Journal of Dispersion Science and Technology

ISSN: 0193-2691 (Print) 1532-2351 (Online) Journal homepage: https://www.tandfonline.com/loi/ldis20

Enhanced adsorption of nicotinic acid by

different types of Mg/Al layered double
hydroxides: synthesis, equilibrium, kinetics, and
thermodynamics

Aslı Gök

To cite this article: Aslı Gök (2020): Enhanced adsorption of nicotinic acid by different types of
Mg/Al layered double hydroxides: synthesis, equilibrium, kinetics, and thermodynamics, Journal of
Dispersion Science and Technology, DOI: 10.1080/01932691.2020.1729795

To link to this article: https://doi.org/10.1080/01932691.2020.1729795

Published online: 20 Feb 2020.

Submit your article to this journal

Article views: 18

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=ldis20
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01932691.2020.1729795

Enhanced adsorption of nicotinic acid by different types of Mg/Al layered

double hydroxides: synthesis, equilibrium, kinetics, and thermodynamics
€k
Aslı Go
Engineering Faculty, Chemical Engineering Department, Istanbul University-Cerrahpaşa, Istanbul, Turkey

ABSTRACT ARTICLE HISTORY

The aim of this study was to investigate the effect of different ions in the interlayer spaces of lay- Received 14 October 2019
ered double hydroxides (LDHs) with different Mg/Al ratios on the adsorption of aqueous nicotinic Accepted 1 February 2020
acid (NAc). For this purpose, three types of LDHs were synthesized for NAc removal using the co-
KEYWORDS
precipitation method with different Mg/Al ratios to include chloride or nitrate anions between the
Nicotinic acid; adsorption;
layers (Cl-LDH2:1, NO3-LDH3:1, and NO3-LDH2:1). The LDHs were characterized with Fourier transform layered double hydroxide;
infrared spectroscopy, X-ray diffraction, and inductively coupled plasma mass spectrometry, and ion-exchange; Mg/Al ratio
the effects of initial acid concentration, time, temperature and adsorbent amount on NAc adsorp-
tion were investigated. The results showed that the Langmuir equilibrium isotherm model was the
best for all three LDHs, and among the kinetic models, the pseudo-second-order agreed the most
with experimental data. DG, DH, and DS were calculated for all LDHs, and according to the data,
the adsorption of NAc was endothermic and spontaneous. When all the results were evaluated
comparatively, it was found that NO3-LDH2:1, with a 2:1Mg/Al ratio and nitrate ions between the
layers, has the best NAc adsorption capacity.

GRAPHICAL ABSTRACT

Introduction materials that are biocompatible and environmentally

The separation of carboxylic acids from aqueous solutions
has been the subject of many studies. Carboxylic acids are
generally produced by fermentation processes, where the
final product is an aqueous solution of the acid mixture. In
many cases, separation of the acid from the aqueous solu-
tion by distillation is problematic due to required energy
cost. Therefore, researchers are still developing low-cost and
high-efficiency separation processes. Some examples include
precipitation, liquid–liquid extraction,[1] reactive extrac-
tion,[2] electromagnetic dialysis, liquid membrane systems[3]
and adsorption[4] processes. Since each process has its
advantages and disadvantages, the appropriate method for
each case should be selected and analyzed thoroughly.
Among these processes, adsorption has been preferred in
recent years in terms of ease of use, high performance, low
cost, and reproducibility.
There are many different adsorbents used in adsorption
processes, one of which is layered double hydroxides (LDHs),
friendly. LDHs are inorganic-based anionic clay particles that
are generally synthesized using the co-precipitation method.
Its chemical compositions are given by the general formula
[MII1-x MIIIx (OH)2]xþ [An-x/n.yH2O]x-, where MII and MIII
are divalent and trivalent metal cations, respectively, An- is an
n-valence anion intercalated between the layers, and x
ranges from 0.1 to 0.5 as the trivalent metal ratio
[MIII/(MIIþMIII)].[5,6] Due to its similar chemical and phys-
ical properties to clay minerals, LDHs have been widely used
as adsorbents. Their structures contain water molecules and
ion-exchangeable anions between the hydroxide layers, diva-
lent and trivalent cations forming a the net positive charge
density on the layer surface.[7] Another feature that makes
LDHs interesting are their memory effects, and they have
been used in many studies as a result.[8] To achieve this effect,
the material must be thermally activated by calcination.[9]
LDHs have high adsorption efficiency and can be prepared in
low cost and simple manners.[10] Considering these reasons,
LDHs are used in both catalyst and catalyst beds as a

CONTACT Aslı G€ok aslig@istanbul.edu.tr Engineering Faculty, Chemical Engineering Department, Istanbul University-Cerrahpaşa, Avcılar, 34320
Istanbul, Turkey.
ß 2020 Taylor & Francis Group, LLC
2 A. GÖK
composite material with different nano materials, as an anion
exchanger and as a flame retardant, in addition to their use as
adsorbent. They can also be used in many fields such as heavy
metal removal and dye removal from water.[11,12] For
example, Thesis et al.[9] used an LDH for removal of radio-
active iodine from aqueous solutions. Mainly due to the net
cationic surface charge and inter-layer ion exchange capacity,
the LDH increases the opportunity to remove carboxylic
acids.[13] Vreysen et al. carried out humic and fulvic acid
adsorption on LDH layers obtained by traditional methods of
adsorption behavior and investigated the parameters that
affect it.[14] G€
ok et al. obtained Mg–Al–Cl LDHs (Mg/Al
atomic ratio: 3:1) capable of adsorbing 96.73% of malic acid
from wastewater and investigated the kinetic parameters of
this physical adsorption mechanism.[15] Similarly, Lalikoglu
et al. reported that the separation of lactic acid using
Mg–Al–Cl LDHs is aspontaneous, monolayer, and physical
adsorption process.[16]
Nicotinic acid (NAc) is a benzoic acid derivative contain-
ing a carboxylic acid group. It is a water-soluble vitamin
obtained by fermentation, and is also known as Niacin or
vitamin B3. The vitamin effects of NAc were discovered at
the beginning of the 20th century. In the following years,
NAc was found to have a low cholesterol effect in plasma,
and so it began to be used to treatment of dyslipide-
mia.[17,18] Although NAc aids in reducing free fatty acids in
plasma, it can cause side effects when more than the recom-
mended amount is consumed. The vasodilator response,
which is one of the main side effects, leads to a decrease in
blood pressure. However, other common undesirable effects
include nausea, abdominal pain and diarrhea, as well as
rashes, itching, and redness. Each year, large amounts of
NAc are produced and inevitably discharged into the waste-
water system. Thus, adsorption as one of the most preferred
separation methods is a cheap and effective approach to sep-
arating NAc from aqueous solutions.[19]
The main objective of this study was to investigate the
adsorption parameters of various types of LDHs on NAc
removal from aqueous solutions. Therefore, LDHs contain-
ing different atomic ratios (Mg/Al ratio) and/or different
amounts of ions (Cl or NO3) between the layers were
synthesized. Fourier transform-infrared (FTIR) spectroscopy,
X-ray diffraction (XRD), and inductively coupled plasma
mass spectrometry (ICP-MS) were used to characterize the
LDHs and NAc-adsorbed LDHs. After characterization, the
parameters affecting adsorption including adsorbent concen-
tration, contact time, initial acid concentration, and tem-
perature were examined. Furthermore various kinetic and
equilibrium models were applied to the experimental data to
obtain kinetic and equilibrium parameters.
Experimental
Materials
NAc, aluminum chloride hexahydrate (AlCl36H2O), magne-
sium chloride hexahydrate (MgCl26H2O), aluminum nitrate
nonahydrate (Al(NO3)39H2O), magnesium nitrate hexahy-
drate (Mg(NO3)26H2O), and sodium hydroxide were
purchased from Sigma (USA). All solutions and standards
were prepared with deionized water.
Methods
Synthesis and characterization of LDHs
Mg-Al LDHs were synthesized at room temperature by a co-
precipitation method. Briefly, for the preparation of NO3-
LDH2:1, Mg(NO3)26H2O and Al(NO3)39H2O were dissolved
in 10 mL of decarbonated water with a 3:1 mmol ratio of
Mg:Al salts. Then, this salt solution was poured at a constant
rate into an NaOH solution (6 mmol in 40 mL). The resulting
slurry was stirred for 10 min and aged for 1 h. Then, the sus-
pension was separated by centrifugation at 4500 rpm for
5 min twice and at 5000 rpm for 10 min once. After that, the
residue was washed with decarbonated water and dried under
vacuum at room temperature. The synthesis of Cl-LDH2:1 was
carried out in a similar manner using MgCl2.6H2O and
AlCl3.6H2O. All LDH syntheses were performed under a
nitrogen atmosphere to ensure minimum carbonate contam-
ination. In order to determine the effect of Mg/Al ratio on
NAc adsorption, NO3-LDH3:1 was also synthesized. First, the
salts of Mg(NO3)26H2O: and Al(NO3)39H2O (3:1 mmol)
were dissolved in 10 mL of decarbonated water, but unlike the
above LDH production methods, an NaOH solution was
poured into this salt solution at a constant rate to maintain a
pH of 10. The remainder of the synthesis was performed in
the same manner and under the same conditions.[6,14]
The LDHs and NAc-adsorbed LDHs were characterized
using sample: KBr (1:200 w/w) disks on a Cary 630 FTIR
spectrometer (Agilent; USA) over a range of 4000–650 cm1,
and the crystalline structures were analyzed by a Rigaku D/
Max-2200/PC X-ray powder diffractometer (Japan) with Cu
Ka radiation (k ¼ 1.5406 nm) at 30 mA and 40 kV (1 /min;
2h ¼ 5 30 ). The Mg:Al ratios of the LDHs were calculated
using the elemental contents determined by ICP-MS with a
Thermo Scientific Element XSERIES 2 ICP-MS (USA). The
samples were prepared in diluted HNO3 (500 mg/50 mL
(10 mL HNO3 þ 40 mL deionized water)).
Adsorption experiments
Adsorption studies were performed with 4 different steps
according to the report by Datta et al.[19] Different amounts
of adsorbent (0.0125–0.2 g) were mixed with 5 mL of an
NAc solution (6 g/L) in an Erlenmeyer flask. The flasks were
placed in a mixer (Nuve 101, Turkey) at 120 rpm for 2 h.
The LDHs were then separated from the main solution in a
centrifuge (NF200, Nuve, Turkey) at 4500 rpm for 10 min.
The NAc amount was determined by volumetric titration
with 0.1 N NaOH. The optimum adsorbent amount was
determined and used in the following experiments.
As the second step, to investigate time the constant
amounts of LDHs (Cl-LDH2:1, 0.05 g; NO3-LDH3:1, 0.025 g;
and NO3-LDH2:1, 0.025 g) were mixed with 5 mL of an NAc
solution at 120 rpm and 298 K. The experiment time varied
between 2 and 120 min. Then as mentioned above the same
 JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 3

Table 1. Chemical composition and formulas of Mg-Al LDHs.

%wt
Atomic ratio
LDH Mg Al Mg/Al Proposed formula pH
Cl-LDH2:1 35.7 21.1 1.88 [Mg0.65Al0.35(OH)2](Cl)0.35. 0.58 H2O 8.3
NO3-LDH2:1 44.9 16.8 1.88 [Mg0.65Al0.35(OH)2](NO3)0.35. 0.87 H2O 8.3
NO3-LDH3:1 35.9 21.2 2.97 [Mg0.75Al0.25(OH)2](NO3)0.25. 0.56 H2O 10

Figure 1. FTIR spectra of LDHs.

procedure was applied to determinate the amount of
adsorbed NAc.
The adsorption procedures were carried out at 298, 313,
323, and 333 K to investigate the effect of temperature. After
2 h, the samples were separated from the LDHs by centrifu-
gation and the final NAc concentrations of the solutions
were measured via the volumetric NaOH titration method.
Isotherm data were collected for different concentrations
of NAc from 2.46 to 14.77 g/L at 298 K.[19] The adsorption
capacity (Qe) was calculated according to
ðC0  Ce ÞV
Qe ¼ , (1)
m determine the effect of inter-layer anion differences on NAc
And the removal efficiency (R%) was calculated according to
ðC0  Ce Þ
R% ¼ x100, (2)
C0
where Co is the initial acid concentration (g/L), Ce is the
equilibrium concentration of NAc (g/L), V is the solution
volume (L), and m is the amount of adsorbent (g).
Results and discussion
Synthesis and characterization of Mg–Al LDHs
The synthesis of all of the LDHs was carried out by the co-pre-
cipitation method, wherein a mixture of aqueous magnesium
and aluminum salts and NaOH solutions were precipitated.
Considering related studies reported in the literature the most
crucial factor for the LDH formation mechanism is the slurry
pH. Seron et al. reported that when the pH of the slurry is
above 8.5, Mg-enriched species precipitate, whereas when the
pH of the slurry is below 8.5, Al-enriched species precipitate.[20]
Therefore, when the hydroxide layers begin to form during the
LDH synthesis, first the Al layers precipitate, followed by the
Mg layers. Therefore, in this study, to determine the effect of
LDH structures with Al-enriched layers on NAc adsorption,
co-precipitation was performed below pH 8.5. At the same
time, these LDH structures (NO3-LDH2:1 and Cl-LDH2:1) were
prepared with chloride or nitrate anions between the layers to
adsorption. For comparison, NO3-LDH3:1 was also synthesized
via co-precipitation at pH 10 according to a conventional
method in the literature.
As shown in Table 1, although the Mg/Al salts molar ratio
was 3:1 mmol for the synthesis of all Mg–Al LDHs, the chem-
ical compositions of Cl-LDH2:1 and NO3-LDH2:1 varied due to
the pH. Therefore, Mg–Al LDHs with Al-enriched layers were
produced by the synthesis of Cl-LDH2:1 and NO3-LDH2:1 with
Mg/Al atomic ratios of 2:1 at pH 8.3. NO3-LDH3:1, with an
atomic Mg/Al ratio of 3:1, was synthesized by a conventional
method and contained Mg-rich layers as expected.
Figure 1 presents the FTIR spectra of NO3-LDH2:1, NO3-
LDH3:1, and Cl-LDH2:1 before and after NAc adsorption
(NAc-NO3-LDH2:1, NAc-NO3-LDH3:1, and NAc-Cl-LDH2:1,
respectively). In the FTIR spectra of the naked LDHs, the
4 A. GÖK
Figure 2. Powder XRD patterns of LDHs.
broad band at approximately 3300–3700 cm1 (maximum at
3548 cm1) is associated with the asymmetric and symmetric
stretching vibrations of OH groups in the brucite-like
hydroxyl layers (Al–OH or Mg/Al–OH) and water in the
interlayer spaces. The weak bands at approximately
1630 cm1 (NO3-LDH2:1 and Cl-LDH2:1) and 1638 cm1
(NO3-LDH3:1) can be assigned to the deformation bending
vibrations of the interlayer water molecules. The characteristic
sharp absorption band with a maximum at 1384 cm1 for
NO3-LDH2:1 and NO3-LDH3:1 was attributed to the asymmet-
ric stretching vibrations of NO3-, and the small, sharp band at
1362 cm1 for Cl-LDH2:1 is due to the asymmetric stretching
vibration of CO32. Although the reactions were performed in
decarbonated water and under a nitrogen atmosphere to avoid
excessive carbonate contamination, a small amount still
occurred in the production of Cl-LDH2:1.[14] The series of
bands in the spectra at 1000–600 cm1 were attributed to the
characteristic lattice vibrations of Mg–O and Al–O.[21]
On the other hand, all of the FTIR spectra of the NAc-LDHs
confirmed the adsorption of NAc. The comparison between
NAc-adsorbed LDHs and naked LDHs illustrates the individual
differences in bands appearing at approximately 3300–3700,
1650–1550, 1450–1350, and 1100-600 cm1. The broad bands
of the naked LDHs at approximately 3300–3700 cm1 (max-
imum at 3548 cm1) were significantly sharper in all the FTIR
spectra of the NAc-adsorbed LDHs due to the OH stretching of
the COOH group of NAc.[22] Other significant differences
from the FTIR spectra of the naked LDHs are the new sharp
absorption bands at approximately 1607 and 1560 cm1 due to
the asymmetric stretching vibrations of the C–C bonds of
the aromatic ring and carboxylate groups.[23,24] Moreover, the
decreased intensity of the sharp NO3- peaks at 1384 cm1
indicates the ion-exchange reaction between NO3 anions and
the anionic groups of NAc.[6,14]
Figure 2 shows the powder XRD patterns of NO3-LDH2:1
and NAc-NO3-LDH2:1. The powder XRD patterns of NO3-
LDH2:1 indicates basal symmetric reflections with a strong
(003) peak near 2h ¼ 10.3 corresponding to d ¼ 0.8574 nm
and a broad (006) peak near 2h ¼ 20.3 corresponding to
d ¼ 0.4375 nm. These peaks indicate that this LDH sample has
a highly crystalline structure. Moreover, the d003 value gives
information about the basal spacings of two consecutive bru-
cite-like hydroxide layers.[21] Accordingly, the adsorption of
NAc onto NO3-LDH2:1 causes expansion of the basal spacing,
as illustrated by the value of d003 near 2h ¼ 5.2 corresponding
to d ¼ 1.7 nm and 2h ¼ 9.8 corresponding to d ¼ 0.9059 nm.
This increase in the basal spacing resulted from ion-exchange
between the nitrate anions in the interlayer spaces and NAc,
which has a larger molecular size.
Effect of adsorbent amount
The effect of the amount of adsorbent was investigated with
different adsorbent amount (0.0125, 0.025, 0.05, 0.075, 0.1,
0.15, and 0.2 g) in 5 mL of a 6 g/L NAc solution at 298 K.
The effect of the adsorbent dose on both the adsorption cap-
acity (Qe) and removal efficiency (R%) is shown in Figure 3.
The amount of adsorbent to be used in the remaining
experiments was determined from the optimum dose, which
was selected as the intersection of the removal efficiency and
adsorption capacity curves.[26] The optimum dosage of Cl-
LDH2:1, NO3-LDH3:1 and NO3-LDH2:1 are 0.05, 0.025, and
0.025–0.05 g, respectively (Figure 3). Therefore, the optimum
dose for both NO3-LDHs was set as 0.025 g, whereas for Cl-

Figure 3. Effect of adsorbent amount on NAc adsorption at 298 K: (A) Cl-LDH2:1, (B) NO3-LDH2:1, and (C) NO3-LDH3:1.
LDH, the amount was set as 0.05 g. Because the energy sites
on the adsorbent vary according to the adsorbent dose, the
adsorption capacity also changes accordingly. Especially,
when the amount of adsorbent decreases, more surface sites
are made available for the adsorption process, and the
adsorption capacity increases. As shown in Figure 3, when
the amount of adsorbent increased, the percentage of
removed NAc from the aqueous solution increased, but the
adsorption capacities decreased for all LDH types.[27] Bekci
et al., in a study on the adsorption behavior of zearalenone
in the synthetic media of canned corn by montmorillonite
K10 and pillared montmorillonite K10, reported that basal
spacing expansion results in a weaker adsorption capacity.
However, they also reported that increasing the basal spac-
ing with pillaring does not affect the adsorption behavior of
clay adsorbents.[28] Similarly, Wu et al. reported in a study
on quinolone antibiotic nalidixic acid adsorption on mont-
morillonite and kaolinite that basal spacing expansion indi-
cated the adsorption and intercalation of nalidixic acid in
the interlayer spaces.[29] The experimental results, apparent
expansion of the basal spacing, and adsorption behavior of
NAc in the interlayer space suggest that the adsorption
occurs mainly by an ion exchange mechanism, as is gener-
ally accepted.
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 5
As shown in Figure 3a, as the adsorbent dose increased, the
NAc removal efficiency increased from 30% to 98.9%, and the
adsorption capacity decreased from 722.9 to 148.4 mg/g for
Cl-LDH2:1. Similarly, for NO3-LDH2:1, the removal efficiency
increased from 38% to 99.4%, and the adsorption capacity
decreased from 921 to 149.1 mg/g (Figure 3b). Finally, for
NO3-LDH3:1, the removal efficiency increased from 43.7% to
99.4%, and the adsorption capacity decreased from 1050.8 to
7.20 mg/g (Figure 3c). Datta et al.[19] previously reported that
the maximum removal percentage of NAc from aqueous solu-
tions using 5 g/L of magnetic activated carbon was 65%,
whereas in this study, these percentages for NO3-LDH2:1,
NO3-LDH3:1, and Cl-LDH2:1 were 66.7%, 61%, and 49.2%,
respectively. However, to remove approximately 90% of NAc
regardless of the optimum adsorbent dose, it is necessary to
use at least 10 g/L of NO3-LDH2:1, 15 g/L of NO3-LDH3:1, and
22 g/L of Cl-LDH2:1. Comparing the Qe values of the LDHs,
NO3-LDH2:1 showed the best performance.
Effect of contact time
According to the kinetic study, all LDHs reached equilibrium
concentrations by 120 min (Figure 4). The pseudo-first-order
(PFO), pseudo-second-order (PSO) and intraparticular
6 A. GÖK

Table 2. Equilibrium and kinetic model parameters.

Equilibrium model parameters
Cl-LDH2:1 NO3-LDH2:1 NO3-LDH3:1
Cl-LDH2:1 NO3-LDH2:1 NO3-LDH3:1
Langmuir parameters QCee ¼ bQ1m þ QCme [30]
Qm 1000 1111 1000
b 2.65  10-4 1.4  10-3 4.3  10-4
R2 0.9998 0.9970 0.9961
Freundlich parameters lnqQe ¼ lnK f þ n1 lnce [31]
Kf 3.72 116.66 19.24
n 1.7 4.08 2.4
2
R 0.9774 0.9890 0.9863
Temkin parameters Qe ¼ Qm lnK t þ Qm lnce [31]
Qm 216.7 171.29 225.46
KT 2.61  10-3 4.79  10-2 4.17  10-3
2
R 0.9948 0.992 0.9912
Kinetic model parameters
Pseudo-first order lnðQe  Qt Þ ¼ lnQe  k1 t [32]
Figure 4. Effect of contact time on NAc adsorption with NO3-LDH3:1, NO3- Qm 256.8 705.7 363.5
LDH2:1, and Cl-LDH2:1 at 298 K. k1 0.057 0.0426 0.0653
R2 0.9225 0.9582 0.9852
t
diffusion (IPD) models were applied to the experimental data; Pseudo-second order Qt ¼ kQ2 þ Qe t
1 1 [31]
e
Qm 370.3 833.3 526.3
the model parameters are given in Table 2. All adsorbents k2 2.94  10-5 7.74  10-3 2.95  10-4
were found to be the best fit by PSO model according to the R2 0.9957 0.9934 0.9995
Intraparticle diffusion Qt ¼ km t 1=2 þ C [31]
regression correlation coefficient (R2). As in the study by km 34.4 80.3 37.8
Vreysen et al.[14] the adsorption mechanism of NAc onto C 57.6 37.2 152.1
LDHs is not controlled by IPD because the reaction kinetics R2 0.9089 0.9055 0.8103
Ce Ce [30]
Langmuir parameters Qe ¼ bQm þ Qm 1
are consistent with the PSO model. There is a rapid increase Qm 1000 1111 1000
in adsorption within the first several minutes, followed by B 2.65  10-4 1.4  10-3 4.3  10-4
deceleration. These results are consistent with previous studies R2 0.9998 0.9970 0.9961
Freundlich parameters lnqQe ¼ lnK f þ n1 lnce [31]
on the adsorption of carboxylic acids with LDHs.[10,13] Kf 3.72 116.66 19.24
n 1.7 4.08 2.4
R2 0.9774 0.9890 0.9863
Effect of initial acid concentration Temkin parameters Qe ¼ Qm lnK t þ Qm lnce [31]
Qm 216.7 171.29 225.46
The equilibrium results with five different concentrations of KT 2.61  10-3 4.79  10-2 4.17  10-3
R2 0.9948 0.992 0.9912
NAc were obtained to determine the effect of initial acid
concentration and are given in Figure 5. The solution con- Kinetic model parameters
Pseudo-first order lnðQe  Qt Þ ¼ lnQe  k1 t [32]
centrations were varied between 2.46 and 14.77 g/L, and the Qm 256.8 705.7 363.5
experiments were performed at 298 K.[19] As shown in k1 0.057 0.0426 0.0653
Figure 5, when the initial acid concentration increased, the R2 0.9225 0.9582 0.9852
Pseudo-second order Qt t ¼ kQ1 2 þ Q1e t [31]
Qe values of Cl-LDH2:1 increased from 168.7 to 669.1 mg/g. Qm 370.3
e
833.3 526.3
Similarly, the Qe values of NO3-LDH2:1 increased from k2 2.94  10-5 7.74  10-3 2.95  10-4
2
405.2 to 1045.5 mg/g, whereas that of NO3-LDH3:1 increased R 0.9957 0.9934 0.9995
Intraparticle diffusion Qt ¼ km t 1=2 þ C [31]
from 269.2 to 888.9 mg/g. Qe increases with increasing initial km 34.4 80.3 37.8
acid concentration because the driving force in the solutions C 57.6 37.2 152.1
R2 0.9089 0.9055 0.8103
likely increases, which induces mass transfer effects.[30]

The R2 values were obtained as 0.9948, 0.992, and 0.9912 for

Equilibrium and kinetic adsorption models
The Langmuir, Freundlich, and Temkin isotherm models
were applied to the experimental data for equilibrium studies,
and the PFO, PSO, and IPD models were applied to the kin-
etic data. The model parameters are given in Table 2. The
Langmuir isotherm parameters were determined by plotting
Ce/Qe against Ce. The R2 values were obtained as 0.9998,
0.9970, and 0.9961 for Cl-LDH2:1, NO3-LDH2:1, and NO3-
LDH3:1, respectively. The Freundlich isotherm parameters
were determined by plotting lnQe against lnCe. The R2 values
were obtained as 0.9774, 0.9890, and 0.9863 for Cl-LDH2:1,
NO3-LDH2:1, and NO3-LDH3:1, respectively. The Temkin iso-
therm parameters were obtained by plotting Qe against lnCe.
Cl-LDH2:1, NO3-LDH2:1, and NO3-LDH3:1, respectively. The
maximum adsorption capacity of NO3-LDH2:1 was found to
be 1111 mg/g, which was the highest. Among the isotherm
models, the most suitable was found to be Langmuir, which
describes adsorption processes with homogeneous monolayer
coverage.[10] The results demonstrate that the adsorption of
NAc onto LDH could feasibly take place by uniform coverage
of the adsorbate onto the adsorbent surface.
The kinetic parameters for the PFO model were deter-
mined by plotting ln(qe-qt) against t. The R2 values were
obtained as 0.9225, 0.9582, and 0.9852 for Cl-LDH2:1, NO3-
LDH2:1, and NO3-LDH3:1, respectively. The PSO model
parameters were determined by plotting t/qt against t. The

Figure 5. Effect of initial NAc concentration on adsorption with NO3-LDH3:1,
NO3-LDH2:1, and Cl-LDH2:1 at 298 K.
Figure 6. Effect of solution temperature on NAc adsorption capacity of
NO3-LDH3:1, NO3-LDH2:1, and Cl-LDH2:1.
R2 values were obtained as 0.9957, 0.9934, and 0.9995 for
Cl-LDH2:1, NO3-LDH2:1, and NO3-LDH3:1, respectively. The
IPD model parameters were determined by plotting qt
against t1/2 . The R2 values were obtained as 0.9089, 0.9055,
and 0.8103 for Cl-LDH2:1, NO3-LDH2:1, and NO3-LDH3:1,
respectively. According to the R2 values, the best agreement
was obtained with the PSO model. These results indicate
that the sorption process is controlled by chemisorption.
Effect of temperature on adsorption
The solution temperature is a prominent factor affecting the
adsorption efficiency of adsorbents depending on if the pro-
cess is endothermic or exothermic. Thus, NAc (6 g/L)
adsorption from water was studied at 298, 313, 323, and
333 K with Cl-LDH2:1, NO3-LDH2:1, and NO3-LDH3:1. The
dependence of Qe on temperature is shown in Figure 6. As
the solution temperature increased, Qe of Cl-LDH2:1
increased from 365.4 to 553.9 mg/g. Similarly, Qe of NO3-
LDH2:1 increased from 738.4 to 861.0, while Qe that NO3-
LDH3:1 increased from 549 to 716.3 mg/g. According to the
results, an increase in the liquid-phase temperature leads to
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 7
expansion of the LDH basal spacing, which increases their
adsorption capacities.
When all the results were evaluated, it became clear that NAc
adsorption onto NO3-LDH2:1 showed the best performance as
an adsorbent comparing to other LDHs. There are two main
reasons for this result. First, nitrate ions create a larger interlayer
spacing compared with chloride ions, and thus the nitrate orien-
tation in the LDH leads to an increase in large molecule adsorp-
tion.[19] Second, the basal spacing between LDH layers changes
according to the different Mg/Al ratios of the LDHs (2:1 vs. 3:1).
Therefore, interlayer nitrate ions are perpendicularly orientate in
NO3-LDH2:1, whereas NO3-LDH3:1 includes a mixture of paral-
lel and perpendicular orientations.[33]
Adsorption thermodynamics: Gibbs free energy model
To determine whether the adsorption process is exothermic
or endothermic, the enthalpy values should be calculated
according to the Gibbs free energy (DG ) model:
 
qe
DG ¼ RTlnKd ¼ RTln , (3)
ce
DG ¼ DH   TDS , (4)
1 1
where R is the universal gas constant (8.314 J mol K ), T is
the temperature of the solution, Kd is the equilibrium con-
stant, Qe is the equilibrium adsorption capacity, Ce is the equi-
librium concentration, and DH and DS are the enthalpy and
entropy, respectively. To calculate DH and DS , first, the DG
values were calculated according to Eq. 3, and then the slope
and intercep of the graph of DG and T provided DS and
DH , respectively.[19] DS for Cl-LDH2:1, NO3-LDH2:1, and
NO3-LDH3:1 were 149.1, 26.9 and 29.7 Jmol1K1, respect-
ively. The positive DS values increase the randomness in the
adsorption system in terms of thermodynamics. The DH val-
ues for Cl-LDH2:1, NO3-LDH2:1, and NO3-LDH3:1 were 49.1,
10.9, and 13.3 kJ mol1, respectively. The positive DH values
indicate that the adsorption process is endothermic.
Conclusions
In this study, LDHs with ions in the interlayer spacings and
different Mg/Al ratios were synthesized and characterized,
and their effects on the adsorption of NAc were investigated.
For the synthesized LDHs, the optimum adsorbent amount
and the resulting equilibrium adsorption capacity values
were determined. Based on the data obtained during this
study, the Mg/Al ratio of LDHs and the different ions pre-
sent between the LDHs layers influence the NAc adsorption
process. It was clear that NO3-LDH2:1 showed the best
adsorbent performance as its endothermic physical adsorp-
tion is less random in nature and is a monolayer process, its
behavior follows the PSO model, and it has the highest NAc
adsorption capacity. Furthermore, future studies should be
performed on the effect of NO3-LDHs containing different
cations and ratios in the presence of different ionic strengths
or contaminants on the adsorption of NAc in aque-
ous solutions.
8 A. GÖK
Acknowledgements
This research did not receive any specific grant from funding agencies
in the public, commercial, or not-for-profit sectors.
References
_ Phase Equilibria of
[1] G€ok, A.; Uslu, H.; Kırbaşlar, ŞI.
(Water þ Levunilic Acid þ Alcohol) Ternary Systems. Fluid
Phase Equilib. 2008, 273, 21–26. DOI: 10.1016/j.fluid.2008.08.
004.
[2] Datta, D.; Aşçı, Y. S.; Tuyun, A. F. Extraction Equilibria of
Glycolic Acid Using Tertiary Amines: Experimental Data and
Theoretical Predictions. J. Chem. Eng. Data 2015, 60,
3262–3267. DOI: 10.1021/acs.jced.5b00497.
[3] €
Baylan, N.; Çehreli, S.; Ozparlak, N. Transport and Separation
of Carboxylic Acids through Bulk Liquid Membranes
Containing Tributylamine. J Disper. Sci. Technol 2017, 38,
895–900. DOI: 10.1080/01932691.2016.1214841.
[4] _
Ilalan, _ Inci,
I.; _ _ Baylan, N. Separation of Lactic Acid by
I.;
Multiwall Carbon Nanotube Adsorption from Water. Dwt.
2017, 93, 339–345. DOI: 10.5004/dwt.2017.21273.
[5] Xie, Y.; Yuan, X.; Wu, Z.; Zeng, G.; Jiang, L.; Peng, X.; Li, H.
Adsorption Behavior and Mechanism of Mg/Fe Layered Double
Hydroxide with Fe3O4-Carbon Spheres on the Removal of Pb
(II) and Cu (II). J. Colloid Interf. Sci. 2019, 536, 440–455. DOI:
10.1016/j.jcis.2018.10.066.
[6] € um€
Ozg€ uş, S.; G€
ok, M. K.; Bal, A.; G€ uçl€
u, G. Study on Novel
Exfoliated Polyampholyte Nanocomposite Hydrogels Based on
Acrylic Monomers and Mg–Al–Cl Layered Double Hydroxide:
Synthesis and Characterization. Chem. Eng. J. 2013, 223,
277–286. DOI: 10.1016/j.cej.2013.02.098.
[7] Das, J.; Patra, B. S.; Baliarsingh, N.; Parida, K. M. Adsorption
of Phosphate by Layered Double Hydroxides in Aqueous
Solutions. Appl. Clay Sci. 2006, 32, 252–260. DOI: 10.1016/j.
clay.2006.02.005.
[8] Mascolo, G.; Mascolo, M. C. On the Synthesis of Layered
Double Hydroxides (LDHs) by Reconstruction Method Based
on the “Memory Effect. Micropor. Mesopor. Mat. 2015, 214,
246–248. DOI: 10.1016/j.micromeso.2015.03.024.
[9] Theiss, F. L.; Ayoko, G. A.; Frost, R. L. Iodide Removal Using
LDH Technology. Chem. Eng. J. 2016, 296, 300–309. DOI: 10.
1016/j.cej.2016.02.039.
[10] Yang, Z.; Wang, F.; Zhang, C.; Zeng, G.; Tan, X.; Yu, Z.;
Zhong, Y.; Wang, H.; Cui, F. Utilization of LDH-Based
Materials as Potential Adsorbents and Photocatalysts for the
Decontamination of Dyes Wastewater: A Review. Rsc Adv.
2016, 6, 79415–79479. DOI: 10.1039/C6RA12727D.
[11] Bakr, A. A.; Mostafa, M. S. Adsorption of Cd(II) from Aqueous
Solutions via Meso Structured Adsorbent Based on Ni/MoLDH:
Kinetics, Thermodynamics, and Adsorption Mechanism. Energ.
Sourc. A 2019, 1–9. DOI: 10.1080/15567036.2019.1607936.
[12] Shanmuganathan, K.; Ellison, K. J. Polymer Green Flame
Retardants; Papaspyrides, C. D., Kiliaris, P., Eds.;
Elsevier: Amsterdam, Netherlands, 2014, pp 675–707. DOI: 10.
1016/B978-0-444-53808-6.00020-2.
[13] Williams, O.; Clark, I.; Gomes, R. L.; Perehinec, T.; Hobman,
J. L.; Stekel, D. J.; Hyde, R.; Dodds, C.; Lester, E. Removal of
Copper from Cattle Footbath Wastewater with Layered Double
Hydroxide Adsorbents as a Route to Antimicrobial Resistance
Mitigation on Dairy Farms. Sci. Total Environ. 2019, 655,
1139–1149. DOI: 10.1016/j.scitotenv.2018.11.330.
[14] Vreysen, S.; Maes, A. Adsorption Mechanism of Humic and
Fulvic Acid onto Mg/Al Layered Double Hydroxides. Appl.
Clay Sci. 2008, 38, 237–249. DOI: 10.1016/j.clay.2007.02.010.
[15] G€ok, A.; G€ ok, M. K.; Aşçı, Y. S.; Lalikoglu, M. Equilibrium,
Kinetics and Thermodynamic Studies for Separation of Malic
Acid on Layered Double Hydroxide (LDH). Fluid Phase
Equilib. 2014, 372, 15–20. DOI: 10.1016/j.fluid.2014.03.023.
[16] Lalikoglu, M.; G€ ok; A.; G€ok, M. K.;.; Asc¸I, Y. S.; Investigation
of Lactic Acid Separation by Layered Double Hydroxide:
Equilibrium, Kinetics, and Thermodynamics. J. Chem. Eng.
Data 2015, 60, 3159–3165. DOI: 10.1021/acs.jced.5b00324.
[17] Carlson, L. A. Nicotinic Acid: The Broad-Spectrum Lipid Drug.
A 50th Anniversary Review. J. Intern. Med. 2005, 258, 94–114.
DOI: 10.1111/j.1365-2796.2005.01528.x.
[18] Mckenney, J. Niacin for Dyslipidemia: Considerations in
Product Selection. Am. J. Health Syst. Pharm. 2003, 60,
995–1005. DOI: 10.1093/ajhp/60.10.995.
[19] Datta, D.; Sah, S.; Rawat, N.; Kumar, R. Application of
Magnetically Activated Carbon for the Separation of Nicotinic
Acid from Aqueous Solution. J. Chem. Eng. Data 2017, 62,
712–719. DOI: 10.1021/acs.jced.6b00784.
[20] Seron, A.; Delorme, F. Synthesis of Layered Double Hydroxides
(LDHs) with Varying pH: A Valuable Contribution to the
Study of Mg/Al LDH Formation Mechanism. J. Phys. Chem.
Solids 2008, 69, 1088–1090. DOI: 10.1016/j.jpcs.2007.10.054.
[21] Yue, X.; Liu, W.; Chen, Z.; Lin, Z. Simultaneous Removal of
Cu(II) and Cr(VI) by Mg–Al–Cl Layered Double Hydroxide
and Mechanism Insight. J. Environ. Sci. 2017, 53, 16–26. DOI:
10.1016/j.jes.2016.01.015.
[22] Deepa, B.; Philominathan, P. Investigation on the Optical,
Mechanical and Magnetic Properties of Organic NLO Single
Crystal: Pyridine 3-Carboxylic Acid. Optik 2016, 127,
8698–8705. DOI: 10.1016/j.ijleo.2016.06.073.
[23] Mondal, S.; Dasgupta, S.; Maji, K. MgAl- Layered Double
Hydroxide Nanoparticles for Controlled Release of Salicylate.
Mater. Sci. Eng. C 2016, 68, 557–564. DOI: 10.1016/j.msec.2016.
06.029.
[24] Xu, W.; Lin, J. L.; Zhu, H. L.; Hu, F. H.; Zheng, Y. Q.
Synthesis, Crystal Structure and Magnetic Properties of an
Iron(III) Pyridine-2,3,5,6-Tetracarboxylate Complex. Z.
Naturforsch 2011, 66, 465–470. DOI: 10.1515/znb-2011-0505.
[25] Chao, Y. F.; Chen, P. C.; Wang, S. L. Adsorption of 2,4-D on
Mg/Al–NO3 Layered Double Hydroxides with Varying Layer
Charge Density. Appl. Clay Sci. 2008, 40, 193–200. DOI: 10.
1016/j.clay.2007.09.003.
[26] Dhoble, R. M.; Lunge, S.; Bhole, A. G.; Rayalu, S. Magnetic
Binary Oxide Particles (MBOP): a Promising Adsorbent for
Removal of as (III) in Water. Water Res. 2011, 45, 4769–4781.
DOI: 10.1016/j.watres.2011.06.016.
[27] Liang, X.; Zang, Y.; Xu, Y.; Tan, X.; Hou, W.; Wang, L.; Sun, Y.
Sorption of Metal Cations on Layered Double Hydroxides.
Colloids and Surfaces A: Physicochem. Eng. Aspects 2013, 433,
122–131. DOI: 10.1016/j.colsurfa.2013.05.006.
[28] Bekci, Z. M.; Antep, M. K.; Merdivan, M.; Yurdakoç, K.
Zearalenone Removal in Synthetic Media and Aqueous Part of
Canned Corn by Montmorillonite k10 and Pillared
Montmorillonite k10. J. Food Prot. 2011, 74, 954–959. DOI: 10.
4315/0362-028X.JFP-10-317.
[29] Wu, Q.; Li, Z.; Hong, H. Adsorption of the Quinolone
Antibiotic Nalidixic Acid onto Montmorillonite and Kaolinite.
Appl. Clay Sci. 2013, 74, 66–73. DOI: 10.1016/j.clay.2012.09.026.
[30] Bulut, Y.; Aydın, H. A Kinetics and Thermodynamics Study of
Methylene Blue Adsorbtion on Wheat Shells. Desalination
2006, 194, 259–267. DOI: 10.1016/j.desal.2005.10.032.
[31] Bhatia, D.; Datta, D.; Joshi, A.; Gupta, S.; Gote, Y. Adsorption
Study for the Separation of Isonicotinic Acid from Aqueous
Solution Using Activated Carbon/Fe3O4 Composites. J. Chem.
Eng. Data 2018, 63, 436–445. DOI: 10.1021/acs.jced.7b00881.
[32] Shahwan, T. Lagergren Equation: Can Maximum Loading of
Sorption Replace Equilibrium Loading?. Chem. Eng. Res. Des.
2015, 96, 172–176. DOI: 10.1016/j.cherd.2015.03.001.
[33] S.; Wang, S.; Liu, C. H.; Wang, M. K.; Chuang, Y. H.; Chiang,
P. N. Arsenate Adsorption by Mg/Al–NO3 Layered Double
Hydroxides with Varying the Mg/Al Ratio. Appl. Clay Sci.
2009, 43, 79–85. DOI: 10.1016/j.clay.2008.07.005.