Mg-Cr Layered Double Hydroxide with Intercalated Oxalic Anion for Removal Cationic Dyes Rhodamine B and Methylene Blue

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 85-94

J. Environ. Treat. Tech.

ISSN: 2309-1185

Journal web link: http://www.jett.dormaj.com

https://doi.org/10.47277/JETT/9(1)94

Mg-Cr Layered Double Hydroxide with Intercalated

Oxalic Anion for Removal Cationic Dyes Rhodamine

B and Methylene Blue

Arini Fousty Badri , Neza Rahayu Palapa , Risfidian Mohadi , Mardiyanto , Aldes Lesbani

¹Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sriwijaya University, Jl. Palembang-Prabumulih, Km. 32, Ogan Ilir, South

Sumatra, Indonesia

Department of Environmental Science, Graduate School, Sriwijaya University, Jl. Padang Selasa No. 524 Ilir Barat 1, Palembang-South Sumatra, Indonesia

Department of Pharmacy, Faculty of Mathematics and Natural Sciences, Sriwijaya University, Jl. Jl. Palembang-Prabumulih, Km. 32, Ogan Ilir 30662,

South Sumatra, Indonesia

Received: 25/07/2020

Accepted: 13/10/2020

Published: 20/03/2021

Abstract

A MgCr-based layered double hydroxide (LDH) was synthesized by a coprecipitation method, followed by an intercalation process

using an oxalic anion. The materials were characterized using X-ray diffraction analysis, FT-IR spectroscopy, and pH pzc measurement.

The materials were then applied as adsorbents for removal of methylene blue (MB) and rhodamine B (RhB) from aqueous solution. Pristine

Mg/Cr LDH exhibited RhB adsorption capacity of 32.154 mg g⁻ , whereas the use of intercalated Mg/Cr LDH caused an increase in the

capacity (139.526 mg g⁻ ). Kinetic studies indicated that the dye adsorption using both LDHs followed a pseudo-second-order kinetic

1 1

model; the K values of pristine and modified Mg/Cr LDH for RhB and MB were 6.970, 0.001, 0.426, and 2.056 g mg⁻ min⁻ ,

respectively. The thermodynamic study identified that the adsorption of both dyes onto the LDHs was a spontaneous process and can be

classified as physical adsorption with adsorption energies of <40 kJ/mol. Moreover, the desorption and regeneration experiments indicated

the high economic feasibility and reusability of the LDHs. By using HCl as the optimal solvent, the LDHs could desorb as much as 98% of

the dye and could be used as adsorbents with high adsorption capacity over three cycles.

Keywords: Layered double hydroxide, MgCr, rhodamine B, methylene blue, intercalation

Various adsorbents have been used to remove dyes from

Introduction

wastewater such as bentonite [9], kaoline, activated carbon,

zeolites, and hydrotalcite [10–12]. Hydrotalcite is a class of clay

materials and serves as effective sorbents [13,14]. However, to

achieve high efficiency for dye adsorption, hydrotalcite must be

modified using an intercalating process with organic [15] or

inorganic anions to increase its surface area [16]. Hydrotalcites

have been extensively modified to impart high adsorption

capacity and efficiency; such modification methods include

The contamination of water bodies due to dyes negatively

affects the ecological system and human health [1]. Industrial

activities such as production of textile, paper, and rubber use

reactive synthetic dyes [2,3]. Such dyes are harmful organic

pollutants because of their carcinogenic effects [3–5]. Dye

contaminants are synthetic dyes that are non-biodegradable;

therefore, it is recommended to remove such pollutants from

wastewater before being discharged into natural water [6].

Several methods have been employed to remove dyes from

wastewater, such as ion exchange, filtration, membrane

separation, electrochemical degradation, and adsorption

methods. Among these methods, adsorption is a suitable method

to remove dyes from wastewater because of its low cost and

high efficiency and because it involves a simple treatment.

Moreover, adsorption efficiency depends on the adsorbent [7,8].

2 4

development of LDH-MnFe O hybrid materials [17] and

intercalation of LDHs with aromatic acid anions [18].

Anionic synthetic clay layered double hydroxides (LDHs)

consist of divalent and trivalent brucite-like layers that have a

positive charge and an anion functioning as a counterion. These

III

compounds have

general formula of [M (1−x)

− x/n

(

OH)

] (An ) ·mH

O, where An is the intercalated anion [19–

1]. The anion in the interlayer of the LDH can be replaced,

under suitable conditions, with inorganic ions such as nitrate,

carbonate [22], and sulfate ions in order to enhance the

interlayer. Modified LDHs have applications in various fields,

especially in dye removal. According to Santos et al., calcined

LDH was used to adsorb acid yellow 42 in aqueous solutions

Corresponding author: Aldes Lesbani, Department of

Chemistry, Faculty of Mathematics and Natural Sciences,

Sriwijaya University, Jl. Palembang-Prabumulih, Km. 32, Ogan

Ilir, South Sumatra, Indonesia. E-mail: Corresponding author:

aldeslesbani@pps.unsri.ac.id

[23]. Deng et al. [24] reported the use of sodium-dodecyl-

sulfate-intercalated and acrylamide-anchored LDH for the

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 85-94

removal of Congo red. In contrast, Xu et al. prepared

polyoxometalate-intercalated ZnAlFe LDH, which exhibited

improved adsorption capacity for cationic dye removal [14].

Similarly, Li et al. used a magnetic core-shell dodecyl-sulfate-

intercalated LDH nanocomposite to adsorb cationic and anionic

organic dyes [25].

then heated at 80 °C for 24 h.

2.2 Intercalation of Mg/Cr LDH with Oxalic Anion

Mg/Cr LDH intercalated with oxalic anions was prepared by

the ion-exchange method. As much as 50 g of Mg/Cr LDH was

mixed with water, and the solution was stirred for 60 min under

a nitrogen atmosphere. The LDH mixture was then added to a

solution of oxalic acid. The pH of the mixture was adjusted to 9

In this study, Mg/Cr LDH was synthesized by

coprecipitation method. The LDH was modified by intercalating

oxalate anions (C

2 4

) into the interlayer space of hydrotalcite

using NaOH. The suspension was stirred for 24 h under a N

atmosphere and dried at 100 °C.

via anion exchange. The pristine and intercalated LDHs were

then applied as adsorbents for removal of rhodamine B (RhB)

and methylene blue (MB). The structures of these dyes are

presented in Fig. 1. The adsorption of the dyes using the

intercalated LDH material was then optimized by varying the

2.3 Adsorption of Methylene Blue and Rhodamine B using

Mg/Cr LDH and Intercalated Mg/Cr LDH

First, 0.02 g of LDH was added to 20 mL of MB and RhB,

each having a concentration of 70 mg/L. The adsorption studies

were carried out under stirring over different durations (5–120

min). After stirring, the suspensions were separated by

centrifugation at 3000 rpm for 10 min and examined via UV-Vis

spectrophotometry at 662 nm for methylene blue and 555 nm for

rhodamine B. After equilibrium was reached, 0.5 g of LDH was

used to adsorb the dyes at different dye concentrations (10–60

mg/L) and temperatures (303–333 K).

contact time, initial concentration, and temperature.

desorption process was conducted to determine a suitable

solvent using several organic solvents, followed by regeneration

over three cycles.

.4 Desorption and Regeneration of Methylene Blue and

Rhodamine B using Mg/Cr LDH and Intercalated Mg/Cr LDH

desorption process was performed to examine the

efficiency of the adsorbent. First, 0.5 g of LDH was added to 50

mL of MB and RhB (100 ppm) and shaken for 120 min. Then,

the dye concentration in the filtrate was determined by UV-Vis

spectrophotometry, followed by drying of the adsorbent for 2 h.

The residue (0.01 g) was shaken in 10 mL solvent (HCl, NaOH,

hydroxylamine hydrochloride, water, and Na-EDTA) for 120

min. The filtrate was examined via UV-Vis spectrophotometry.

The regeneration process was carried out using three cycles of

the adsorption–desorption process.

(

(b)

Figure 1: Structures of (a) rhodamine B and (b) methylene blue

Materials and Methods

The chemicals used in this study were Mg(NO

)

∙6H

·9H

(

Sigma-Aldrich,

400.15

g/mol),

Cr(NO

)

EMSURE ACS, Reag. Ph Eur, 256.41 g/mol), Na

EMSURE ACS, Reag. Ph Eur, 126.07 g/mol), NaOH

Results and Discussion

The diffraction patterns of the pristine and modified Mg/Cr

EMSURE ACS, Reag. Ph Eur, 40 g/mol), HCl

MallinckrodtAR , 37%), and H C O ·2H O (EMSURE ACS,

2 2 4 2

LDHs are shown in Fig. 2. The diffractogram of the pristine

Mg/Cr LDH (Fig. 2a) consisted of both sharp and symmetrical

peaks and some high-intensity asymmetrical peaks. This result

explains the highly crystalline and ordered layered structure of

Mg/Cr LDH. The typical pattern corresponding to hydrotalcite is

evident, which is a set of four reflection lines at 2θ = 11°, 22°,

Reag. Ph Eur, 126.07 g/mol). All chemicals were used as

received without further purification. X-ray diffraction (XRD)

analysis was performed using

diffractometer, and the sample was scanned at 10°/min The

Brunauer–Emmett–Teller (BET) surface area was measured

using a Quantachrome adsorption–desorption apparatus. The

sample was degassed prior to analysis at 77 K. Fourier transform

infrared (FT-IR) spectroscopy was performed using a Shimadzu

Prestige-21 device, with the use of KBr pellets; each sample was

a Rigaku Miniﬂex-6000

36°, and 60° that are ascribed to the reflections of the (003),

(

006), (115), and (110) basal planes, respectively. The interlayer

distance of the pristine LDH was 7.62 ꢀ (Fig. 2a). The XRD

pattern of Mg/Cr-oxalate LDH exhibits a lower intensity than

that before intercalation, indicating a decrease in the crystallinity

of the LDH interlayer due to the presence of oxalate (Fig. 2b).

The (003) reflection suggests that the reflection shifted to lower

angles which indicated an increase in the basal spacing of

Mg/Cr-oxalate LDH (11.35 Å). The peak shift from 2θ = 11° to

analyzed at wavenumbers in the range of 400–4000 cm⁻ . The

concentrations of the dyes were measured using a Biobase BK

800 UV-Visible spectrophotometer.

.1 Synthesis Mg/Cr LDH

Mg/Cr LDH was synthesized by a coprecipitation method.

10° indicates the replacement of nitrate ions with oxalate ions in

First,

3 2 2

solution of Mg(NO ) ∙6H O was mixed with

∙9H O (3:1) and stirred for 30 min. A solution of

(1 M) and NaOH (2 M) was added to the reaction

the interlayer. Hence, the intercalation process with the oxalate

anion was successful, and significant interlayer separation was

achieved.

Cr(NO

)

2 3

Na CO

mixture. The mixture was then mixed under continuous stirring

until a precipitate was formed, and then the pH of the solution

was adjusted to 10 using NaOH. The reaction was maintained at

0 °C for 24 h to produce Mg/Cr LDH. The solid material was

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 85-94

Figure 2: X-ray Powder diffraction patterns of Mg/Cr LDH (a) and

intercalated Mg/Cr LDH(b)

Figure 4: FT-IR spectra of Mg/Cr LDH (a) and intercalated Mg/Cr LDH

(b)

Figs. 3a and b show the graphs of the BET curves of Mg/Cr

LDH and intercalated Mg/Cr LDH; these graphs indicated that

both materials followed type IV isotherm patterns according to

IUPAC classifications and that the materials were mesoporous;

occurrence of hysteresis was also confirmed. The materials

Mg/Cr and intercalated Mg/Cr LDH contained mesopores that

were 2–50 nm in size, based on IUPAC classifications. The

isotherms of both Mg/Cr LDH and intercalated Mg/Cr LDH

were ascribed to type H2 because the material contained large

mesopores [26]. Table 1 summarizes the surface areas and pore

sizes of Mg/Cr LDH and intercalated Mg/Cr LDH. The results

indicated an increase in the surface area by as much as 26.1153

Fig. 4 presents the FT-IR spectra of the materials. All samples

exhibited broad bands at around 3400 cm⁻ , indicating the

presence of an OH group. This band may be attributed to the

hydroxyl group of water molecules, and the interlayer anions

could also account for the broadening of this band. The bending

mode of water gave rise to a rather weak band around 1635 cm⁻

in the FT-IR spectra of Mg/Cr LDH (Fig. 4a). The vibrational

modes of the interlayer nitrate ions are indicated by the peak at

381 cm⁻ . This spectrum is observed for every hydroxide

irrespective of nature. The octahedral sheets suggest a rather

symmetric environment for the interlayer anions. The absorption

peaks below 1000 cm⁻ correspond to M-O and M-O-M

m /g after intercalation, which resulted in a decrease in the pore

diameter of the LDH.

vibrations. The presence of oxalate anions in the LDH was

confirmed by the presence of a peak at 1381 cm⁻ (Fig. 4b),

which could be assigned to the stretching modes of the

carboxylate group.

Furthermore, the relatively weak peaks at 779 and 594 cm⁻¹

correspond to the carbon-oxygen bond in the carboxyl group

[27]. In addition, the strong absorption peak of the nitrate anions

in Fig. 4a decreased after the ion-exchange reaction (Fig. 4b).

This result indicated that oxalate anions replaced the

interlamellar nitrate anions, as previously evidenced by X-ray

analysis.

The stabilities of the pristine and modified LDHs were

determined by pH point zero charges (pzc), as shown in Fig. 5.

The pristine and modified LDHs prior to use as dye adsorbents

were examined using pH pzc to determine the charge of the

materials. As shown in Fig. 5, the cross point was identified at

pH 9 for both pristine and modified LDHs. A pH of 9 was

ascribed to the material when it has no charge. As such, the

materials have positive charges below pH 9 and negative

charges above pH 9.

Figure 3: N

Adsorption–desorption of Mg/Cr LDH (a) and intercalated

Mg/Cr LDH (b)

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 85-94

where q

min), q

equilibrium, k

(mg/g) is the concentration of dye adsorbed at time t

(

(mg/g) is the concentration of dye adsorbed at

is the rate constant of first-order sorption, and k

is the rate constant of pseudo-second-order (PSO) sorption. The

results of such calculations are shown in Table 2. This table

shows that the sorption of the dyes on pristine LDH and

modified LDH conform to the PSO kinetic model. The results

suggest that interactions between the sorbate and sorbent were

presented.

Figure 5: pH pzc graphs of Mg/Cr LDH (a) and intercalated Mg/Cr LDH

(b)

The results of the adsorption of MB by MgCr LDH and

MgCrC O LDH, which was conducted at pH 9, are shown in

2 4

Fig. 6. The adsorption equilibrium was reached after 70 min

with a MB uptake of 4.9 mg/L for pristine LDH and 6.5 mg/L

for the modified LDH. This contact time was considered optimal

for the next experiment. The adsorption of RhB using modified

LDH, as shown in Fig. 7, improved slightly and reached

equilibrium after 70 min; equilibrium was reached after 20 min

for pristine LDH. The RhB uptake using the modified Mg/Cr

LDH was twice that of pristine Mg/Cr LDH, with each

adsorbing 43 mg/L and 19 mg/L of RhB, respectively. The

effect of contact time on the adsorption of dyes on pristine and

modified Mg/Cr LDHs was shown in Fig. 8. The amount of dye

adsorbed by LDHs notably increased with increasing contact

time. However, the sorption rate of the dyes on the pristine LDH

was slightly lower than that on the modified LDH. The kinetics

results indicate that the modified LDH exhibited a higher

sorption efficiency for both dyes. Pseudo-first-order and pseudo-

second-order kinetic models were applied to determine the

kinetic sorption process; such models are respectively expressed

as follows:

Figure 6: Time variation of adsorption of methylene blue on Mg/Cr

LDH (a) and intercalated Mg/Cr LDH (b)

Figure 7: Time variation adsorption of rhodamine B on Mg/Cr LDH (a)

and intercalated Mg/Cr LDH (b)

ln (q

−q

) = lnq

– k

²) + (1/q

) t,

(1)

(2)

t/qt = 1/(k

Table 2: Kinetic parameters of dyes adsorption onto Mg/Cr-LDH and intercalated Mg/Cr LDH

PFO

PSO

LDH

R²

(g mg min^-¹)

R²

Co (mg/L)

qe (mg/g)

41.572

47.022

7.786

(min )

qe(mg/g)

0.409

Mg/Cr

Rh-B

0.003

0.056

0.040

0.081

0.801

0.897

0.935

0.904

6.970

0.426

0.001

2.056

0.9878

0.988

0.940

0.992

Mg/Cr-oxalate

Mg/Cr

2.350

10.225

0.486

Mg/Cr-oxalate

10.022

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 85-94

The data on the effect of dye concentration and temperature,

as shown in Figs. 8 and 9. It can be observed that increasing the

concentration and temperature would increase the amount of dye

adsorbed on both pristine and modified LDHs. There is a

specific increase in the concentration of adsorbed RhB at 30

mg/L (Fig. 8a), which is probably due to the physical adsorption

of RhB as the interaction between the sorbate and sorbent was at

equilibrium. The increasing trend for the adsorption isotherm of

RhB on modified LDH was determined from the data in Fig. 8a

using Langmuir and Freundlich equations. Fig. 8b exhibits a

similar behavior for the adsorption of RhB, which was at a

concentration of 15 mg/L, as observed for the curves with

increasing temperature.

Figure 9: MB uptake by initial concentration at several temperatures by

Mg/Cr LDH (a) and intercalated Mg/Cr LDH (b)

The Freundlich isotherm indicates a multilayer adsorption

process. Based on the adsorption capacity of RhB on pristine

and modified Mg/Cr LDHs, an increase in temperature is

correlated with increasing adsorption capacity at equilibrium, as

summarized in Table 3. The adsorption data of MB on pristine

and modified Mg/Cr LDH is summarized in Table 4. The data

indicates that the adsorption using pristine and modified Mg/Cr

LDHs was best represented by the Freundlich isotherm. The

increase in temperature caused the adsorption capacity to be

higher at 333 K than at room temperature. The maximum

adsorption capacities for both dyes using modified Mg/Cr LDH

were higher than those using pristine Mg/Cr LDH. According to

Leon et al. [28], the higher content of available carboxylic

groups promotes electrostatic interactions between the sorbate

and sorbent. summarized in Tables 5 and 6. The data in Tables 5

and 6 indicate increasing adsorption capacity with increasing

temperature in the range of 303–333 K. The adsorption process

was described by thermodynamic parameters such as Gibbs free

energy, enthalpy, and entropy, which can be expressed in a

single equation as follows:

Figure 8: RhB uptake by initial concentration at various temperatures by

Mg/Cr LDH (a) and intercalated Mg/Cr LDH (b)

The results of the adsorption of MB onto pristine LDH and

modified LDH are shown in Fig. 9. For the adsorption of MB on

both adsorbents, the difference in dye uptake at different

temperatures was not significant. As shown in Fig. 9a, the

adsorption rate of MB on pristine LDH was 23 mg/g at 333 K,

which indicated a higher adsorption capacity. Tables 3 and 4

summarize the isotherm parameters for the adsorption of the

dyes on pristine LDH and modified LDH. The adsorption

isotherm data for RhB is shown in Table 5. The data indicated

that the isotherm was best represented by the Freundlich

isotherm.

G = H-TS

(3)

where G is the change in Gibbs free energy (kJ/mol), S is the

change in entropy (kJ/mol), andH is the change in entropy

(

kJ/mol).

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 85-94

Table 3: Isotherms parameter of adesorption rhodamine B onto Mg/Cr-LDH and intercalated Mg/Cr LDH

T(K)

LDH

Adsorption isotherm

Langmuir

Adsorption constant

313

323

333

Mg/Cr

max

20.960

0.023

0.723

0.744

1.909

0.947

74.828

0.003

0.020

1.039

1.109

0.930

27.855

28.011

32.154

0.03

0.034

0.684

0.642

2.279

0.914

120.482

0.010

0.135

0.900

1.084

0.912

0.032

0.665

0.67

R²

0.637

0.75

Freundlich

Langmuir

Freundlich

1.758

0.866

77.778

0.004

0.067

0.945

1.106

0.962

1.866

0.896

139.526

0.029

0.659

0.661

1.691

0.913

R²

Mg/Cr - Oxalate

max

R²

Table 4: Isotherms parameter of adsorption methylene blue onto Mg/Cr-LDH and intercalated Mg/Cr LDH

T(K)

LDH

Adsorption isotherm

Adsorption constant

303

313

323

333

Mg/Cr

Langmuir

max

1.636

1.323

0.926

0.446

2.912

1.517

5.131

0.955

0.497

1.625

1.452

1.534

0.938

0.572

1.142

1.538

1.195

0.964

0.629

2.160

R²

Freundlich

R²

0.991

0.993

0.981

0.980

Mg/Cr – Oxalate

Langmuir

max

8.741

0.107

0.814

0.501

1.957

0.961

4.854

0.934

0.918

0.630

7.638

0.938

2.879

0.771

0.902

0.644

7.132

0.877

2.625

0.851

0.784

0.562

2.160

0.981

R²

Freundlich

R²

The amount of dye adsorbed as a function of temperature is

the H and S values were determined from the y-intercept and

slope (eq. 3), respectively, as listed in Tables 5 and 6. The S

values were positive, which indicated an increase in randomness

during the ongoing process. The positive H values indicated

that the adsorption was endothermic and proceeded via a

physisorption process. The likelihood of the adsorption

proceeding via a physisorption process was supported by the G

values which were within the range of −20–0 kJ/mol. The

negative Gibbs free energy values indicate that the adsorption

was spontaneous. In addition, the H values calculated in this

study (−20 kJ/mol) are consistent with the hydrogen bond and

dipole bond forces of the adsorbent. The adsorption capacities

for MB and RhB in this study are comparable to those of other

adsorbents reported in previous literature, which are listed in

Table 7.

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 85-94

Table 5: Thermodynamic adsorption parameter of rhodamine B onto Mg/Cr-LDH and intercalated Mg/Cr LDH

T (K)

△H (kJ/mol)

△S (kJ/mol)

△G (kJ/mol)

-0.362

△H (kJ/mol)

△S (kJ/mol)

△G (kJ/mol)

0.812

-1.171

-0.081

40 mg/L

24.160

0.081

27.883

0.089

-1.981

-0.975

-2.790

-1.868

-1.255

-1.582

-1.910

-2.238

-1.350

-1.876

-2.401

-2.927

-0.180

-1.076

-1.973

-2.869

-0.229

-1.043

-1.857

-2.671

0 mg/L

8.681

0.033

0.053

26.981

24.437

0.090

0.081

14.584

Table 6: Thermodynamic adsorption parameter of methylene blue onto Mg/Cr-LDH and intercalated Mg/Cr LDH

T (K)

△H (kJ/mol)

△S (kJ/mol)

△G (kJ/mol)

-2.145

-2.453

-2.761

-3.070

-2.581

-3.396

-4.211

-5.026

-3.871

-4.187

-4.502

-4.817

△H (kJ/mol)

△S (J/Kmol)

△G (kJ/mol)

-2.972

-3.568

-4.163

-4.758

-3.209

-3.722

-4.234

-4.746

-2.840

-3.179

-3.518

-3.857

0.031

0 mg/L

7.198

15.070

0.060

5 mg/L

0 mg/L

22.114

5.682

0.081

0.032

12.311

7.431

0.051

0.034

Table 7: Comparison of adsorption capacity of some adsorbents for RhB and MB removal

Dyes

RhB

Adsorbent

Ti-Al-Si-O

Nanocomposite Adsorbent

Nanocomposite SNF/MNP/PS

Casuarina Equisetifolia Needle (CEN)

Activated Cotton Stalks (CSAC)

Adsorption Capacity (mg/g)

References

162.96

142.8

103.1

82.34

133.33

153.85

22.47

324.6

1,388

556.9

936

(29)

(30)

(31)

(32)

(33)

Magnetic Lignosulfonate (MLS)

Magnetic AC/CeO

Boron Organic Polymers

Chitosan graft poly

(34)

(35)

(36)

(37)

(38)

RhB

SA/HEC/HA Membrane

Nanocomposite hydrogel

18.814

20.83

122.5

RhB

32.154

1.636

139.526

8.741

MgCr

This work

Intercalated MgCr

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 85-94

(

Figure 11: Regeneration of RhB (a) and MB (b) on MgCr LDH and on

intercalated Mg/Cr LDH

Conclusion

MgCr and MgCr intercalated anion oxalate were easily

prepared by the ion-exchange method. MgCr modified anion

oxalate has higher adsorbed capacity in equilibrium than pristine

amount MgCr modified anion oxalic has higher adsorption

(

Figure 10: Desorption of RhB (a) and MB (b) on Mg/Cr-LDH and on

intercalated Mg/Cr LDH

-1

capacity than pristine LDH amount from 32.154 mg.g for

pristine LDH and 139.526 mg.g for intercalated MgCr LDH in

RhB dye. The adsorption of both sorbents for MB and RhB was

-1

The desorption study was conducted in several solvents onto

MgCr and MgCr modified. Figure 10 shows the y axis is percent

desorption using RhB onto MgCr and MgCr modified. As our

best acknowledgment, a few the researchers have focused to

recovery used material. Several solvent organic, acid, and base

were conducted in this treatment for suitable solvents (ie, water,

classified as physical adsorption with H value in the range

under 40 kJ/mol. Moreover, both adsorbents can be reused for

further adsorption process. This result based on the desorption

results that the RhB and MB can be desorbed from the adsorbent

as much as 98%.

HCl, NaOH, HONH Cl and Na-EDTA). The result on Figure 10

shows that the higher desorption is HCl. In this case, MgCr

modified has lower desorption than MgCr pristine. we assumed

that the dye is more trapped in the active site of adsorbents and

requires a long time to be desorbed. On the other hand, in acid

solution, the hydrotalcite pristine is more desorbed than

modified caused the hydrotalcite can be exfoliated (Palapa et al.

Acknowledgment

Author thanks to Ministry of Research Technology and

Higher Education Repulic Indonesia Through “Hibah Penelitian

Dasar Unggulan Perguruan Tinggi” in Fiscal Year 2019/2020.

Competing interests

The authors declare that there is no conflict of interest that

would prejudice the impartiality of this scientific work.

020). The regeneration of MgCr LDH and intercalated MgCr

LDH was investigated by three times cycles. The recycling

process of LDHs adsorption-desorption was illustrated in Figure

1. The high effectivity of reuse material showed after

intercalated with oxalic anions than pristine. These phenomena

caused that LDH pristine can be broken in the acid solution for

extended uses. The decreases in removal efficiency from LDH

pristine indicated that the structure of LDH is exfoliated and

ruined.

Authors’ contribution

All authors of this study have a complete contribution for data

collection, data analyses and manuscript writing

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 85-94

Layered double hydroxide intercalated with aromatic acid anions for

the efficient capture of aniline from aqueous solution, J. Hazard.

Mater. 321 (2017) 111–120.

References

. F. Zhang, X. Tang, Y. Huang, A. A. Keller and J. Lan, Competitive

removal of Pb2+ and malachite green from water by magnetic

phosphate nanocomposites, Water Res. (2019) 442–451.

9. N. R. Palapa, Y. Saria, T. Taher, R. Mohadi and A. Lesbani,

Synthesis and Characterization of Zn/Al, Zn/Fe, and Zn/Cr Layered

Double Hydroxides: Effect of M3+ ions Toward Layer Formation,

Sci. Technol. Indones. 4 (2019) 36–39.

0. H. Starukh and S. Levytska, The simultaneous anionic and cationic

dyes removal with Zn–Al layered double hydroxides, Appl. Clay

Sci. 180 (2019) 0–5.

1. M. Shafigh, M. Hamidpour and G. Furrer, Zinc release from Zn-Mg-

Fe(III)-LDH intercalated with nitrate, phosphate and carbonate: The

effects of low molecular weight organic acids, Appl. Clay Sci. 170

. E. H. Elkhattabi, M. Lakraimi, M. Berraho, A. Legrouri, R. Hammal

and L. El Gaini, Acid Green 1 removal from wastewater by layered

double hydroxides, Appl. Water Sci. 8 (2018) 1–11.

. F. A. Dawodu, C. U. Onuh, K. G. Akpomie and E. I. Unuabonah,

Synthesis of silver nanoparticle from Vigna unguiculata stem as

adsorbent for malachite green in a batch system, SN Appl. Sci. 1

(2019) 1–10.

. Q. Zhang, Q. Lin, X. Zhang and Y. Chen, A novel hierarchical stiff

carbon foam with graphene-like nanosheet surface as the desired

adsorbent for malachite green removal from wastewater, Environ.

Res. 179 (2019) 108746.

. S. Boubakri, M. A. Djebbi, Z. Bouaziz, P. Namour, N. Jaffrezic-

Renault, A. B. H. Amara, M. Trabelsi-Ayadi, I. Ghorbel-Abid and

R. Kalfat, Removal of two anionic reactive textile dyes by

adsorption into MgAl-layered double hydroxide in aqueous

solutions, Environ. Sci. Pollut. Res. 25 (2018) 23817–23832.

. Y. Lu, B. Jiang, L. Fang, F. Ling, J. Gao, F. Wu and X. Zhang, High

performance NiFe layered double hydroxide for methyl orange dye

and Cr(VI) adsorption, Chemosphere 152 (2016) 415–422.

(2019) 135–142.

2. M. N. Sepehr, T. J. Al-Musawi, E. Ghahramani, H. Kazemian and

M. Zarrabi, Adsorption Performance of Magnesium/Aluminum

Layered Double Hydroxide Nanoparticles for Metronidazole From

Aqueous Solution, Arab. J. Chem. 10 (2017) 611–623.

3. R. M. M. dos Santos, R. G. L. Gonçalves, V. R. L. Constantino, C.

V. Santilli, P. D. Borges, J. Tronto and F. G. Pinto, Adsorption of

Acid Yellow 42 dye on calcined layered double hydroxide: Effect of

time, concentration, pH and temperature, Appl. Clay Sci. 140 (2017)

32–139.

4. L. Deng, H. Zeng, Z. Shi, W. Zhang and J. Luo, Sodium dodecyl

sulfate intercalated and acrylamide anchored layered double

. F. Mohamed, M. R. Abukhadra and M. Shaban, Removal of safranin

dye from water using polypyrrole nanofiber/Zn-Fe layered double

hydroxide nanocomposite (Ppy NF/Zn-Fe LDH) of enhanced

adsorption and photocatalytic properties, Sci. Total Environ. 640–

hydroxides:

removal of Congo red, J. Colloid Interface Sci. 521 (2018) 172–

82.

A multifunctional adsorbent for highly efficient

41 (2018) 352–363.

5. Y. Li, H. Y. Bi, Y. Q. Liang, X. M. Mao and H. Li, A magnetic core-

shell dodecyl sulfate intercalated layered double hydroxide

nanocomposite for the adsorption of cationic and anionic organic

dyes, Appl. Clay Sci. 183 (2019) 105309.

6. M. Oktriyanti, N. R. Palapa, R. Mohadi and A. Lesbani, Indonesian

Journal of Environmental Management and Sustainability

Modification Of Zn-Cr Layered Double Hydroxide With Keggin

Ion, Indones. J. Environ. Manag. Sustain. 3 (2019) 93–99.

7. E. Coronado, C. Martí-Gastaldo, E. Navarro-Moratalla and A.

Ribera, Intercalation of [M(ox)3]3- (M = Cr, Rh) complexes into

NiIIFeIII-LDH, Appl. Clay Sci. 48 (2010) 228–234.

8. O. León, A. Muñoz-Bonilla, D. Soto, D. Pérez, M. Rangel, M.

Colina and M. Fernández-García, Removal of anionic and cationic

dyes with bioadsorbent oxidized chitosans, Carbohydr. Polym. 194

. S. Mallakpour and M. Hatami, An effective, low-cost and recyclable

bio-adsorbent having amino acid intercalated LDH@Fe3O4/PVA

magnetic nanocomposites for removal of methyl orange from

aqueous solution, Appl. Clay Sci. 174 (2019) 127–137.

. T. Taher, D. Rohendi, R. Mohadi and A. Lesbani, Thermal Activated

of Indonesian Bentonite as A Low-Cost Adsorbent for Procion Red

Removal from Aqueous Solution, J. Pure Appl. Chem. Res. 7 (2018)

9–93.

0. H. Zhou, Z. Jiang and S. Wei, A new hydrotalcite-like absorbent

FeMnMg-LDH and its adsorption capacity for Pb2 + ions in water,

Appl. Clay Sci. 153 (2018) 29–37.

1. I. Harizi, D. Chebli, A. Bouguettoucha, S. Rohani and A. Amrane, A

New Mg–Al–Cu–Fe-LDH Composite to Enhance the Adsorption of

Acid Red 66 Dye: Characterization, Kinetics and Isotherm Analysis,

Arab. J. Sci. Eng. 44 (2019) 5245–5261.

(2018) 375–383.

9. U. Pal, A. Sandoval, S. I. U. Madrid, G. Corro, V. Sharma and P.

Mohanty, Mixed titanium, silicon, and aluminum oxide

nanostructures as novel adsorbent for removal of rhodamine 6G and

methylene blue as cationic dyes from aqueous solution,

Chemosphere 163 (2016) 142–152.

0. M. I. Mohammed and S. Baytak, Synthesis of Bentonite–Carbon

Nanotube Nanocomposite and Its Adsorption of Rhodamine Dye

From Water, Arab. J. Sci. Eng. 41 (2016) 4775–4785.

1. Z. Li, X. Tang, K. Liu, J. Huang, Q. Peng, M. Ao and Z. Huang,

Fabrication of novel sandwich nanocomposite as an efficient and

regenerable adsorbent for methylene blue and Pb (II) ion removal, J.

Environ. Manage. 218 (2018) 363–373.

2. K. Abdellaoui, I. Pavlovic, M. Bouhent, A. Benhamou and C.

Barriga,

A comparative study of the amaranth azo dye

adsorption/desorption from aqueous solutions by layered double

hydroxides, Appl. Clay Sci. 143 (2017) 142–150.

3. S. Yanming, L. Dongbin, L. Shifeng, F. Lihui, C. Shuai and M. A.

Haque, Removal of lead from aqueous solution on glutamate

intercalated layered double hydroxide, Arab. J. Chem. 10 (2017)

S2295–S2301.

4. M. Xu, B. Bi, B. Xu, Z. Sun and L. Xu, Polyoxometalate-

intercalated ZnAlFe-layered double hydroxides for adsorbing

removal and photocatalytic degradation of cationic dye, Appl. Clay

Sci. 157 (2018) 86–91.

5. T. Kameda, H. Takeuchi and T. Yoshioka, NiAl layered double

hydroxides modified with citrate, malate, and tartrate: Preparation

by coprecipitation and uptake of Cu 2 from aqueous solution, J.

Phys. Chem. Solids 72 (2011) 846–851.

6. A. Lesbani, D. R. Maretha, T. Taher, Miksusanti, R. Mohadi and R.

Andreas, Layered double hydroxides Mg/Fe intercalated H3[α-

PW12O40]· n H2O as adsorbent of cadmium(II), AIP Conf. Proc.

2. M. R. R. Kooh, M. K. Dahri and L. B. L. Lim, The removal of

rhodamine

equisetifolia needles as adsorbent, Cogent Environ. Sci. 2 (2016) 1–

B dye from aqueous solution using Casuarina

3. M. Özdemir, Ö. Durmuş, Ö. Şahin and C. Saka, Removal of

methylene blue, methyl violet, rhodamine B, alizarin red, and

bromocresol green dyes from aqueous solutions on activated cotton

stalks, Desalin. Water Treat. 57 (2016) 18038–18048.

4. J. Geng, F. Gu and J. Chang, Fabrication of magnetic lignosulfonate

using ultrasonic-assisted in situ synthesis for efficient removal of

Cr(Ⅵ) and Rhodamine B from wastewater, J. Hazard. Mater. 375

049 (2018).

7. O. Mrózek, P. Ecorchard, P. Vomáčka, J. Ederer, D. Smržová, M. Š.

Slušná, A. Machálková, M. Nevoralová and H. Beneš, Mg-Al-La

LDH-MnFe2O4 hybrid material for facile removal of anionic dyes

from aqueous solutions, Appl. Clay Sci. 169 (2019) 1–9.

(2019) 174–181.

5. M. Tuzen, A. Sarı and T. A. Saleh, Response surface optimization,

8. S. Yu, X. Wang, Z. Chen, J. Wang, S. Wang, T. Hayat and X. Wang,