fuged at about 6000g to recover the supernatants and the remaining
Cr(VI) concentrations in the supernatants were analyzed by a spectro-
metric method (Spectrophotometer UV mini-1240, Shimadzu
Instruments, Japan) at 540 nm. The equilibrium sorption capacity
(qe) of each adsorbent was calculated from the following expression Eq.
(1).
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Journal of Solid State Chemistry 245 (2017) 200–206
⎛ C − Ce ⎞
qe = ⎜ 0 ⎟V
⎝ m ⎠ (1)
Where qe (mg/g) was the amount of Cr(VI) adsorbed; C0 and Ce(mg/l)
were initial and equilibrium hexavalent chromium concentration, m (g)
was adsorbent dose, V (ml) was the volume of the Cr(VI) solution.
Adsorption kinetics were also carried out to evaluate the rate of Cr(VI)
sorption. The experiments were conducted at the initial concentration
of 50 mg/l. 0.08 g Al-Ca precursor sample or the chloride mixed
precursor one were added to 50 ml of Cr(VI) solution and shaken at
250 rpm. The capacity of the adsorbent qt (mg/g) at time was obtained
from Eq. (2): where Ct (mg/l) was the concentration of hexavalent
chromium at time t.
⎛ C − Ct ⎞
qt = ⎜ 0 ⎟V
⎝ m ⎠ (2)
3. Results and discussion
3.1. Comparative study of the adsorption capacity of the prepared Al-
Ca precursor
Fig. 1 shows the XRD patterns of three typical samples prepared
under different conditions. With sample A of the ground Al(OH)3 and
Ca(OH)2 at a fixed molar ratio of 2:3, only peaks of a katoite phase
(Ca3Al2(OH)12) appeared in the pattern. In other words, the Al-Ca
precursor without adding other compositions would crystallize as the
katoite phase easily and this phenomenon was reported in previous
publication [16]. With sample (B) from the agitation of the sample (A)
in the aqueous solution with Cr(VI) at concentration of only 80 mg/L,
different pattern was obtained. Although weak peaks of katoite phase
were still observable, new phase of 3CaO·Al2O3·CaCrO4·12H2O ap-
peared in the pattern as the main one, indicating that it was quite easy
to incorporate Cr(VI) into the kaotite phase to synthesize a LDH phase
as 3CaO·Al2O3·CaCrO4·12H2O. In the pattern of the sample (C) of the
Al-Ca-MgCl2 co-ground precursor agitated in water as a reference
sample, strong peaks of a Ca-Al-Cl LDH phase as 3CaO·Al2O3·MgCl2·
10H2O were observed. XRD analysis clearly indicated that the prepared
Al-Ca precursor at a molar ratio of 2:3:0 exhibited a strong tendency to
synthesize a LDH phase with a molar ratio of 2:3:1 when adsorbing
another composition just through the agitation in the aqueous solution
with the target composition.
Maximum adsorption capacity experiments for Cr(VI) were con-
Fig. 1. XRD patterns of the prepared samples: (A) the dry milling product of Ca and Al
hydroxides; (B) sample (A) agitated in Cr(VI) solution; (C) Al-Ca-MgCl2 precursor
agitated in deionized water.
L. Zhong et al.
Fig. 2. Maximum adsorption capacity of different adsorbents for Cr(VI): (A) Al-Ca=2:3
co-ground; (B) Al-Ca-MgCl2=2:3:0.5 co-ground; (C) Al-Ca-MgCl2=2:3:1 co-ground; (D)
Al-Ca mixture without grinding; (E) only Al(OH)3 ground; (F) Al-Ca=2:3 in solution with
0.5 mol MgCl2; (G) Al-Ca=2:3 in solution with 1 mol MgCl2.
ducted on the prepared Al-Ca precursor as well as several reference
samples and the results are shown in Fig. 2. First sample D of the
Ca(OH)2 and Al(OH)3 mixture without milling and sample E of
Al(OH)3 only ground gave a Langmuir adsorption capacity of the same
low value of 0.79 mg/g. These two samples had only ignorable
adsorption ability to Cr(VI). The sample A of the Al-Ca hydroxides
co-ground had a Langmuir adsorption capacity as high as 59.45 mg/g,
presenting the excellent performance for Cr(VI) removal through LDH
formation. Sample D is the physical mixture of two hydroxides and
remained as the mixture after agitation in the solution. Sample E of the
ground Al(OH)3 exhibited a nearly amorphous phase and remained
unchanged after agitation in the solution. Compared with the samples
D and E without evident changes when agitated in the solution, it was
understood that the mechanochemical treatment of Al and Ca hydro-
xides to prepare the precursor and subsequent transformation of the
precursor into LDH phase was the key action for Cr(VI) removal.
In addition, many industries of the major users of Cr(VI) species
usually produce wastewater containing Cr(VI) along with other cations
like Mg2+, Zn2+ and anions like Cl- [32]. The effects of the existences of
CaCl2 and MgCl2 with Cr(VI) in the aqueous solution were examined.
The results with MgCl2 were presented since there were no noticeable
differences between two chlorides. The maximum Cr(VI) adsorption
capacity of Al-Ca precursor in the solutions together with 0.5 mol
MgCl2 (concentration of MgCl2 in solution=223.2 mg/l) as sample F
and 1 mol MgCl2 (concentration of MgCl2=401.6 mg/l) as sample G
maintained still high values of 51.26 mg/g and 47.53 mg/g, respec-
tively, demonstrating a slight decrease in capacity with the existence of
MgCl2. Five times higher of the MgCl2 concentration than Cr(VI) in the
solution did not deteriorate much the removing efficiency of Cr(VI) by
using the prepared precursor, a clear advantage over other adsorbents
with obvious deterioration reported due to anionic ion competition.
Further comparative experiments were performed by cogrinding MgCl2
with the two hydroxides before the agitation in the solution, trying to
give the chloride a chance to be preferentially incorporated into a Ca-
Al-Cl LDH phase. The prepared sample B with Al-Ca-MgCl2=2:3:0.5
and sample C with Al-Ca-MgCl2=2:3:1 had Langmuir adsorption
capacity of 44.88 mg/g and 44.98 mg/g, respectively, a little decrease
than that by agitation in the solution but still relatively high values. In
other words, it could be understood that the prepared precursor
exhibited a preferred adsorption of Cr(VI) to chloride salts, indicating
a high potential application for Cr(VI) removal particularly coexisting
with high concentration of chloride salts.
The solid residues after the adsorption of both Cr(VI) and MgCl2
were recovered and the compositions were analyzed by XRD. Fig. 3
shows the XRD patterns of the samples after adsorption with mixed
Cr(VI) and MgCl2 at 0.5 mol (sample A) and 1 mol (sample B), with the
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Journal of Solid State Chemistry 245 (2017) 200–206
Fig. 3. XRD patterns of the Ca-Al precursor after adsorption: (A) with mixed Cr(VI) and
0.5 mol MgCl2; (B) with mixed Cr(VI) and 1 mol MgCl2; (C) with Cr(VI) only; (D) with
MgCl2 only.
separate adsorption of Cr(VI) (sample C) or MgCl2 (sample D) as
reference samples. Compared with the clear formations of Ca-Al-CrO4
LDH as 3CaO·Al2O3·CaCrO4·12H2O in sample C and Ca-Al-Cl LDH as
3CaO·Al2O3·MgCl2·10H2O in sample D, a mixture of these LDHs was
observed with the sample A and B due to the adsorption of both Cr(VI)
and MgCl2. However, Ca-Al-CrO4 LDH was clearly identified as the
main phase considering the very weak peaks of Ca-Al-Cl LDH phase. It
is interesting to note that two phases of Ca-Al-CrO4 LDH as 3CaO·
Al2O3·CaCrO4·12H2O and 3CaO·Al2O3·CaCrO4·14H2O were formed
with the existence of MgCl2. The formation of 3CaO·Al2O3·CaCrO4·
14H2O, which did not appear in the pattern of sample C, suggested the
possible incorporation of more water molecules with the coexistence of
chloride salts.
On the other hand, the remaining Cr(VI) concentrations were
measured and the removal efficiency of the Cr(VI) of 94.5%, 95.5%
and 96.7%, respectively, was obtained with the added MgCl2 mole at 0,
0.5 and 1 in the 80 mg/l Cr(VI) solution. It is believed that the stable
formations of 3CaO·Al2O3·CaCrO4·12H2O and 3CaO·Al2O3·CaCrO4·
14H2O rather than the physical adsorption allowed the constantly high
efficiency of Cr(VI) removal, irrespective of the concentrations of
coexisting MgCl2. These results confirmed that the incorporation of
CrO42− in a special LDH structure occurred to form a relatively stable
one without suffering evident interference of coexisting MgCl2.
Considering that adsorbents prepared elaborately with much high
specific surface area may still suffer obvious decrease in adsorption
performance with the coexistence of other competition ions, the
chemical incorporation of the CrO42− ions into the LDH structure,
confirmed by XRD analysis here, may have played an important role in
overcoming the competition effect.
The FT-IR patterns of the Al-Ca-Cl and Al-Ca-CrO4 LDHs samples
with different addition ratios of MgCl2 in the solution after the
adsorption of Cr(VI) are showed in Fig. 4. In all samples, the infrared
bands at 1638 cm−1and around 3424–3675 cm−1 were observed from
the vibrations of –OH groups of the adsorbed and interlayered H2O.
The adsorption centered at around 1416 cm−1 was assigned to the
presence of the CO3 group because of a possible adsorption of CO2 by
Ca(OH)2 during agitating and sample handling to form CaCO3 [16,33].
Besides the typical vibrations of Al-OH and Ca-O around 530 and
787 cm−1 in the spectra of Al-Ca-CrO4 LDH samples, the mode of
intercalated CrO42− ions is therefore important to the structural order
of the LDH. Since CrO42− ion has been reported to have the asymmetric
stretch (ν3=863 cm−1) and the symmetric deformation (ν4=375 cm−1)
[34,35], the observed peak around 876 cm−1 may be attributed to ν3
vibration of the intercalated CrO42− ion inside. The existence of the
L. Zhong et al.
Fig. 4. FT-IR spectra of the Ca-Al precursor after adsorption with Cr(VI) and: (A) 1 mol
MgCl2; (B) 0.5 mol; (C) 0 mol.
mode was observed within all three samples, indicating the successful
incorporation of Cr(VI) into the LDH structure even with the coex-
istence of MgCl2, consistent with the results by XRD analysis and
quantitative adsorption measurement of Cr(VI). When the peaks
corresponding to the ν3 mode were compared carefully, changes in
the sharpness of the peak were noticeable and with more addition of
MgCl2, the peak became slightly more weakened, indicating that the
formation of Ca-Al-CrO4 LDH was affected to some degree by the
coexistence of MgCl2.
TEM images of the prepared Ca-Al precursor before and after
Fig. 5. TEM images of the Ca-Al precursor before adsorption (a) and (b); precursor after adsorption (c) and (d).
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Journal of Solid State Chemistry 245 (2017) 200–206
adsorption are shown in Fig. 5. It is clear as shown in (a) and (c), that
both samples before and after adsorption exhibited in a heavy
agglomeration with primary particles less than 100 nm, although the
places without too many particles were chosen for easy observation.
The particle surfaces of the Ca-Al sample look in a rough feature and
aggregated as irregular spherical particles with a diameter of 60–
80 nm. It is observed that these particles became smaller when
hydrated in the Cr(VI) ion solution to form LDH phase. In other
words, after adsorption, the formed Ca-Al-CrO42− LDH sample demon-
strated smaller size but maintained the similar agglomeration struc-
tures. The larger precursor particles divided into several smaller ones
when incorporating water and Cr(VI) composition to form the LDH
phases. However, as shown in (b) and (d), even with the high resolution
microscope image, it was difficult to observed clear lattice fringes with
both samples before and after adsorption, indicating the very poor
crystallinity of the samples prepared by milling operation.
3.2. Adsorption isotherm and kinetics
Adsorption isotherms were studied on the Al-Ca precursor with
CaCl2 and MgCl2 at different molar ratios and the results are presented
in Fig. 6. The evaluations of maximum adsorption capacity of the
samples were fitted with Langmuir and Freundlich isotherm models,
with Eq. (3) for Langmuir model and Eq. (4) for Freundlich model:
Ce 1 C
= + e
qe qm b qm (3)
1
lnq e = lnkF + Ce
n (4)
L. Zhong et al. Journal of Solid State Chemistry 245 (2017) 200–206

Fig. 6. Adsorption isotherms of several samples fitting on Langmuir and Freundlich models: (a) Al-Ca with 0/0.5/1 CaCl2 by Langmuir model fitting; (b) Al-Ca with 0/0.5/1 MgCl2 by
Langmuir model fitting; (c) Al-Ca with 0/0.5/1 CaCl2 by Freundlich model fitting; (d)Al-Ca with 0/0.5/1 MgCl2 by Freundlich model fitting; Conditions: adsorbent dosage 0.08 g/50 ml;
Temperature 25 °C;contacting time 180 min.

Table 1 contribution to the high performance of Cr(VI) ion removal may not
Langmuir and Freundlich isotherm constants for Cr(VI) adsorption on different result from the surface adsorption on the sample, but from the
adsorbents.
chemical combination into the LDH structure, as indicate by XRD
Adsorbent Molar ratio for Al Langmuir constants Freundlich constants
and IR analyses.
(OH)3:Ca Adsorption kinetics of Cr(VI) by Al-Ca-CaCl2 and Al-Ca-MgCl2 are
(OH)2:CaCl2/ qm b R2 KF 1/n R2 shown in Fig. 7. Equilibrium time for the adsorption of Cr(VI) onto the
MgCl2 (mg/ (mg/ Al-Ca precursor with various molar ratio of the chlorides was found to
g) g)
be 3 h. Pseudo-first-order (Eq. (5)) and pseudo-second-order (Eq. (6))
Al-Ca 2:3:0 59.45 0.14 0.82 7.97 0.65 0.81 were examined to investigate the kinetic mechanism of Cr(VI) sorption.
precur-
ln(q e − qt) = lnq e − k1t (5)
sor
Al-Ca-CaCl2 2:3:0.5 41.98 0.16 0.98 6.97 0.49 0.93
2:3:1 46.95 0.23 0.99 9.67 0.46 0.89 t 1 t
= +
Al-Ca- 2:3:0.5 44.88 0.22 0.98 8.65 0.50 0.84 qt k2kq e 2 qe (6)
MgCl2 2:3:1 44.98 0.28 0.99 10.35 0.44 0.94
Where qe (mg/g) and qt (mg/g) are the amounts of Cr(VI) adsorbed per
unit weight of adsorbent at equilibrium and time t, respectively. K1 and
where qm is the maximum adsorption capacity (mg/g); b is free energy K2 are the pseudo-first-order and pseudo-second-order rate constant,
of adsorption (L/mg); n and KF are Freundlich parameters. The respectively. The constants K1 K2, and qe were calculated from the
linearized Langmuir and Freundlich isotherms are shown in Fig. 6. linear plots shown in Fig. 7 and the results were listed in Table 2. The
The isotherm parameters at three different mole ratios were obtained values of correlation coefficients R2=0.99 for pseudo-second-order
and presented in Table 1. Whether CaCl2 or MgCl2 was added, the model were better than those of pseudo-first-order model, indicating
correlation coefficients (R2) for Langmuir model were higher than that that the adsorption process fitted pseudo-second-order kinetic better.
for Freundlich model, indicating the better fitting of Langmuir Adsorption rate-determining step was believed to be a chemical
adsorption model. With the maximum adsorption capacity of sorption, particularly considering the chemical combination of the
59.45 mg/g on Al-Ca precursor without chloride coexistence, decrease adsorbate Cr(VI) into the Ca-Al precursor to form the LDH phase as
in the maximum adsorption was observed with chloride existence. finally the adsorbent.
However the values still remained relatively high in the range around Different from the general reported adsorption researches by
42–47 mg/g. No difference was observed between CaCl2 and MgCl2, adsorbents which are synthesized first and then used to adsorb the
suggesting the similar behaviors within chloride salts. Considering a target pollutants through physical or chemical sorption, the concept
relatively low value of specific surface area of the sample due to the proposed here is to use a precursor and transform the precursor into
heavy agglomeration as confirmed by TEM observation, the main adsorbent by agitation only in a solution with the target pollutant

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L. Zhong et al. Journal of Solid State Chemistry 245 (2017) 200–206

Fig. 7. Adsorption kinetics fitting of pseudo-first/second-order on samples Al-Ca-CaCl2/MgCl2: (a)first with CaCl2; (b) second with CaCl2; (c) first with MgCl2; (d) second with MgCl2;
Conditions: adsorbent dosage 0.08 g/50 ml, T 25 °C, C0=50 mg/l.

Table 2
Comparison between the pseudo-first-order and pseudo-second-order kinetics fitting.

Adsorbent Molar ratio Pseudo-first-order Pseudo-second-order

−1
qe, cal (mg/g) K1 (mg g min 0.5
) R 2
qe, cal (mg/g) K2 (mg g−1 min0.5) R2

Al-Ca precursor 2:3:0 24.71 0.0400 0.79 30.63 0.0030 0.996

Al-Ca-CaCl2 2:3:0.5 32.92 0.0313 0.65 33.30 0.0021 0.994
2:3:1 22.60 0.0404 0.96 31.22 0.0034 0.999
Al-Ca-MgCl2 2:3:0.5 37.35 0.0381 0.86 32.62 0.0021 0.999
2:3:1 35.58 0.0369 0.71 33.49 0.0027 0.990

which is incorporated in situ into the structure of the formed
adsorbent, offering an easy and effective way for the removal of
pollutant Cr(VI). Different from other LDH phases of M-Al (M=Mg,
Zn etc. divalent metal) as adsorbents, Ca-Al hydroxides only will form a
stable phase of katoite, rather than a LDH phase. A third phase such as
carbonate, chloride, or chromate confirmed in this research is required
to transform the katoite phase into a corresponding Ca-Al-X LDH
phase. The stable phase of Ca-Al-CrO4 LDH allowed the preferred
incorporation of Cr(VI) composition even with the coexistence of
chloride anion competition, again a different phenomenon from the
typical physical and chemical sorption beginning on the surface, which
may be easily affected by the coexisting competition ions.
4. Conclusion
It is an effective and reasonable way to use Al-Ca precursor
prepared by mechanical ball milling to increase the removal efficiency
of Cr(VI) because of the much easy incorporation of Cr(VI) into the
structure during the formation of LDH phase. The equilibrium data
fitted well to the Langmuir isotherm model with the maximum
adsorption capacity of 59 mg/g. Sorption kinetics followed pseudo-
second-order kinetic model. The adsorption efficiency of the Al-Ca
precursor slightly decreased and remained as high as 42–47 mg/g with
the coexistence of Ca/Mg chlorides, indicating the preferred incorpora-
tion of adsorbate Cr(VI) into Al-Ca-CrO4 LDH phase to the chloride
anion competition. The prepared sample may contribute to the
treatment of complex wastewater of Cr(VI) with high salinity.
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