Colloids and Surfaces A 537 (2018) 268–280

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Colloids and Surfaces A

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

Recovery of cesium from saline lake brine with potassium cobalt T

hexacyanoferrate-modified chrome-tanned leather scrap adsorbent
⁎
Jiayi Yanga,b, Xuegang Luob, , Tingsong Yana,b, Xiaoyan Linb
a
Department of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang, Sichuan 621010, China
b
Engineering Research Center of Biomass Materials, Ministry of Education, Mianyang, Sichuan 621010, China

G RA P H I C A L AB S T R A C T

Chrome-tanned leather scrap is made up of collagen fibers with substantial eCOOH, eOH and eCONHR. After hydrolysis with NaOH, the amounts of eOH and
eCOOH increase, and they exist in the form of sodium salt. Co2+ replaced Na+ and chelated with eOH, eCOOH and eCONHR. Subsequently, K4Fe(CN)6·3H2O
reacted with Co2+ loaded on AHLS to form KCoFC. During the process of adsorption, Cs+ was exchnged with K+ located in the body center of KCoFC on AHLS.

A R T I C L E I N F O A B S T R A C T

Keywords: Potassium cobalt hexacyanoferrate was modified on alkali-hydrolyzed leather scrap (AHLS/KCoFC) to prepare a
Chrome-tanned leather scrap novel adsorbent for cesium (Cs+) adsorption. AHLS/KCoFC was characterized with SEM, FT-IR, XRD, and XPS to
Potassium cobalt hexacyanoferrate affirm the correct modification. Batch experiments were performed to investigate the adsorption performance of
Adsorption AHLS/KCoFC for Cs+ under various conditions, including pH, initial concentration, contact time and tem-
Cesium
perature. The equilibrium data was fitted well with Langmuir model and the maximum adsorption capacity was
Saline lake
36.75 mg g−1 at pH 6.0, 298.15 K and concentration 100 mg L−1. Thermodynamic and kinetic studies showed
that the adsorption process was spontaneous and endothermic, the pseudo-second-order kinetic model fitted
accurately the data, and the adsorption process was controlled by intraparticle diffusion, but it was not the only
rate-limiting step. Moreover, selective adsorption was investigated systematically. It was found that AHLS/
KCoFC exhibited high selectivity for Cs+ in presence of coexisting ions. At the optimum conditions, AHLS/
KCoFC could be employed to the recovery of Cs+ from saline lake brine, and the adsorption efficiency was
achieved 97.33%, suggesting AHLS/KCoFC is potential application advantage as an efficient adsorbent.

1. Introduction chemical activity and excellent photoelectric property [1–5]. In recent

years, cesium has been playing an important role in the development of
Cesium has been widely applied to electronics, defense industries, efficient energy devices. Studies have showed that the thermal effi-
fiber optical communication system, organic synthesis catalysts and ciency of the magnetic fluid power generation device with cesium
night-vision equipment due to its unique characteristics, such as high compounds as the ionization source is 70%, which is twice as much that

⁎
Corresponding author at: School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China.
E-mail address: 1006277132@qq.com (X. Luo).

http://dx.doi.org/10.1016/j.colsurfa.2017.10.015
Received 20 July 2017; Received in revised form 26 September 2017; Accepted 6 October 2017
Available online 08 October 2017
0927-7757/ © 2017 Elsevier B.V. All rights reserved.
J. Yang et al.
of the traditional thermal power plant. However, a 600 Mw magnetic
fluid power generation device requires annually 3175 t Cs2CO3 [6].
Therefore, the demand for cesium is enormous. To the best of our
knowledge, the distribution of cesium is not concentrated in nature, and
the extractionof cesium from solid ore requires sophisticated techni-
queand the purity is not desirable. In addition, cesium resources in
oreshave been reduced over time due to unreasonable exploitation.
Thus, the research on the extraction of cesium from other resources,
such as oilfield, seawater and saline lake brine, is attracting more and
more attention [7–9]. In fact, there are many saline lakes in China, and
surveys found that the concentration of cesium in the saline lake were
about several times or hundreds as much that of any other sources [10].
It is predictable that saline lake brine will become the main source of
cesium resources in the future. However, the uptake of cesium from
saline lake brine has been facing a big challenge for a long time because
cesium coexists with substantial alkali and alkaline earth metal (so-
dium, potassium, lithium, rubidium, calcium and magnesium) in salt
lake brine [11].
Some available methods of cesium extraction from saline lake brine,
including solvent extraction [12,13], precipitation [14,15] and ad-
sorption [7,16–20], have been employed. Among them, adsorption is
preeminent as an efficient, convenient and cleanseparation method.
However, the excellent selectivity of adsorbent is critical. Inorganic
exchanger based on potassium metal hexacyanoferrate has been re-
ported to be selective adsorbent for cesium adsorption and has gained
an increasing attention of researchers [21]. Potassium metal hex-
acyanoferrate has a structural formula of KxMy[Fe(CN)6], where M re-
presents divalent transition metal (Fe, Ni, Cu, Zn and Co) Potassium
metal hexacyanoferratehas a face-centered cubic structure, the Fe (II) is
surrounded by cyanide groups to form octahedra and transition metal
ion is located at the corner of the cube, and the exchangeable K+ oc-
cupies the cube center in order to balance the negative charge of the
crystal structure [22]. Numerous studies have shown that the order of
adsorption selectivity is Co > Ni > Cu > > Zn > > > Fe, and
adsorption capacity of potassium metal hexacyanoferrate is in the order
of Cu > Ni > Zn > Co > > Fe [23–25]. Thus, in the terms of the
adsorption selectivity and adsorption capacity, potassium cobalt hex-
acyanoferrate (KCoFC) was preferentially considered as an adsorbent
for cesium adsorption from the complex saline lake environment.
However, the major drawback of KCoFC is nano-size, which is not
conducive to the separation of adsorbent from the solid-liquid system.
Furthermore, its application in fixed-bed columns is limited due to the
low permeability, column blockage, and head pressure loss. In view of
its undesirable properties, it appeared that KCoFC was immobilized on
suitable materials, such as silica, zeolite, polymer and biopolymer
[26–30]. Among them, the biopolymer by virtue of its cheapness, less
pollution, and regeneration is used as a support of powder adsorbent.
Leather industry has created significant benefits for the national
economy in several developing countries, but its enormous solid waste
byproduct has produced a serious environmental problem [31]. Ac-
cording to statistics [32], the equivalent of approximately 10% of the
quality of the raw hide is discarded in environment as solid waste such
as shavings and trimmings, constituting disposal problems and en-
vironmental nuisance. In addition, chromium (III) is usually used as
tanner agent to produce wet blue leather [33]. It is possible that
chromium (III) in leather shavings is oxidized to mutagenic chromium
(IV) in a complex natural environment [34,35]. To solve the pollution
problem, it is an interesting idea that to use solid wastes from leather
industry as an effective adsorbent to remove the hazardous substance
from the environment. For instance, Oliveira and Onenc [36,32] used
chromium-containing solid waste as adsorbent to remove organic con-
taminants, Cr (VI) and phenol from aqueous solution. Beyond that,
leather, as a natural polymer, is comprise of collagen fibers with three-
dimensional helical structure, which supplies many functional groups
(eOH, eCOOH and eCONHR) that can chelate with cobalt ions in the
raw material for the synthesis of KCoFC [37]. Thus, it is possible for
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Colloids and Surfaces A 537 (2018) 268–280
leather to act as a support of KCoFC.
In this study, potassium cobalt hexacyanoferrate-modified chrome-
tanned leather scrap adsorbent (AHLS/KCoFC) was prepared by two
steps. The adsorbent was characterized by SEM, XRD, XPS and FT-IR.
Adsorption properties of the adsorbent for Cs+ were investigated under
various experimental conditions, such as pH, temperature, contact time
and initial concentration of Cs+. Moreover, in order to discuss the
adsorption mechanism, the equilibrium capacity, kinetics, competitive
adsorption experiments with co-existing ions were investigated.
Remarkably, the adsorbent was used to recover Cs+ from the brine of
Qarham playa to evaluate its potential application.
2. Materials and methods
2.1. Materials and reagents
Chrome-tanned leather scrap was collected from the National
Engineering Laboratory for Clean Technology of Leather Manufacture
of Sichuan University, China. Cobalt nitrate hexahydrate (Co
(NO3)2·6H2O), potassium ferrocyanide trihydrate (K4Fe(C)6·3H2O),
CsCl, NaOH, HCl, KCl and other reagents were purchased from Chengdu
Kelong Chemical Reagent Co., Ltd., China. 1 mg mL−1 cesium stock
solution was from National Center for Analysis and Testing of
Nonferrous Metals and Electronic Materials. All the reagents used for
the study were of analytical grade without further purification.
2.2. Prepraration of adsorbent
2.2.1. Preparation of AHLS
Chrome-tanned leather scrap was cut into 0.2 × 0.2 cm2 particles.
These particles were soaked with deionized water for 12 h and further
dried in air at 50 °C, and the granular leather scrap was obtained (GLS).
As described by Yan [38], alkali-hydrolyzed leather scrap (AHLS) was
prepared by adding 1 g GLS into 150 mL conical flask containing
100 mL of 0.05 mol L−1 NaOH solution to hydrolyze for 4 h at 60 °C.
Then, the AHLS was washed with deionized water to neutral and freeze-
dried for 24 h in vacuum.
2.2.2. Preparation of AHLS/KCoFC
The KCoFC was modified on AHLS by two steps. The processes as
follow: a weighed amount of Co(NO3)2·6H2O (0.1–5 g) was completely
dissolved in 50 mL deionized water to form a homogeneous solution,
and 0.5 g AHLS was added with continuous stirring for 24 h at 25 °C.
After that, the prepared mixture was filtered and residue was washed
repeatedly with deionized water for removal excess reactant. The
sample was freeze-dried for 24 h in vacuum to receive the AHLS
modified with Co2+ (AHLS-Co).
0.5 g AHLS-Co was suspended in 50 mL solution containing required
amounts of K4Fe(CN)6·3H2O (1–5 g), and the obtained suspension was
shaken for 24 h at 25 °C. Whereafter, the suspension was filtrated and
washed repeatedly with deionized water to remove excessive K4Fe
(CN)6 and adjust pH to neutral. After freeze-drying, the adsorbent,
AHLS modified with KCoFC (AHLS/KCoFC), was obtained.
2.3. Characterization
The surface morphology images and elemental of samples were
obtained by scanning electron microscopy coupled with energy dis-
persive X-rayanalysis (SEM-EDX, Ultra 55, Carl Zeiss, Germany). To
clarify the structure of samples, the fourier transform infrared spec-
troscopic analysis (FT-IR, Nicolet-5700, PerkinElmer, USA) was per-
formed with KBr tablet method in frequency range of 400–4000 cm−1.
Moreover, X-ray diffraction (XRD) data of samples were collected using
a X’Pert-Pro powder X-ray diffractometer with Cu Kα radiation. Further,
X-ray photoelectron spectroscopy (XPS, ESCALAB250, Thermo Fisher
Corportation, USA) was employed to obtain the elements binding
J. Yang et al.
energies of the adsorbent. The thermogravimetric curve was recorded
(TG, Q500, TA Corporation, USA) at a heating rate of 10 °C min−1
varying from 25 °C to 600 °C with high-purity nitrogen carrier gas.
2.4. Batch adsorption experiments of Cs+ onAHLS/KCoFC
0.05 g AHLS/KCoFC was immerged in 50 mL of Cs+ solution to
investigate the influence of different factors on Cs+ adsorption on
AHLS/KCoFC, including pH, initial concentration, temperature, and
contact time. The pH values of Cs+ solution ranging from 2 to 13 were
adjusted by 0.1 mol L−1 HCl and 0.1 mol L−1 NaOH. In order to discuss
the effects of concentration and temperature on adsorption capacity,
the recovery of Cs+ by AHLS/KCoFC with initial concentrations varying
from 10 mg L−1 to 140 mg L−1 was investigated at temperature range
of 288.15–328.15 K 140 mg L−1 Cs+ solution was used at a preset time
to study the effect of contact time on adsorption capacity. On account of
the studies above, adsorption kinetic and adsorption equilibrium iso-
therm were performed. After adsorption, the residual concentration of
Cs+ in solution was determined with an atomic absorption spectro-
photometer (AAS, Hitachi Z-2300, Japan). All experiments were im-
plemented in triplicate, and the average values were recorded for
analysis to ensure that the error value of parallel experiment was
within ± 3%. The adsorption capacity (qe) and adsorption efficiency (R
%) for Cs+ at equilibrium were calculated by using the following
equations [39,40]:
(C0 − Ce ) V
qe =
m (1)
(C0 − Ce ) × 100%
R% =
C0 (2)
−1 −1
where C0 (mg L ) and Ce (mg L ) are the initial and equilibrium
concentration of Cs+, respectively, V (mL) is the volume of the solution
and m (g) is the mass of adsorbent.
2.5. Cs+ adsorption from saline lake brine
Saline lake brine contains substantial alkali and alkaline earth me-
tals that interfere with Cs+ adsorption, whose concentrations are about
hundreds or even hundreds of thousands times that of Cs+ [10]. In
order to investigate that AHLS/KCoFC has high adsorption efficiency
for Cs+ at low concentration, 0.05 g AHLS/KCoFC was contacted with
50 mL of low concentration solution ranging from 0.1 to 10 mg L−1 for
24 h. After adsorption, the adsorption efficiency of Cs+was calculated
by Eq. (2). Furthermore, 0.05 g AHLS/KCoFC was employed to recover
Cs+ from brine of Qarham playa at optimum pH.
3. Results and discussion
3.1. Characterization
3.1.1. Chemical composition analysis
The chemical formula of KCoFC loaded on AHLSwas determined by
the method of Nilchi [41], 0.05 g AHLS/KCoFC was dispersed in 1 mL
concentrated sulfuric acid (H2SO4), and the mixture was heated at
150 °C for 8 h. Subsequently, 50 mL of 0.02 mol L−1 H2SO4 was added
to resiude, and filtered through a sand core funnel with 0.45 millipore
filter. Then, the concentrations of K+, Fe2+ and Co2+ in solution were
quantified with AAS. The same experiment was conducted in triplicate,
and the average value was used to determine the chemical formula of
KCoFC. The results of chemical analysis is showed in Table 1. The
maximum loading of KCoFC was 128 mg-KCoFC/g-AHLS when the
mass ratio of Co(NO3)2·6H2O to K4Fe(CN)6·3H2O was 3:4. Theoretically,
the ideal chemical formula of KCoFC follows a stoichiometric compo-
sition of K2CoFC. However, on the basis of previous studies, KCoFC with
nonstoichiometric composition was obtained typically, which it can be
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Colloids and Surfaces A 537 (2018) 268–280
ascribed that it is impossible to obtain KCoFC with absolutely ideal
chemical formula due to non-single-phase reaction environment
[26,42]. In the present study, the chemical formula of KCoFC loaded on
AHLS was characterized by nonstoichiometric composition. The result
is consistent with previous study of Mardan A [26]. Furthermore, the
adsorption capacity of Cs+ on AHLS/KCoFC was affected by the loading
and chemical formula of KCoFC. The results showed that the maximum
adsorption capacity of Cs+ by AHLS/KCoFC could be reached, when the
mass ratio of Co(NO3)2·6H2O to K4Fe(CN)6·3H2O was 3:4.
3.1.2. SEM analysis
The SEM images were taken to observe the surface morphologies of
the materials, including GLS, AHLS/KCoFC before and after Cs+ ad-
sorption. The surface of GLS is rough, and substantial collage fibers are
tightly interwined (Fig. 1a). After modification, numerous cavities can
be observed distinctly on the surface of AHLS/KCoFC, which increase
surface area of AHLS/KCoFC and is propitious to the transfer of Cs+ on
surface and inside of AHLS/KCoFC (Fig. 1b). To verify that KCoFC was
successfully modified on leather scrap, a higher magnification image
appears in Fig. 1. As shown in Fig. 1d, a large number of KCoFC par-
ticles can be observed. In order to confirm that these particles are
KCoFC, EDX analysis was carried out. As shown in Fig. 1e, the corre-
sponding EDX pattern of AHLS/KCoFC clearly demonstrated the ex-
istence of each elemental of C, N, K, Fe, and Co. Furthermore, the
atomic ratio of Co/Fe was 1.86, which was consistent with chemical
composition of KCoFC, giving further proof that the particles coated by
collagen on the leather scrap are KCoFC. In addition, the surface mor-
phology of AHLS/KCoFC has no obvious change after Cs+ adsorption,
and is still porous, suggesting the structure of AHLS/KCoFC is stable
(Fig. 1c).
3.1.3. FT-IR analysis
The FT-IR spectra of samples are shown in Fig. 2, including GLS (a),
AHLS/KCoFC (b) and KCoFC (c). The spectrum of GLS (a) represents the
typical infrared information of collagen fiber, which is characterized by
amide bands. The characteristic peak around 3412.3 cm−1 corresponds
to stretching vibration of eOH and eNH of collagen fibers [43]. The
speak is observed at 1641.83 cm−1, which is assigned to C]O
stretching vibration of eCONHR and shear vibration of eNH2. The
speak at 1546.96 cm−1 can be imputed bending vibration of NeH, and
the peak located at 1238.94 cm−1 is ascribed to N—H bending vibra-
tion and CeN stretching vibration [44–46]. As shown in the spectrum
of AHLS/KCoFC (b), in comparison with GLS (a), the characteristic
peaks of amide band was bule-shifted, which moved to 3440.09,
1654.81, 1554.98 and 1252.32 cm−1, respectively. It was causedby
hydrolysis with NaOH and complexation between Co2+ and functional
groups (eNH2, eCOOH, eOH, eCONHR) [7,47]. For the spectrum of
KCoFC (c), the peaks appear at 2081.7 cm−1 and 593.9 cm−1, which
correspond to stretching vibration peak of eCN and FeeCNeCo
[48,49], respectively. Simultaneously, these characteristic peaks could
be observed in the spectrum of AHLS/KCoFC (b). Accordingly, the re-
sults confirmed that the KCoFC has been successfully loaded on leather
scrap.
3.1.4. XPS analysis
In order to explain the mechanisms of AHLS/KCoFC preparation and
adsorption for Cs+, theXPS analyses of AHLS, AHLS-Co, AHLS/KCoFC
before and after Cs+ adsorption were manipulated (Fig. 3). For the
survey spectrumof AHLS (Fig. 3a), the peaks of C 1s, O 1s,N 1 s and Cr
2p can be observed [50]. Among them, the peaks of N 1s at 399.67 eV,
O 1s at 531.09 eV and 532.08 eV are derived from the nitrogen of
CeNH2, oxygen of C]O and CeO [51,52], which are shown in Fig. 3d
and b, respectively. After AHLS was modified with Co2+, a new peak of
Co 2p appears in the spectrum of AHLS-Co (Fig. 3a), and the signal of
double Co 2p, Co 2p1/2 (798.31 eV) and Co 2p3/2 (782.59 eV), can be
observedin Fig. 3e. Moreover, the peaks of N 1 s and O 1 s slightly
J. Yang et al. Colloids and Surfaces A 537 (2018) 268–280

Table 1
Chemical composition of KCoFC.

Sample Preparation conditions Analysis Empirical formula Experimental loading of KCoFC/mg g−1 Adsorption capacity of Cs+/mg g−1

a1/g b2/g K/% Co/% Fe/%

1 0.1 1 1.079 0.867 0.785 K1.96Co1.05Fe(CN)6 50 6.888

2 0.5 2 1.093 1.262 0.675 K2.32Co1.78Fe(CN)6 34 7.010
3 1 3 1.096 1.278 0.994 K1.58Co1.22Fe(CN)6 44 7.030
4 3 4 2.632 3.469 1.753 K2.14Co1.88Fe(CN)6 128 16.793
5 5 5 2.598 3.349 1.615 K2.30Co1.97Fe(CN)6 120 16.628

1
The mass of Co(NO3)2·6H2O.
2
The mass of K4Fe(CN)6·3H2O.

Fig. 1. SEM images of GLS (a), AHLS/KCoFC (b), AHLS/KCoFC after Cs+ adsorption (c), higher magnification of AHLS/KCoFC (d), and EDX spectra of AHLS/KCoFC (e).

altered to 399.96 eV, 531.32 eV and 532.28 eV due to the complexation

between Co2+ and nitrogen atom of CeNH2, oxygen atom of C]O and
CeO (Fig. 3d and c). It could be explained that the coordination reac-
tion results in the decrease of the electron density around the oxygen
and nitrogen atom, which contrarily increases binding energy of N 1s
and O 1s [53]. The survey spectrum of AHLS/KCoFC in Fig. 3 aindicates
the new elements K and Fe present after AHLS-Co reacted with K4Fe
(CN)6·3H2O. All results illustrated exactly that KCoFC has been ideally
synthesized on leather scrap in the form of coordination bond. Besides,
the survey spectrum of AHLS/KCoFC-Cs in Fig. 3a appears the peak of
Cs 3d after Cs+ adsorption, which could be concluded that Cs+ was
adsorbed effectively by AHLS/KCoFC.

3.1.5. XRD analysis

As shown in Fig. 4, the diffraction peaks at
17.76°,24.87°,35.78°,40.65° and 43.62° are observed in the XRD pattern
of AHLS/KCoFC and KCoFC, and KCoFC was synthetized according to
the literature [48], confirming AHLS/KCoFC and KCoFC have the same
crystal structure. The result is consistent with previous studies [49,54],
Fig. 2. FT-IR spectra of GLS (a), AHLS/KCoFC (b) and KCoFC (c).
and all diffraction peaks can be indexed to pure phase KCoFC (JCPDS
31-1000), validating ulteriorly that KCoFC was loaded on leather scrap,
whose structure did not change compared with the pure phase KCoFC.

271
J. Yang et al.
Fig. 3. The XPS survey of (a) AHLSL, AHLS-Co, AHLS/KCoFC before and after Cs+ adsorption; high resolution sans XPS spectra of (b) and (c) O 1s; (d) N 1 s of AHLS before and after
loading Co2+; (e) Co 2p.
3.1.6. Thermal analysis
The TGA and DTG curves of AHLS/KCoFC are shown in Fig. 5. Two
weight loss steps were obtained at temperature rang of 0–600 °C. It can
be observed from DTG curve that the first one extends from ambient to
225 °C, which is maximised at approximately 150 °C, and it is attributed
to the evaporation of physical water and chemical water originating
from the dehydration of substantial carboxyl and hydroxyl in leather
scrap. The weight loss at this stage is 7.28%. The second one occurs at
temperature between 225 °C and 600 °C, which is accompanied by a
weight loss of 50.04%, and the maximum weight loss was achieved at
272
Colloids and Surfaces A 537 (2018) 268–280
336 °C. During this process, the weight loss derives from the decom-
position of aliphatic and protein compounds in leather scrap, as well as
the decomposition of KCoFC loaded on leather scrap.
3.2. Adsorption properties of AHLS/KCoFC
3.2.1. Effect of pH on adsorption of Cs+ by AHLS/KCoFC
pH value is one of the most important parameters affecting the
adsorption capacity. Thus, the influence of pH on Cs+ adsorption was
discussed at pH rang of 2–13, and the result was represented in Fig. 6.
J. Yang et al.
Fig. 4. XRD peaks of KCoFC powder and AHLS/KCoFC.
Fig. 5. TGA and DTA curvesof AHLS/KCoFC.
Fig. 6. Effect of pH on adsorption of Cs+.
The adsorption capacity of Cs+ on AHLS/KCoFC increases quickly with
the increasing of pH value from 2 to 6, which is attributed to the in-
fluence of the proton-rich (H+) environment at low pH, resulting in the
competition between H+ and Cs+ for adsorption sites and low ad-
sorption capacity [55]. With the increase of pH value, the increase in
the concentration of OH− causes that AHLS/KCoFC carries negative
charge, which is in favor of electrostatic attraction between Cs+ and
AHLS/KCoFC [56]. Whereafter, the adsorption capacity of Cs+ fluc-
tuates slightly when pH is in range of 7–13, and the maximum
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Colloids and Surfaces A 537 (2018) 268–280
Fig. 7. Effect of initial Cs+ concentration on adsorption of Cs+.
adsorption capacity of Cs+ is obtained at pH 6 as shown in Fig. 6. It can
be inferred from the above results that AHLS/KCoFC can be applied in a
wide pH environment and all subsequent experiments were performed
at pH 6.
3.2.2. Effect of initial concentration on adsorption of Cs+
The effect of initial Cs+ concentration on adsorption capacity of
Cs ranging from 10 mg L−1 to 140 mg L−1 at 288.15 K and pH 6 is
+
described in Fig. 7. The adsorption capacity increases sharply with the
increase of the initial Cs+ concentration and the adsorption equilibrium
was achieved at 100 mg L−1, and the maximum adsorption capacity is
36.75 mg g−1. Relevant interpretation is drawn that the larger con-
centration difference of Cs+ exists between adsorbent surface and bulk
solution at higher initial Cs+ concentration, which increases the driving
force of mass transfer and is conducive to the adsorption of Cs+ [57].
However, the adsorption capacity tends to be saturated when less ad-
sorption sites are available at higher concentration.
3.2.3. Efffect of temperatue on adsorption of Cs+
Fig. 8 shows the effect of temperature on adsorption of Cs+ with
different initial Cs+ concentration ranging from 10 to 140 mg L−1. As
shown in Fig. 8, adsorption capacity increases slightly with the increase
of temperature. Moreover, the adsorption capacity increased greatly
under high concentration, compared with low concentration. The
maximum adsorption capacity was 36.85 mg g−1 at 328.15 K. The re-
sults illustrated that the adsorption process has an endothermic
Fig. 8. Effect of temperature on adsorption of Cs+ with different initial concentration.
J. Yang et al.
property and it is favorable for the adsorption of Cs+ to increase tem-
perature [58]. However, in terms of energy conservation, the sub-
sequent experiments were conducted at 298.15 K.
3.2.4. Isotherm model
In oreder to elucidate isothermal adsorption behaviors, the
Langmuir and Freundlich isotherm models were employed in this study
for analyzing data. The Langmuir isotherm model assumes that the
adsorbent with homogeneous surface can only adsorb one layer of
molecules, and the molecules are essentially non-interacting. The
Freundlich isotherm equation is only an empirical formula based on a
large number of similar experimental results. The linear and non-linear
form of the Langmuir isotherm equations can be written as Eqs. (3) and
(4), respectively [59]:
Ce 1 C
Linear: = + e
qe K L qm qm (3)
KL qm Ce
Nonlinear: qe =
1 + KL Ce (4)
−1
where Ce (mg L ) is the equilibrium concentration, qe is the adsorp-
tion capacity at equilibrium, qm (mg g−1) is the maximum adsorption
capacity, KL (L mg−1) is Langmuir constant related to energy of ad-
sorption.
The Freundlich isotherm equation is only an empirical formula
based on a large number of similar experimental results. Its linear and
non-linear forms of the Freundlich isotherm equations were given by
Eqs. (5) and (6), respectively [59]:
1 sive available adsorption sites on the surface of AHLS/KCoFC at the
Linear: ln qe = ln KF + ln Ce
n (5)
Nonlinear: qe = KF Ce1/ n (6)
where n is the heterogeneity parameter of the adsorbent surface, and KF
(mg g−1)(L mg−1)1/n is the Freundlich isotherm parameter.
The Langmuir and Freundlich equations were used to fit the ex-
perimental data, and the regression lines obtained are shown in Fig. 9.
The values of parameters (KL, qm, KF, and n) are listed in Table 2. From
Table 2, the values of the correlation coefficient (R2) for the linear
Langmuir model are 0.994, 0.995, 0.996, 0.998 and 0.998 at tem-
perature range used in this study, which are higher than non-linear
Langmuir and Freundlich model. Hence, the linear Langmuir model can
be better used to describe experimental data, indicating the adsorption
process of Cs+ on AHLS/KCoFC is monolayer adsorption and the
sorption sites are homogeneous on adsorbent surfaces [60]. Further-
more, the fitting maximum adsorption capacities (qm) are 36.941,
37.147, 37.327, 36.792 and 37.258 mg g−1 when the temperature
rangs from 288.15 K to 328.15 K.
Further, on basis of Eq. (7), the dimensionless separation factor RL
defined by Hall et al. was calculated by using the Langmuir parameter
KL, which represents the affinity between the adsorbent and the ad-
sorbate [51].
1 slope and intercept of linear regression, respectively.
RL =
1 + KL C0 (7)
The value of RL represents four possible adsorptions like favorable
(0 > RL < 1), linear (RL = 1), unfavorable (RL > 1), and irrever-
sible (RL = 0). The value of RL (0.011-0.285) for adsorption of Cs+ on
AHLS/KCoFC is 0 < RL < 1, suggesting that the adsorption of Cs+ on
AHLS/KCoFC is favorable.
3.2.5. Thermodynamics
The thermodynamic parameters were calculated to explore ther-
modynamic feasibility and spontaneity of the adsorption process by the
following equations [61]:
ΔG 0 = −RT ln K 0 (8)
274
Colloids and Surfaces A 537 (2018) 268–280
ΔS 0 ΔH 0
ln K 0 = −
R RT (9)
where the value of K0, thermodynamic equilibrium constant, was cal-
culated by formula K0 = qm × KL (qm and KL derive from the Langmuir
isotherm model), R (8.314 J mol−1 K−1) is the ideal gas constant and T
is the temperature (K). ΔG0 (KJ mol−1), ΔH0 (kJ mol−1) and ΔS0
(J mol−1 K−1) are the Gibbs free energy change, enthalpy change and
entropy change in adsorption process, respectively. The values of ΔH0
and ΔS0 were calculated by the slope and intercept of the linear plot of
lnK0 versus 1/T that is shown in Fig. 10.
As presented in Table 3, the values of ΔG0 were negative within the
range of temperatures investigated, elaborating that the adsorption
process of Cs+ on AHLS/KCoFC is spontaneous. In addition, the values
of ΔH0 and ΔS0 were positive, indicating that the sorption process is
endothermic and increasing temperature is favorable for the adsorption
of Cs+ and the disorder increases at solid-liquid interface during ad-
sorption process. However, excessive temperature can enhances the
molecular movement, which results in cesium is not easily adsorbed
and the affinity between the adsorbent and cesium decreased, which
corresponds to the result that the lower KL value at 328.15 K than at
318.15 K [62,63].
3.2.6. Effect of contact time on adsorption of Cs+ and adsorptionkinetics
Fig. 11 shows the effect of contact time on the adsorption capacity
of Cs+. The result displayed that adsorption capacity increases rapidly
with the increasing of contact time from 0 to 60 min and adsorption
equilibrium reaches at 180 min. It can be deduced that there are mas-
beginning of adsorption. Over time, adsorption sites are completely
occupied, and Cs+ enters into the inner of adsorbent to attack the active
sites, which causes adsorption rate decreases correspondingly. Finally,
adsorption equilibrium was achieved.
In order to figure out adsorption mechanism of Cs+ adsorption on
AHLS/KCoFC, the pseudo-first-order and pseudo-second-order models
were employed to analyze the experimental data. The pseudo-first-
order and pseudo-second-order equations are described as follows, re-
spectively [64].
Pseudo-first-order: ln(qe − qt) = lnqe − k1t (linear) (10)
−k1
qt = qe(1 − e t) (non-linear) (11)
t 1 t
Pseudo-second-order: = + (linear)
qt k2 qe2 qe (12)
k2 tqe2
qt = (non-linear)
1 + k2 qe t (13)
−1 +
where qe and qt (mg g ) are adsorption capacity of Cs at equilibrium
and specific reaction time t, respectively, and k1 (min−1) and k2
(g mg−1 min−1) are the pseudo-first-order constant and pseudo-second-
order rate constant. The values of k1, k2 and qe can be calculated by the
The linear and non-linear fittings of pseudo-first-order and pseudo-
second-order models and values of the correlation coefficient (R2) are
shown in Fig. 12 and in Table 4. Apparently, for the linear form of
pseudo-second-order model,the values of R2 is 0.999, which is higher
than pseudo-first-order model and non-linear pseudo-second-order
model, indicating that the adsorption process agreed well with linear
pseudo-second-order kinetics model. Furthermore, the theoretical value
of qe (38.241 mg g−1) in linear pseudo-second-order kinetics model is
in better agreement with experimental result (37.613 mg g−1). There-
fore, the kinetics data is better described by the linear pseudo-second-
order model, which suggests that the adsorption process of Cs+on
AHLS/KCoFC is mainly dominated by chemical adsorption involving
sharing or exchange of electrons [65].
J. Yang et al. Colloids and Surfaces A 537 (2018) 268–280

Fig. 9. (a), (c) the linear and non-linear fitting of Langmuir models of Cs+; (b), (d) the linear and non-linear fitting of Freundlich models of Cs+.

Table 2
The linear and non-linear of Langmuir and Freundlich models.

Type T/K Langmuir Freundlich

2
qm/(mg/g) KL/(L/ R n KF/(mg/g) R2
mg) (L/mg)1/n

linear 288.15 36.941 0.269 0.994 3.905 11.827 0.877

298.15 37.147 0.394 0.995 4.515 14.012 0.817
308.15 37.327 0.469 0.996 5.009 15.525 0.828
318.15 36.792 0.677 0.998 5.258 16.339 0.889
328.15 37.258 0.616 0.998 5.365 16.637 0.988
Non-linear 288.15 34.768 0.533 0.940 4.420 13.136 0.934
298.15 35.144 1.006 0.921 5.087 15.311 0.906
308.15 35.190 1.679 0.935 5.612 16.720 0.916
318.15 35.151 2.172 0.973 6.009 17.631 0.939
328.15 35.829 1.013 0.857 5.812 17.395 0.982

3.2.7. Diffusion study

The adsorption of Cs+ on AHLS/KCoFC can be considered as a li- Fig. 10. Plot of lnK0 versus 1/T for the adsorption of Cs+ on AHLS/KCoFC.
quid-solid phase reaction, including film diffusion, intraparticle diffu-
sion, and interface reaction. Among them, the interface reactioncan be
qt = kip t 1/2 + C (14)
completed quickly, which is negligible in kinetics study. Therefore, the
study of diffusion mainly involves liquid film diffusion and intraparticle
where qt (mg·g−1) is the adsorption capacity at time t (min), kip
diffusion, one or both of which could control the adsorption rate.
(mg g−1 min−1/2) is intraparticle diffusion rate constant and C is a
Supposing that intraparticle diffusion controls the rate of adsorption
constant associated with the layer thickness and the boundary layer.
process, Weber-Morris intrapartical diffusion model was employed for
Weber-Morris model holds that the adsorption rate is controlled
investigation. The expression is written as given [66]:
mainly by intraparticle diffusion when the plot of qt versus t1/2 would

275
J. Yang et al. Colloids and Surfaces A 537 (2018) 268–280

Table 3
Thermodynamics parameters for adsorption of Cs+ on AHLS/KCoFC.

T/K ΔG0/KJ mol−1 ΔH0/KJ mol−1 ΔS0/J mol−1 K−1

288.15 −5.501 17.520 80.573

298.15 −6.652
308.15 −7.333
318.15 −8.505
328.15 −8.549

Fig. 13. Intraparticle diffusion kinetics of Cs+ on AHLS/KCoFC.

be negligible [68,69]. The initial portion can be ascribed to external

Fig. 11. Effect of contact time on adsorption of Cs+.
surface adsorption that Cs+ diffused from the liquid film boundary
layer to the surface of AHLS/KCoFC. The second portion can be im-
puted intraparticle diffusion that Cs+ on the surface of AHLS/KCoFC
entered the channels of KCoFC on AHLS. By linear fitting, the values of
kip for the two steps above were obtained, which are 3.819 and
0.783 mg g−1 min−1/2, respectively, indicating that the rate of the li-
quid film diffusion process is faster than that of intraparticle diffusion.
The third portion can be attributed to the exchange between Cs+ and
K+ located in the body center of the cubic caged KCoFC, which can
often be negligible because it can be completed in a fairly short period
of time. The results suggested that adsorption process was controlled by
intraparticle diffusion, but it was not the only rate-limiting step.

3.2.8. Adsorption selectivity

For extracting Cs+ from complex saline lake brine, the high se-
lectivity of adsorbent is critical. In this study, the selectivity of AHLS/
KCoFC for Cs+ was investigated at pH 6 by the adsorption of Cs+ from
a mixed solutionin presence of coexisting ions including Na+, K+, Li+,
Mg2+, Ca2+ and Cs+, and individual initial concentrations were
20 mg L−1. After adsorption, the concentrations of Na+, K+, Li+,
Mg2+, Ca2+ and Cs+in the solution were quantified by AAS. Then, the
adsorption capacities of coexisting ions on AHLS/KCoFC were obtained,
and the selectivity separation coefficien (αM Cs
) of Cs+ with respect to
other ions was calculated using Eq. (15) [70].

Cs qCs CM
αM =
qM CCs (15)
Fig. 12. (a) (c) the linear and non-linear fitting of pseudo-first-order kinetic models of
Cs+;(b), (d) the linear and non-linear fitting of pseudo-secondorder kinetic models of where qCs and qM (mg g−1) are the adsorption capacity of Cs+ and
Cs+. coexisting ions, respectively. CCs and CM (mg L−1) represent the equi-
librium concentration of Cs+ and other ions, repectively.
As shown in Fig. 14, the adsorption capacity of Cs+ on AHLS/KCoFC
be a straight line through the origin [67]. Fig. 13 shows the linear re-
is much higher than other ions. Futhermore, the αM Cs
for Cs+ with re-
gression line is separated into a few regions and does not pass through + + + 2+ 2+
spect tothe Na , K , Li , Mg and Ca were 300.96, 69.35, 320.60,
the origin, indicating that two or more steps occurred in the adsorption
84.76and 117.18, respectively, and followed the descending order of
process and the effect of liquid film diffusion on adsorption rate can not
Li+ > Na+ > Ca2+ > Mg2+ > K+. The result can probably be

Table 4
Parameters of linear and non-linear pseudo-first-order kinetics and pseudo-second-order kinetics.

Type qe(exp)/(mg g−1) Pseudo-first-order model Pseudo-second-order model

qe/mg g−1 k1/min−1 R2 qe/mg g−1 k2/g mg−1 min−1 R2

Linear 37.613 61.687 0.033 0.921 38.241 1.343E-03 0.999

Non-liner 37.760 0.023 0.986 39.957 8.643E-04 0.937

276
J. Yang et al.
Fig. 14. Selective adsorption capacities of coexisting ions by AHLS/KCoFC.
explained by structural factors. The size of the KCoFC cavity within the
lattice is 1.47 Å, and the unhydrated radii of Na+, Li+, Mg2+ and
Ca2+are 0.95, 0.60, 0.66 and 0.99 Å, respectively, which are smaller
than the size of the KCoFC cavity [18,71]. Although these ions easily
enter the cavity of KCoFC, it is difficult for them to exchange with K+ in
the lattice as their unhydrated radiiare smaller than that of K+ (1.33 Å).
Theoretically, the presence of Na+, Li+, Mg2+ and Ca2+ hardly affects
the adsorption of Cs+, but the experimental results showed that AHLS/
KCoFC had higher adsorption capacity for Mg2+ and Ca2+ than Na+,
Li+. It can be imputed that AHLS as a support of KCoFC contains
functional groups (eCOOH, eOH, eCONHR) that chelated with Mg2+
and Ca2+, but the complexation did not affect the adsorption of Cs+
because Mg2+ and Ca2+ did not occupy adsorption sites of Cs+.
However, it is likely that Cs+ and K+ enter the channels of KCoFC and
Cs+ and K+ are exchanged with structural K+located in the body
center of KCoFC because of the similar size to the cavity of KCoFC,
which leads K+ to interfere seriously with the adsorption of Cs+. In
fact, resorcinol formaldehyde polycondensate resin can be used to re-
move K+ before adsorption, which is a well-established technology
[65]. The results suggested the AHLS/KCoFC exhibited high selectivity
for Cs+.
3.3. Adsorption of trace cesium from saline lake brine
+ +
At low concentration of Cs , high adsorption efficiency of Cs by
AHLS/KCoFC was revealed in Fig. 15a. The lower concentration, the
higher adsorption efficiency, confirming AHLS/KCoFC can be a pro-
mising adsorbent for adsorption of low concentration Cs+ in saline
Fig. 15. (a) Effect of low concentration on Cs+ adsorption, (b) Cs+ adsorption from saline lake brine.
277
Colloids and Surfaces A 537 (2018) 268–280
lake.
The concentrations of Mg2+, Na+, K+, Li+, Ca2+ and Cs+ in saline
lake brine were determined to be 45.99 g L−1, 42.41 g L−1,
839.50 mg L−1,7.37 mg L−1, 16.53 mg L−1 and 73.90 μg L−1. For the
studyof selectivity, it was found that large amounts of Mg2+ and Ca2+
can be adsorbed by AHLS, which increases the difficulty of purification.
Thus, based on the study of adsorption selectivity, saline lake brine
samples were treated with NaOH before adsorption to remove Mg2+
and Ca2+. The result is shown in Fig. 15b. The adsorption efficiency of
Cs+ by AHLS/KCoFC achieved 72.37%. pH was found to be a critical
parameter for Cs+ adsorption on AHLS/KCoFC. The Ph value of brine of
Qarham playa is 6.6, while the optimum pH of adsorption is 6.0. Ac-
cordingly, the value pH of sample was adjusted to 6.0, which resulted in
an increase in adsorption efficiency to 97.33%. The results above in-
dicated that although the concentrations of other coexisting ions are
nearly saturation, the adsorption efficiency of Cs+ by AHLS/KCoFC is
fairly high, illustrating AHLS/KCoFC can be an efficient adsorbent for
the adsorption of Cs+ from saline lake.
3.4. Mechanism analysis
On the basis of characterization results, thermodynamic and kinetic,
a possible mechanism of AHLS/KCoFC preparation and Cs+ adsorption
by AHLS/KCoFC can be deduced in Fig. 16. Chrome-tanned leather
scrapis made up of collagen fibers with substantial eCOOH, eOH and
eCONHR. After hydrolysis with NaOH, the amounts of eOH and
eCOOH increase, and they exist in the form of sodium salt. Co2+ re-
placed Na+ and chelated with eOH, —COOH and eCONHR. Subse-
quently, K4Fe(CN)6·3H2O reacted with Co2+ loaded on AHLS to form
KCoFC. During the process of adsorption, Cs+ was exchnged with K+
located in the body center of KCoFC on AHLS.
3.5. Comparison with other adsorbent
A comparison of the adsorption capacity of Cs+ between AHLS/
KCoFC and various adsorbents reported previously is shown in Table 5.
The result showed that AHLS/KCoFC has better potential for the ad-
sorption of Cs+ than other adsorbents [29,30,72–76].
4. Conclusion
In order to recover Cs+ from saline brine, KCoFC was modified on
AHLS to prepare a new adsorbent of AHLS/KCoFC. The AHLS/KCoFC
was characterized by FT-IR and XPS, and it was found that KCoFC was
effectively loaded on AHLS in the form of coordination bond. The re-
sults of batch experiments showed the maximum adsorption capacity
J. Yang et al. Colloids and Surfaces A 537 (2018) 268–280

Fig. 16. Simply schematic of AHLS/KCoFC preparation and adsorption of Cs+.

Table 5 Acknowledgements
Cs+ adsorption capacities from other studies related to different adsorbents.
This work is financially supported by National Nuclear Gnergy
Adsorbent Adsorption capacity (mg g−1) References
Development Research Project (Grant no. 13ZG6103) and Postgraduate
FC-Cu-EDA-SAMMS 17.27 [72] Innovation Fund Project by Southwest University of Science and
CHCF–PAN 25.25 [73] Technology (Grant no. 17ycx006).
NiHCF-WS 0.5 [74]
PB-Fe3O4 16.20 [75]
KCoFC-fiber 20 [29]
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