Article
Patent Blue V Dye Adsorption by Fresh and Calcined Zn/Al
LDH: Effect of Process Parameters and Experimental
Design Optimization
Aicha Machrouhi 1 , Nawal Taoufik 1 , Alaâeddine Elhalil 2 , Hanane Tounsadi 3 , Zakia Rais 3
and Noureddine Barka 1, *






Citation: Machrouhi, A.; Taoufik, N.;
Elhalil, A.; Tounsadi, H.; Rais, Z.;
Barka, N. Patent Blue V Dye
Adsorption by Fresh and Calcined
Zn/Al LDH: Effect of Process
Parameters and Experimental Design
Optimization. J. Compos. Sci. 2022, 6,
115. https://doi.org/10.3390/
jcs6040115
Academic Editor: Francesco
Tornabene
Received: 3 March 2022
Accepted: 6 April 2022
Published: 11 April 2022
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iations.
Copyright: © 2022 by the authors.
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distributed under the terms and
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Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
J. Compos. Sci. 2022, 6, 115. https://doi.org/10.3390/jcs6040115
1 Multidisciplinary Research and Innovation Laboratory, Sultan Moulay Slimane University of Beni Mellal,
FP Khouribga, 25000 Khouribga, Morocco; machrouhi.aicha90@gmail.com (A.M.);
nawal.taoufik@gmail.com (N.T.)
2 Laboratory of Process and Environmental Engineering, Higher School of Technology,
Hassan II University of Casablanca, 20000 Casablanca, Morocco; elhalil.alaaeddine@gmail.com
3 Laboratoire d’Ingénierie, d’Electrochimie, de Modélisation et d’Environnement,
Faculté des Sciences Dhar El Mahraz, Université Sidi Mohamed Ben Abdellah, 23000 Fes, Morocco;
hananetounsadi@gmail.com (H.T.); raiszakia@yahoo.fr (Z.R.)
* Correspondence: barkanoureddine@yahoo.fr; Tel.: +212-661-66-66-22
Abstract: This work focuses on the adsorptive removal of patent blue V (PBV) dye from aqueous
solution by Zn/Al layered double hydroxide in fresh (LDH) and calcined (CLDH) forms. The
material was synthesized via coprecipitation and samples were characterized by XRD, FTIR and
TGA-DTA. Dye retention was evaluated under different experimental conditions of contact time,
pH, adsorbent dosage, temperature and initial dye concentration. Experimental results show that
highest adsorption capacity occurred at acidic medium. Kinetics data were properly fitted with
the pseudo-second-order model. Equilibrium data were best correlated to Langmuir model with
maximum monolayer adsorption capacities of 185.40 and 344.37 mg/g, respectively, for LDH and
CLDH. The process was endothermic and spontaneous in nature. Based on the preliminary study,
full factorial experimental design (24 ) was used for the optimization of the effect of solution pH,
adsorbent dose, initial dye concentration and the calcination. Thus, the optimal conditions to reach
high equilibrium adsorption capacity were achieved at pH of 5, adsorbent dosage of 0.1 g/L, and
initial dye concentration of 15 mg/L by CLDH.
Keywords: patent blue V; calcined LDH; sequestration; experimental design
1. Introduction
Water is an essential substance for daily life. Due to the expansion of industrial, agri-
cultural and domestic activities, this substance is highly contaminated by industrial sludge,
heavy metals, pesticides, organic dyes and other chemicals. This results in serious diseases
affecting biomes and biota. According to the UNESCO World Water Assessment Program
(WWAP), 100 million people, 1 million sea birds and 1 lakh marine mammals die each year
due water pollution [1]. As ones of the most water polluting industries, textile and paper
industries emit many organic dyes during the coloring process [2]. Even a tiny amount
of these dyes can affect the quality of water. Among the dyes, patent blue V from the
class of azo dyes is commonly used in cosmetic and food industry, which provides direct
contact with human body. It is known to cause headache, asthma and allergic reactions [3,4].
However, various technologies are used in the treatment of wastewaters containing the
excess level of dyes, including photodegradation [5], chemical coagulation [6], biodegrada-
tion [7], catalytic reduction [8] and electro-chemical treatment [9]. Among these processes,
adsorption is proven to be one of the most attractive and effective techniques [10]. There-
fore, several materials have attracted considerable attention as adsorbents in dye removal
https://www.mdpi.com/journal/jcs
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 2 of 16

J. Compos. Sci. 2022, 6, 115 2 of 14

[9]. Among these processes, adsorption is proven to be one of the most attractive and
effective techniques [10]. Therefore, several materials have attracted considerable
attention as adsorbents in dye removal applications. Layered double hydroxides (LDH)
applications. Layered double hydroxides (LDH) or anionic clays are known by their high
or anionic clays are known by their high retention capacity for anionic dyes [11] and are
retention capacity for anionic dyes [11] and are easily synthesized, less expensive, regen-
easily synthesized, less expensive, regenerable, large surface area, super anion exchange
erable, large surface area, super anion exchange capacity and environmental friendliness.
capacity and environmental friendliness. These compounds can be described by the
These compoundsIIcan be described by the general formula:II[MII 1−x MIII x (OH)2 ]x+ .(An− x/n ).
general formula: [MII 1−xM x(OH)2] .(A x/n). mH2O, where
III x+ n− M represents a2+ divalent cation
mH O, where M represents a divalent cation (Mg2+ , Zn2+ , Ni2+ , Mn , Fe2+ . . . ), MIII
(Mg2+, 2Zn2+, Ni2+, Mn2+, Fe2+ …), MIII 3+ represents
3+ a3+trivalent
3+ cation
3+ (Al3+, Cr
n
3+, Fe3+, Co3+, Mn3+
−
represents a trivalent cation (Al − , Cr− , Fe − , Co 2− , Mn . . . ), A the compensating
…), An− the compensating anion (Cl , NO 3, ClO 4, CO 3…), n the charge of the anion, and
anion (Cl− , NO− 3 , ClO− 4 , CO2− 3 . . . ), n the charge of the anion, and m is the number of
m is the number of water molecules located in the interlayer region together with the
water molecules located in the interlayer regionIIItogether with the anion. The coefficient, x,
anion. The coefficient, x, isIII the molar fraction, [M /(MII + MIII)] [12].
is the molar fraction, [M /(MII + MIII )] [12].
The main purpose of this work was to evaluate the potential of fresh and calcined
The main purpose of this work was to evaluate the potential of fresh and calcined
Zn/Al
Zn/AlLDHLDH as as
adsorbent
adsorbent forfor
thethe
removal
removal of ofPBVPBV dye from
dye from aqueous
aqueous solution.
solution. Various
Various
factors such as contact time, solution pH, adsorbent dose, temperature
factors such as contact time, solution pH, adsorbent dose, temperature and initial and initial dyedye
concentration were studied. This paper also investigated the combined
concentration were studied. This paper also investigated the combined effect of the most effect of the most
influencing
influencingparameters,
parameters,whichwhich areare
solution
solution pH,pH,adsorbent
adsorbent dose, initial
dose, dye
initial concentration
dye concentration
and nature of adsorbent. Full factorial experimental design with
and nature of adsorbent. Full factorial experimental design with two levels two levels (24(2
) was used
4 ) was used
to to
acquire the optimal conditions for high removal
acquire the optimal conditions for high removal efficiency. efficiency.

2. Materials and
2. Materials Methods
and Methods
AllAllused
usedchemicals
chemicals were of ofanalytical
analyticalgrade
grade
andand
werewere
usedused without
without furtherfurtherpurifica-
purification. Zinc nitrate
tion. Zinc nitrate (Zn(NO (Zn(NO
)
3 2 · 6H 3
2 )
O)2 •6H
( ≥ O)
99%),
2 (≥99%), aluminum
aluminum nitrate nitrate
(Al(NO (Al(NO
)
3 3 · 9H 23 )
O) 3.9H O)
(≥298%),
sodium carbonate (Na2 CO3 ) (99.5–100.5%), sodium hydroxide (NaOH) (≥99%), hydrochlo-
(≥98%), sodium carbonate (Na 2 CO 3 ) (99.5–100.5%), sodium hydroxide (NaOH) (≥99%),
hydrochloric
ric acid (HCl)acid (HCl)
(37%), (37%),
sodium sodium
chloride NaClchloride
(99.5%)NaCl (99.5%)
and patent blueand
V (Cpatent
27 H31 Nblue 2 NaOV7 S2 )
(100%)
(C27 were7Sobtained
H31N2NaO 2) (100%)from
wereSigma-Aldrich (Germany). Bidistilled
obtained from Sigma-Aldrich (Germany).water was used
Bidistilled as the
water
wassolvent
used asthroughout
the solventthis study. The
throughout thischaracteristics and chemicaland
study. The characteristics structure
chemical of structure
the dye are
of listed
the dyein are
Table 1. in Table 1.
listed

Table
Table 1. Molecular
1. Molecular structure
structure andand physical
physical characteristics
characteristics of of patent
patent blue
blue V.V.

Name
Name Molecular Structure
Molecular Structure MWW(g/mol)
M (g/mol) λmax
λmax (nm)
(nm)

Patent
Patentblue
blueVV
582.66
582.66 637
637
(Acidblue
(Acid blue3)
3)

LDH LDH was

wassynthesized
synthesized by by several
severalauthors
authors previously,
previously, usingusing the coprecipitation
the coprecipitation method
method at constant pH [12,13]. A mixture solution of Zn(NO 3)2.6H2O and Al(NO3)3.9H2O
at constant pH [12,13]. A mixture solution of Zn(NO3 )2 ·6H2 O and Al(NO3 )3 ·9H2 O with a
with a total
total concentration
concentration of metal
of metal ionsand
ions (Zn (ZnAl)andofAl) of 2 mol/L
2 mol/L and NaandCO Na2CO 3 (1 mol/L) was
2 3 (1 mol/L) was added
added
drop-wise in a backer containing 50 mL of bidistilled water. The pH of the of
drop-wise in a backer containing 50 mL of bidistilled water. The pH the mixture
mixture solution
solution was adjusted and kept constant at 8.5 ± 0.2 during the
was adjusted and kept constant at 8.5 ± 0.2 during the synthesis by addition synthesis by addition of
of suitable
suitable amounts of NaOH solution (2 mol/L). The formed gel was
amounts of NaOH solution (2 mol/L). The formed gel was stirred vigorously for 4 h andstirred vigorously for
4 hthen
andtransferred
then transferred
into aninto an autoclave
autoclave and hydrothermally
and hydrothermally treated attreated
75 ◦ C at
for75
16°Ch. for 16 h.the
Finally,
Finally, the precipitate
precipitate was washed wasseveral
washed several
times withtimes with deionized
deionized water until water until thewas
the solution solution
neutral
was neutral and ◦
dried at 100 °C for 24 h. The resulting product (LDH)
and dried at 100 C for 24 h. The resulting product (LDH) was ground into fine powder was ground into
and
fine powder and stored in sample bottle for further use. Part of the resulting
stored in sample bottle for further use. Part of the resulting material was calcined at 500 material was◦ C
calcined at 500 furnace
in a tubular °C in a tubular
for 6 h tofurnace
obtainfor 6 h toPowder
CLDH. obtain CLDH. PowderofXRD
XRD patterns patterns were
the samples of
therecorded
samplesinwere recorded
2θ range from in
5 to2θ ◦
70range
at roomfrom 5 to 70° atonroom
temperature a D2 temperature on a D2
PHASER diffractometer,
PHASER
using CuKαdiffractometer,
radiations using
with 30CuKα
KV andradiations
10 mA.with FT-IR30spectra
KV and were10 recorded
mA. FT-IR in spectra
the range
of 4000 to 400 cm−1 using a Perkin Elmer (FTIR-2000) spectrophotometer. The sample
was prepared by finely mixing 1 mg of adsorbent with 100 mg of KBr to prepare pellet.
J. Compos. Sci. 2022, 6, 115 3 of 14

Thermogravimetric and differential thermal analysis (TGA-DTA) curves were recorded on

a SETARAM (SENSYSevo) instrument, in the temperature range from 30 to 700 ◦ C with a
heating rate of 10 ◦ C/min under argon atmosphere. The pH of point of zero charge (pHpzc)
was determined according to the method described by Noh and Schwarz [14]. The pH of
NaCl aqueous solution (50 mL at 0.01 mol/L) was adjusted to successive initial values in
the range of 2–12 by addition of HNO3 and/or NaOH. Moreover, 0.05 g of each biosorbent
was added in the solution and stirred for 6 h. The final pH was measured and plotted vs.
the initial pH. The pHpzc was determined at the value for which pHfinal = pHinitial .
Adsorption experiments were conducted at different conditions by adding different
dosages (0.05–0.8 g/L) of LDH or CLDH to 100 mL of dye solution of predetermined
concentrations (15–150 mg/L). The initial solution pH was varied in the range of 3–12, the
contact time was in the range of 2–120 min, and temperature was in the range of 25–55 ◦ C.
After each adsorption experiment completed, the solid phase was separated from the
liquid phase by centrifugation at 3000 rpm for 10 min. Then, the dye concentration was
determined using a TOMOS V-1100 UV type Spectrophotometer.
The adsorption yield (%Removal) of the dye and the adsorption capacity (q (mg/g))
were evaluated by the following equations:

%Removal = ((C0 − C)/C0 ) ∗ 100 (1)

q = (C0 − C)/R (2)

where C0 and C are respectively initial and residual dye concentration a time t (mg/L), and
R is the adsorbent dosage (g/L).
Based on the effect of each individual factor, the most influencing factors were used
for the optimization of the process by experimental design. Table 2 shows the four factors
used and their levels. The experiments were performed according to a full factorial design
at two levels (24 ), with 16 experiments. The adsorption behavior was optimized by using a
first-order polynomial model (Equation (3)):

Y = b0 + b1 A + b2 B + b3 C + b4 D + b12 AB + b13 AC + b14 AD + b23 BC + b24 BD +

(3)
Yb34 CD + b123 ABC + b124 ABD + b134 ACD + b234 BCD + b1234 ABCD

where, Y is the response of interest (adsorption capacity of PBV dye).

Table 2. Process factors and their levels.

Factors Levels
Low (−) High (+)
A. Adsorbent dosage (mg/g) 0.1 0.3
B. Solution pH 5 7
C. Dye concentration (mg/L) 15 30
D. Nature of adsorbent LDH CLDH

3. Results and Discussion

3.1. Characterization
3.1.1. X-ray Diffraction (XRD) Study
The XRD patterns of the fresh and calcined Zn-Al-LDH are shown in Figure 1. The
figure exhibits the characteristic reflections of the LDH structure for fresh sample with
planes (003), (006), (012), (015), (018), (110) and (113). Remarkable changes were observed
after calcination at 500 ◦ C. The lamellar structure collapsed and new peaks corresponding
to ZnO oxide started to appear indicated by the peaks at 2θ = 31.8◦ , 34.5◦ , 36.3◦ , 47.6◦ , 56.6◦ ,
62.9◦ , 66.4◦ , 68◦ and 69.1◦ . These peaks correspond to the reflections from (100), (002), (101),
(102), (110), (103), (200), (112) and (201) planes, respectively. This is also confirmed by the
JCPDS data (Card No. 36-1451) [15].
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 4 of 16
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 4 of 16

56.6°, 62.9°, 66.4°, 68° and 69.1°. These peaks correspond to the reflections from (100),
56.6°,(101),
(002), 62.9°,(102),
66.4°,(110),
68° and 69.1°.
(103), These
(200), (112)peaks
and correspond
(201) planes,torespectively.
the reflections from
This (100),
is also
J. Compos. Sci. 2022, 6, 115 4 of 14
(002), (101), (102), (110), (103), (200), (112)
confirmed by the JCPDS data (Card No. 36–1451) [15]. and (201) planes, respectively. This is also
confirmed by the JCPDS data (Card No. 36–1451) [15].

Figure 1. XRD patterns of LDH material before and after calcination at 500 °C.
Figure1.1.XRD
Figure XRDpatterns
patternsof
ofLDH
LDHmaterial
materialbefore
beforeand
andafter
aftercalcination 500◦°C.
calcinationatat500 C.
3.1.2.
3.1.2.Fourier Transform Infrared (FTIR) Analysis
3.1.2. Fourier
Fourier Transform
TransformInfrared
Infrared(FTIR)
(FTIR)Analysis
Analysis
Figure
Figure 2 2shows
shows the
theFTIR
FTIR spectra
spectra of
of LDH
LDH before
before and after
and after calcination.
calcination.The Thespectrum
spectrumof
ofthe Figure
thefresh
fresh LDH 2 shows
shows the
a FTIR spectra
broad band of LDH
between before
3600 and and
3200 after
cm calcination.
−1
− ,1 which is The spectrum
attributed toto
LDH
ofstretching
the fresh LDHshows a broad
shows athe
broad band
bandbetween
between 36003600and 3200
and 3200cmcm−1, ,which
which isisattributed
attributed to
the
the stretching vibration
vibration ofof theOHOH groups
groups of physically
of physically adsorbed
adsorbed andandinterlamellar
interlamellar water
water
the stretching
molecules vibration of the OH groups of physically adsorbed and interlamellar water
molecules[16].[16].Another
Anothercommon
commonband bandforforthe
theLDHLDHmaterials
materialsisisfound
foundatatabout
about1600 1600cm
cm−, −1
−1 1
,
molecules
attributed [16]. Another common band for the LDH materials is found at about 1600cm1−1is,
cm
attributedtotothe theO-H
O-Hbending
bending vibrations
vibrations of of water
water molecules
molecules[16]. [16].TheTheband
bandatat13641364cm −
attributed
isassigned
assignedto toto thestretching
the O-H bending vibrations
vibration of the of
COwater
the CO molecules [16].
2−−groups The band at[16]. 1364 cm−1
the stretching vibration of 3
32 groupsininthe theLDH
LDHinterlayer
interlayer [16].ThisThis
is assigned
band rapidly to the stretching
disappears after vibration
calcination ofdue
the COto 3 groups in the LDH interlayer [16]. This
2−
the thermal decomposition of carbonate
band rapidly disappears after calcination due to the thermal decomposition of carbonate
band rapidly
ions. disappears after calcination
−could due to the thermal decomposition of carbonate
ions.Bands
Bandsaround
around700–400
700–400cm cm−1 1 couldbeberelated
related toto the
thelattice
latticevibration
vibrationmodes modessuchsuchasas
theions. Bands
translation around 700–400
vibrations by M-Ocm −1 could be related to the lattice vibration modes such as
(590 and 670 cm −1−
) and
1 O-M-O (430 cm −1) −
[17,18].
1
the translation vibrations by M-O (590 and 670 cm −1 ) and O-M-O (430 cm−1 ) [17,18].
the translation vibrations by M-O (590 and 670 cm ) and O-M-O (430 cm ) [17,18].

FTIRspectra
Figure2.2.FTIR spectraofofLDH
LDHmaterial
materialbefore
beforeand
andafter
aftercalcination
calcinationatat500 ◦ C.
500°C.
Figure
Figure 2. FTIR spectra of LDH material before and after calcination at 500 °C.
3.1.3. Thermal Analysis (TGA-DTA)
3.1.3. Thermal Analysis (TGA-DTA)
3.1.3.The thermal
Thermal decomposition
Analysis (TGA-DTA) of the LDH was investigated by TGA-DTA analysis.
The
According thermal decomposition
to the literature, of the LDH was
the decomposition of investigated
LDH includesby TGA-DTA
three analysis.
main stages which
AccordingThe thermal
to the decomposition
literature,water, of the
the decomposition LDH was investigated
of LDHofincludes by
three TGA-DTA
main stages analysis.
which
are the loss
According of adsorbed
toadsorbed
the literature, the the decomposition H
includes three main stages .which
2 O, OH and finally CO 3 The
are the loss of
TGA-DTA curves of water,
LDH thedecomposition
decomposition
material obtained
ofofLDH
shown Hin
2O, OH and finally CO3. The TGA-
Figure 3 are quite similar to those
DTAare the loss of
curves of adsorbed water,obtained
LDH research
material the decomposition in of H2O, 3OH areand finally CO3. to
The TGA-
reported
DTA in previous
curves of LDH works
material [19].shown
obtained The TGA-DTA
shown in
Figurecurves
Figure 3 ofquite
are quite
similar
synthesized LDH
similar
those
to show
those
reported
areportedin previous
first mass at ∼research
◦ C, works [19]. The TGA-DTA tocurveslossofof
synthesizedwater.
LDH show
in loss
previous 100
researchwhich
workscan be
[19]. accredited
The TGA-DTA the
curves of adsorbed
synthesized LDHItshow was
followed by a second more pronounced and sharp endothermic phenomenon around 160
to 240 ◦ C. This mass loss was due to loss of hydration water from the interlayer region. A
third step, extending up to 320 ◦ C, is assigned to the overlapped mass losses due to the
dehydroxylation of the layers and the decomposition of the carbonates.
 a first mass loss at∼100 °C, which can be accredited to the loss of adsorbed water. It was
followed by a second more pronounced and sharp endothermic phenomenon around 160
to 240 °C. This mass loss was due to loss of hydration water from the interlayer region. A
J. Compos. Sci. 2022, 6, 115 third step, extending up to 320 °C, is assigned to the overlapped mass losses due to5theof 14

dehydroxylation of the layers and the decomposition of the carbonates.

Figure
Figure3.3.TGA/DTA
TGA/DTAcurve ofof
curve LDH material.
LDH material.

3.2.Dye
3.2. DyeRemoval
Removal from
fromAqueous
AqueousSolution
Solution
3.2.1. Effect of Solution pH
3.2.1. Effect of Solution pH
The effect of solution pH on the removal of PBV was investigated in a pH range
The effect of solution pH on the removal of PBV was investigated in a pH range
varying from 3 to 12 as shown in Figure 4. It was observed that the highest adsorption was
varying from 3 to 12 as shown in Figure 4. It was observed that the highest adsorption
obtained in the pH range of 3 to 5 and then continually decreased with pH increase. The pH
was obtained in the pH range of 3 to 5 and then continually decreased with pH increase.
change would directly affect the negatively and positively charged site distribution profile
The
on the pHsurface
change would
of the directly The
adsorbents. affect
pH the
pointnegatively and (pHpzc)
of zero charge positively charged
of the site
adsorbents
distribution profile on the surface of the adsorbents. The pH point of zero charge
and the pKa value of dye molecule are important factors controlling this behavior. The pKa (pHpzc)
ofofthe
PBV adsorbents and the pKa
is 2.78, displaying thatvalue of dye
the dye molecule
molecules are important
present factorsanions
as monovalent controlling this
in solution
behavior. The pKa of PBV is 2.78, displaying that the dye molecules present
in the studied pH range. The pHpzc of adsorbents were 7.47 and 8.1 for LDH and CLDH, as monovalent
anions in solution
respectively. in the at
Therefore, studied pH range.
pH > pHpzc The pHpzc
the surface of is
charge adsorbents were 7.47 and
negative, disfavoring the8.1 for
anions
LDH and CLDH, respectively. Therefore, at pH > pHpzc the surface
forms of dye molecules adsorption. At pH < pHpzc, the surface of adsorbents becomes charge is negative,
disfavoring
more positivelythe anions
chargedforms of dyetomolecules
leading an increaseadsorption.
in the dyeAt pH < pHpzc,
removal due to the surface of
strengthening
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 6 of 16
adsorbents
attractive forces among the positive charge of the surface of the adsorbents andremoval
becomes more positively charged leading to an increase in the dye negative
due
chargeto strengthening attractive forces among the positive charge of the surface of the
of the dye molecules.
adsorbents and negative charge of the dye molecules.
140
CLDH
120
LDH
100
qe (mg/g)

80
60

40
20
0
0 2 4 6 8 10 12
pH
Figure
Figure4.4.Effect
EffectofofpH
pHon
onthe
theadsorption
adsorptionofofPBV:
PBV:C0C=0 15 mg/L,
= 15 R =R0.1
mg/L, g/L,g/L,
= 0.1 agitation timetime
agitation = 2 h,= T2 =h,
25 °C. ◦
T = 25 C.

3.2.2.Effect
3.2.2. Effectof
ofAdsorbent
AdsorbentDosage
Dosage
Figure55represents
Figure representsthe
theeffect
effect
of of adsorbent
adsorbent dosage
dosage on PBV
on PBV removal
removal by fresh
by fresh and
and cal-
calcined LDH. The figure shows that the effectiveness of retention increases with
cined LDH. The figure shows that the effectiveness of retention increases with the increase the
of adsorbent dosage from 0.05 g/L to a value of 0.4 g/L, where it shows a plateau. This
result is due to the fact that the increase in the adsorbents dosage increases the number of
adsorption sites available for non-adsorbed dye molecules. The figure also shows that the
removal efficiency does not reach 100% despite the continuous increase of adsorbent dos-
 pH
Figure 4. Effect of pH on the adsorption of PBV: C0 = 15 mg/L, R = 0.1 g/L, agitation time = 2 h, T =
25 °C.

J. Compos. Sci. 2022, 6, 115 3.2.2. Effect of Adsorbent Dosage 6 of 14

Figure 5 represents the effect of adsorbent dosage on PBV removal by fresh and cal-
cined LDH. The figure shows that the effectiveness of retention increases with the increase
of adsorbent
increase dosage from
of adsorbent 0.05
dosage g/L0.05
from to ag/Lvalue
to aofvalue
0.4 g/L, where
of 0.4 g/L, it shows
where a plateau.
it shows This
a plateau.
result is dueisto
This result duethetofact
thethat
fact the
thatincrease in the
the increase inadsorbents
the adsorbentsdosage increases
dosage the the
increases number
numberof
adsorption
of adsorption sitessites
available for non-adsorbed
available for non-adsorbed dyedyemolecules. The The
molecules. figure also also
figure shows that that
shows the
removal efficiency
the removal doesdoes
efficiency not reach 100%100%
not reach despite the continuous
despite the continuousincrease of adsorbent
increase dos-
of adsorbent
age behind
dosage 0.4 g/L.
behind This suggests
0.4 g/L. low to
This suggests lowmoderate interaction
to moderate of theofadsorbents
interaction by the
the adsorbents bydye
the
molecules at low
dye molecules atconcentration
low concentrationin solution. FromFrom
in solution. the figure, it canitbe
the figure, canalso
be concluded that
also concluded
the
thataffinity of PBV
the affinity dye to
of PBV CLDH
dye is greater
to CLDH than than
is greater that of fresh
that LDH.LDH.
of fresh

100

80
% Removal

60

40
CLDH

20 LDH

0
0 0.2 0.4 0.6 0.8
R (g/L)
Figure
Figure5.5. Effect
Effect of
of adsorbent
adsorbent dosage
dosage on
on the
the adsorption
adsorption of
of PBV:
PBV: C00 == 15
15 mg/L,
mg/L,agitation
agitationtime
time==22h,h,
initial
initialpH
pH==5.68
5.68and
andTT==25 ◦ C.
25°C.

3.2.3.Adsorption
3.2.3. AdsorptionKinetics
Kinetics
Contacttime
Contact timeisisan
animportant
importantdesign
designparameter
parameteron onwhich
whichdepends
dependsadsorption
adsorptionprocess
process
as it provides information about the dynamic of the reaction in terms
as it provides information about the dynamic of the reaction in terms of order and ofof order and ofthe
the
rate constant. As shown in Figure 6, the removal capacity of PBV by CLDH
rate constant. As shown in Figure 6, the removal capacity of PBV by CLDH and LDH both and LDH both
exhibited aa rapid
exhibited rapid increase
increaseininthe thefirst
first1010
min
minof of
reaction time,
reaction then,
time, gradually
then, increased
gradually until
increased
reaching equilibrium at 30 min. Adsorption kinetics data were analyzed
until reaching equilibrium at 30 min. Adsorption kinetics data were analyzed using using pseudo-first-
order model (Equation
pseudo-first-order model (4))(Equation
[20] and pseudo-second-order model (Equation
(4)) [20] and pseudo-second-order model(5)) (Equation
[21].
(5)) [21].
q = qe (1 − e−K1t ) (4)

q = (K2 qe 2 t)/(1 + K2 qe t) (5)

where qe and q (both in mg/g) are, respectively, the amounts of dye adsorbed at equilibrium
and at any time t (min), k1 (1/min) is the rate constant of pseudo-first-order model and k2
(g/mg min) is the rate constant of pseudo-second-order model.
Parameters of the pseudo-first-order and pseudo-second-order models were estimated
with the aid of the nonlinear regression. The obtained data and the correlation coefficients,
r2 , are given in Table 3. The Table indicates that the r2 values are higher and closer to 1 for
the pseudo-second-order model compared to those of the pseudo-first-order model. The
calculated equilibrium values (qcal ) of the pseudo-second-order model are consistent with
the experimental data. This result suggests that the adsorption of PBV onto LDH and CLDH
could be better described by the pseudo-second-order model instead of pseudo-first-order
kinetic model.
 Pseudo First-Order Pseudo Second-Order
Adsorbent qexp(mg/g)
qcal (mg/g) K1(1/min) r2 qcal(mg/g) K2(g/mg min) r2
CLDH 99.36 94.52 0.347 0.991 101.47 0.005 0.998
LDH 49.48 47.47 0.368 0.959 50.83 0.012 0.990
J. Compos. Sci. 2022, 6, 115 7 of 14

120 (a) 60 (b)

100 50

80 40
qe (mg/g)

qe (mg/g)
60 30
Experimental point Experimental point
40 Pseudo first order 20 Pseudo first order
Pseudo second order Pseudo second order
20 10

0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
t (min) t (min)

Figure 6. Adsorption kinetics of PBV by (a) CLDH and (b) LDH: C = 15 mg/L, R = 0.1 g/L, initial
Figure 6. Adsorption ◦kinetics of PBV by (a) CLDH and (b) LDH: C0 0 = 15 mg/L, R = 0.1 g/L, initial pH
pH = 5.52 and T = 25 C.
= 5.52 and T = 25 °C.
Table 3. Kinetics models constants for PBV adsorption by CLDH and LDH.
3.2.4. Adsorption Isotherms
Pseudo First-Order
Adsorption isotherm plays a crucial role in Pseudo Second-Order
analyzing the adsorption capacity of ma-
Adsorbent qexp (mg/g)
terials
qcal and providing
(mg/g) informationrabout solution-surface
K1 (1/min) 2 qcal (mg/g) interaction.
K2 (g/mg min)The adsorption
r2 ca-
CLDH 99.36 pacities of
94.52 LDH and CLDH
0.347 with increasing
0.991 the
101.47initial dye concentration
0.005 are shown
0.998 in
LDH 49.48 Figure47.47
7. The figure0.368
indicates that the adsorbed
0.959 50.83amounts of PBV 0.012increased with
0.990the in-
crease in equilibrium dye concentration. It’s evident that high concentration in solution
implicates high dye
3.2.4. Adsorption molecule fixed at the surface of the adsorbent. However, when the
Isotherms
equilibrium concentration exceeded 60 mg/L, the adsorbents reached a saturated state.
Adsorption isotherm plays a crucial role in analyzing the adsorption capacity of
Obtained equilibrium data were analyzed using Langmuir (Equation (6)) [22] and Freun-
materials and providing information about solution-surface interaction. The adsorption
dlich (Equation
capacities (7)) and
of LDH [23] CLDH
isotherm models.
with increasing the initial dye concentration are shown
in Figure 7. The figure indicates that the adsorbed amounts of PBV increased with the
qe = (qm KL Ce)/(1 + KL Ce) (6)
increase in equilibrium dye concentration. It’s evident that high concentration in solution
implicates high dye molecule fixed at the surface of the adsorbent. However, when the
equilibrium concentration exceeded 60 mg/L, the adsorbents reached a saturated state. Ob-
tained equilibrium data were analyzed using Langmuir (Equation (6)) [22] and Freundlich
(Equation (7)) [23] isotherm models.

qe = (qm KL Ce )/(1 + KL Ce ) (6)

qe = KF Ce 1/n (7)
where qm (mg/g) is the Langmuir maximum monolayer adsorption capacity, KL (L/mg) is
the Langmuir equilibrium constant related to the adsorption affinity, KF (mg1−1/n g−1 L1/n )
is the Freundlich constant related to the adsorption capacity and n is the heterogeneity
factor related to the adsorption intensity.
The fitting parameters and correlation coefficient values (r2 ) are all listed in Table 4.
According to the r2 values, the more suitable model for this system is the Langmuir model.
This result indicates that the adsorption processes is more likely to be homogeneous
and monolayer. The obtained qm values indicate that the adsorption capacity of CLDH
(344.37 mg/g) is much higher than of LDH (185.40 mg/g). In addition, KL value obtained
for CLDH is higher compared to that obtained for LDH, which confirm the high affinity
of PBV dye to calcined LDH. This increase in the adsorption capacity of LDH with cal-
cination could be attributed to the reconstruction phenomena. The calcination of LDH
structure leads to the decomposition of the carbonate anion CO3 2− in the interlayer space
and the formation of mixed oxides with memory effect. When these mixed oxides are
 Table 4. Isotherm models constants calculated for PBV adsorption by Fresh and calcined LDH.

Langmuir Freundlich
Adsorbent
J. Compos. Sci. 2022, 6, 115 qm(mg/g) KL(L/mg) r2 KF (mg1–1/n/g.L−1/n) n 8 ofr14
2

CLDH 344.37 0.074 0.993 83.231 3.487 0.943

LDH 185.40 0.057 0.967 41.608 3.453 0.906
hydrated in solution, they reconstruct LDH structure by intercalation of dye molecules in
its intermalleolar space [24].

350 (a) 180

(b)
300
150
250
120

qe(mg/g)
qe(mg/g)

200
Experimental point 90
150 Experimental point
Langmuir fit
100 Freundlich fit 60 Langmuir fit
Freundlich fit
50 30

0 0
0 25 50 75 100 125 0 30 60 90 120 150
Ce(mg/L) Ce(mg/L)

Figure 7. Experimental points and nonlinear fitted isotherm curves of PBV adsorption by (a) CLDH
Figure 7. Experimental points and nonlinear fitted isotherm curves of PBV adsorption by (a)
and (b)and
CLDH LDH:
(b)RLDH:
= 0.1 R
g/L, agitation
= 0.1 time = 2time
g/L, agitation h, initial
= 2 h,pH = 5.62
initial pHand 25 ◦ C.
T = and
= 5.62 T = 25 °C.
Table 4. Isotherm models constants calculated for PBV adsorption by Fresh and calcined LDH.
3.2.5. Effect of Temperature
The changesLangmuir
observed in the adsorption of PBV by Freundlich
varying solution temperature in
Adsorbent 2 1–1/n /g·it 2
the range of 25–55 qm °C are shown
(mg/g) in Figurer8. FromKthe
KL (L/mg) figure,
F (mg L−can
1/n ) be seen
n that rthe ad-
sorption
CLDH yield was enhanced
344.37 by rise
0.074 in temperature.
0.993 Thermodynamic
83.231 parameters;
3.487 0.943ΔH°,
ΔG°, and
LDHΔS° were applied to 0.057
185.40 assess the 0.967
spontaneity and heat exchange3.453
41.608 during0.906
the ad-
sorption process. They were calculated using the following equation:
3.2.5. Effect of Temperature
LnKD = − ΔG°/RT = − ΔH°/RT + ΔS°/R (8)
The changes observed in the adsorption of PBV by varying solution temperature in the
range of 25–55 ◦ C are shown in Figure 8. From the figure, it can be seen that the adsorption
yield was enhanced by rise in temperature. Thermodynamic parameters; ∆H◦ , ∆G◦ , and
∆S◦ were applied to assess the spontaneity and heat exchange during the adsorption
process. They were calculated using the following equation:

LnKD = −∆G◦ /RT = −∆H◦ /RT + ∆S◦ /R (8)

where KD is the distribution constant of dye between solid phase and liquid phase (qe /Ce ),
R is the universal gas constant (8.314 J/mol K), T is solution temperature in K, ∆G◦ is the
Gibbs free energy, ∆S◦ is the entropy, and ∆H◦ is enthalpy. ∆S◦ and ∆H◦ were estimated
from the slope and intercept of the plot of lnKD vs. 1/T yields.
The calculated parameters are illustrated in Table 5. The negative values of ∆G◦ and
positive values of ∆S◦ imply that the removal process of PBV on both LDH and CLDH
is feasible and spontaneous. Meanwhile, ∆H◦ > 0 further demonstrates the endothermic
nature of the process. Additionally, the values of ∆H◦ are lower 40 kJ/mol, suggesting
physical adsorption process.

J. Compos. Sci. 2022, 6, 115
Gibbs free energy, ΔS° is the entropy, and ΔH° is enthalpy. ΔS° and ΔH° were estimated
from the slope and intercept of the plot of lnKD vs. 1/T yields.
The calculated parameters are illustrated in Table 5. The negative values of ΔG° and
positive values of ΔS° imply that the removal process of PBV on both LDH and CLDH is
feasible and spontaneous. Meanwhile, ΔH° > 0 further demonstrates the endothermic na-
ture of the process. Additionally, the values of ΔH° are lower 40 kJ/mol, suggesting phys-
9 of 14
ical adsorption process.

120
100
80

qe (mg/g)
60
40
LDH-500°C
20
LDH
0
20 30 40 50 60
T(°C)
Figure
Figure8.8.Effect
Effectof
oftemperature
temperature on
on the
the adsorption
adsorption of PBV by CLDH and LDH:
LDH: C
C00 == 15
15 mg/L,
mg/L,agitation
agitation
time
time==22h,h,initial
initialpH
pH==5.57
5.57and
andRR==0.1
0.1g/L.
g/L.

Table 5.
Table Thermodynamic parameters
5. Thermodynamic parameters of
of the
the adsorption
adsorption of
of PBV
PBV by
by CLDH
CLDH and
and LDH.

Adsorbent
Adsorbent T(K)
T (K) KDKD ΔG° ◦ (kJ/mol)
∆G(kJ/mol) ∆H ◦(kJ/mol)
ΔH° (kJ/mol) ∆S◦(J/K.mol)
ΔS° (J/K·mol)
CLDH
CLDH 298
298 16.48
16.48 −6.94
−6.94 11.67
11.67 62.41
62.41
308
308 18.36
18.36 −7.46
−7.46
318
318 21.06
21.06 −8.09
−8.09
328 25.31 −8.82
328 25.31 −8.82
LDH
LDH 298
298 4.79
4.79 −3.89
−3.89 13.71
13.71 59.01
59.01
308 6.10 −4.63
308
318 6.10
6.64 −4.63
−5.01
318
328 6.64
8.18 −5.01
−5.73
328 8.18 −5.73
3.3. Process Optimization
3.3. Process
3.3.1. Optimization
Experimental Results
3.3.1. The
Experimental Results
experimental results obtained at the designed conditions according to the full
factorial
The experimental design results are presented
obtained at thein Table 6. According
designed conditions toaccording
the table, the highest
to the full
adsorption capacity of 92.2 mg/g was obtained by CLDH at initial dye
factorial experimental design are presented in Table 6. According to the table, the highest concentration
of 15 mg/L,
adsorption pH of 5,
capacity of and adsorbent
92.2 mg/g dosage of
was obtained by0.1 g/L.atStatistical
CLDH initial dyeanalysis was used
concentration to
of 15
determine
mg/L, pH ofa 5,
well-fitted regression
and adsorbent dosagemodel.
of 0.1Values of the main
g/L. Statistical effectswas
analysis of individual variables
used to determine
aand their interaction
well-fitted regressioneffects
model.obtained
Values of are
thepresented in Table
main effects 7. From variables
of individual the table,and
it can be
their
observed that
interaction the calcination
effects obtained are of presented
LDH has ain positive effect
Table 7. From onthe
PBV adsorption.
table, it can beMeanwhile,
observed
the the
that other remaining
calcination of individual terms present
LDH has a positive a negative
effect on effect onMeanwhile,
PBV adsorption. the adsorption. The
the other
analysis of the interaction effects shows that the most significant interaction
remaining individual terms present a negative effect on the adsorption. The analysis of was between
adsorbent
the dosage
interaction andshows
effects initial dye
thatconcentration with a positive
the most significant effect
interaction was(b13 = +4.93),
between followed
adsorbent
by the interaction between adsorbent dosage and the nature
dosage and initial dye concentration with a positive effect (b13 = +4.93), of LDH (b = − 6.93).
14 followed by the
interaction between adsorbent dosage and the nature of LDH (b14 = −6.93).
Table 6. Factorial experimental design matrix in coded and real values and experimental results.

Coded Values Actual Values

Run qe (mg/g)
A B C D A B C D
1 −1 −1 −1 −1 5 0.1 15 LDH 48.62
2 −1 1 −1 −1 5 0.3 15 LDH 32.36
3 1 −1 −1 −1 7 0.1 15 LDH 26.67
4 1 1 −1 −1 7 0.3 15 LDH 20.45
5 −1 −1 1 −1 5 0.1 30 LDH 15.90
6 −1 1 1 −1 5 0.3 30 LDH 22.00
7 1 −1 1 −1 7 0.1 30 LDH 11.81
8 1 1 1 −1 7 0.3 30 LDH 14.20
9 −1 −1 −1 1 5 0.1 15 CLDH 92.24
10 −1 1 −1 1 5 0.3 15 CLDH 40.47
J. Compos. Sci. 2022, 6, 115 10 of 14

Table 6. Cont.

Coded Values Actual Values

Run qe (mg/g)
A B C D A B C D
11 1 −1 −1 1 7 0.1 15 CLDH 72.48
12 1 1 −1 1 7 0.3 15 CLDH 37.88
13 −1 −1 1 1 5 0.1 30 CLDH 59.80
14 −1 1 1 1 5 0.3 30 CLDH 36.56
15 1 −1 1 1 7 0.1 30 CLDH 47.78
16 1 1 1 1 7 0.3 30 CLDH 32.59

Table 7. Values of model coefficients for adsorptive removal of PBV.

Main Coefficient Value

b0 38.24
b1 −8.67
b2 −5.26
b3 −8.16
b4 14.24
b12 1.97
b13 4.93
b14 −6.93
b23 1.77
b24 0.13
b34 0.05
b123 −1.43
b124 1.18
b134 1.06
b234 −0.08
b1234 0.04

3.3.2. Analysis of Variance (ANOVA)

ANOVA is a statistical technique that subdivides the total variation in a set of data into
component parts associated with specific source of variation for adequacy and significance
of predicted model. Data obtained from ANOVA analysis for the coded quadratic model
at a confidence level of 95% are represented in Table 8. The table shows that the equation
adequately represents the actual relationship between response and the significant variables.
This is confirmed by a higher F value while the p value < 0.05. In this model the F value
is 361.05 and p value is 0.0002 (which is less than 0.05, justifying the significance of the
model). Moreover, interaction effects as significant model terms can be used for modeling
the experimental system. According to the ANOVA analysis, the significant terms are the
adsorbent dosage (A), solution pH (B), initial dye concentration (C), nature of LDH (D),
the interaction between adsorbent dosage and pH solution (AB), the interaction between
adsorbent dosage and initial dye concentration (AC) and the interaction between solution
pH and initial dye concentration (BC). From the obtained fitting equation (Equation (9)), it
appears that the adsorption of PBV was positively correlated to the nature of LDH, and
the interaction between adsorbent dosage and solution pH, adsorbent dose and initial
dye concentration, and between solution pH and initial dye concentration. Meanwhile,
the increase in adsorbent dosage, solution pH and initial dye concentration resulted in a
reduction of PBV adsorption.

Y = 38.24 − 8.67 A − 5.26 B − 8.16 C + 14.24 D + 1.97 AB + 4.93 AC + 1.77 BC (9)

J. Compos. Sci. 2022, 6, 115 11 of 14

Table 8. Analysis of variance for PBV adsorption.

Source Sum of Squares df Mean Square F Value p-Value Prob > F

Model 7310.92 7 609.24 361.05 0.0002 significant
A 1203.9 1 1203.9 713.46 0.0001
B 441.96 1 441.96 261.91 0.0005
C 1064.86 1 1064.86 631.06 0.0001
D 3242.99 1 3242.99 1921.87 <0.0001
AB 62.21 1 62.21 36.87 0.0090
AC 389.18 1 389.18 230.64 0.0006
BC 50.16 1 50.16 29.72 0.0121
Residual 5.06 3 1.69
Cor Total 7315.99 10
R2 = 0.980; Radj2 = 0.997.

For testing significant effects of regression coefficients for the proposed model, pre-
dicted values were compared with experimental values as shown is Table 9. From the table,
it can be seen that the values nearly coincide, which indicates a correspondence between
the mathematical model and the experimental data. The correlation between the theoretical
and experimental response calculated by the model is satisfactory. The normality of the data
can be checked by plotting normal probability plot of the residuals. The data are normally
distributed, when the data points on the plot fall fairly close to the straight line. Normal
probability plot of residual calculated for the considered model are shown in Figure 9. The
figure shows a linear relationship with high correlation coefficient which suggests good
applicability of the model for the explanation of experimental data.

Table 9. Predicted vs. experimental response for the equilibrium adsorption capacity of PBV.

Run Actual Predicted Residual

1 20.45 20.76 −0.31
2 14.20 14.82 −0.62
3 72.48 71.59 0.89
4 59.80 60.11 −0.31
5 48.62 48.00 0.62
6 92.24 92.86 −0.62
7 32.59 31.97 0.62
8 15.90 15.59 0.31
9 47.78 47.74 0.04
10 40.47 40.50 −0.03
11 32.36 32.32 0.04
12 37.88 37.57 0.31
13 11.81 11.85 −0.04
14 36.56 37.45 −0.87
15 22.01 21.11 0.89
16 26.67 27.56 −0.89

3.3.3. Response Surface Analysis

Response surface methodology (RSM) was developed by considering the significant
interactions in the full experimental design to optimize the critical factors and describe
the nature of the response in the experiment. 3D surface plots of interaction effects are
given in Figure 10. The figure presents three significant interactions between adsorbent
dosage/solution pH, adsorbent dosage/dye concentration and dye concentration/solution
pH. From Figure 10a, it could be seen that the equilibrium adsorption capacity of PBV
increased with decreasing adsorbent dosage and solution pH. The greater adsorption
efficiency was obtained at initial concentration of 15 mg/L with CLDH. However, the
adsorption increased with decreasing adsorbent dosage and dye concentration (Figure 10b).
The highest value was obtained at pH of 5 with CLDH. Figure 10c indicates that the PBV
adsorption capacity increased when the solution pH and dye concentration decreased.
The highest equilibrium adsorption capacity was obtained at adsorbent dose of 0.1 g/L
with CLDH.
 J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 12 of 16

J. Compos. Sci. 2022, 6, 115 12 of 14

16 26.67 27.56 −0.89

J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 13 of 16

Figure
Figure 9.
9. Normal
Normalprobability
probabilityplot
plotofof
residual forfor
residual thethe
removal of PBV.
removal of PBV.

3.3.3. Response Surface Analysis

Response surface methodology (RSM) was developed by considering the significant
interactions in the full experimental design to optimize the critical factors and describe the
nature of the response in the experiment. 3D surface plots of interaction effects are given
in Figure 10. The figure presents three significant interactions between adsorbent
dosage/solution pH, adsorbent dosage/dye concentration and dye concentration/solution
pH. From Figure 10a, it could be seen that the equilibrium adsorption capacity of PBV
increased with decreasing adsorbent dosage and solution pH. The greater adsorption
efficiency was obtained at initial concentration of 15 mg/L with CLDH. However, the
adsorption increased with decreasing adsorbent dosage and dye concentration (Figure
10b). The highest value was obtained at pH of 5 with CLDH. Figure 10c indicates that the
PBV adsorption capacity increased when the solution pH and dye concentration
decreased. The highest equilibrium adsorption capacity was obtained at adsorbent dose
of 0.1 g/L with CLDH.

3.3.4. Optimization Analysis

The optimum conditions for four variables; adsorbent dosage, solution pH, dye
concentration and nature of LDH were obtained. The best conditions for the removal of
PBV are obtained by calcined LDH at initial concentration of 15 mg/L, pH of 5, and
adsorbent dosage of 0.1 g/L. Under these conditions, the highest equilibrium adsorption
capacity was obtained. In addition, it was observed that the experimental values obtained
were in good agreement with the values predicted from the models, with relatively small
errors between the predicted and the experimental values, which were only 0.02%.

Figure Response
10.10.
Figure Response surface plotsfor
surface plots for
PBVPBV removal.
removal. Solution
Solution pH vs.pH vs. Adsorbent
Adsorbent dosage
dosage (a), dye (a), dye
concentration vs. Adsorbent dosage (b), and dye concentration vs. Solution pH
concentration vs. Adsorbent dosage (b), and dye concentration vs. Solution pH (c). (c).

4. Conclusions
In summary, the synthesized zinc/aluminum layered double hydroxides were
utilized for the removal of patent blue V dye from aqueous solution under different
conditions. It can be observed that calcination of LDH strongly enhances its adsorption
potential. The process is very rapid and the adsorption yield increased with an increase
J. Compos. Sci. 2022, 6, 115 13 of 14

3.3.4. Optimization Analysis

The optimum conditions for four variables; adsorbent dosage, solution pH, dye
concentration and nature of LDH were obtained. The best conditions for the removal
of PBV are obtained by calcined LDH at initial concentration of 15 mg/L, pH of 5, and
adsorbent dosage of 0.1 g/L. Under these conditions, the highest equilibrium adsorption
capacity was obtained. In addition, it was observed that the experimental values obtained
were in good agreement with the values predicted from the models, with relatively small
errors between the predicted and the experimental values, which were only 0.02%.

4. Conclusions
In summary, the synthesized zinc/aluminum layered double hydroxides were utilized
for the removal of patent blue V dye from aqueous solution under different conditions.
It can be observed that calcination of LDH strongly enhances its adsorption potential.
The process is very rapid and the adsorption yield increased with an increase in the
adsorbent dosage. The highest adsorption occurred in acidic medium. Kinetic data were
best fitted to the pseudo-second-order kinetic model. Dye adsorption increased with the
increase in the initial concentration according to Langmuir adsorption isotherm model.
The adsorption process was endothermic. The effects of significant variables and their
interactions in the adsorption were determined by full factorial experimental and optimum
were established. The predicted values were in good agreement with the experimental with
relatively small errors.

Author Contributions: Conceptualization, A.M., A.E. and N.B.; methodology, A.M., H.T. and Z.R.;
writing—original draft, A.M. and N.T.; writing—review and editing, A.E., H.T., Z.R. and N.B.;
supervision, N.B. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data presented in this study are available in the article.
Conflicts of Interest: The authors declare no conflict of interest.

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